JP2002526480A - Method for producing N-alkyl or N-arylcarbamoyl derivative - Google Patents

Abstract

(57) Abstract: The present invention provides an amine represented by the general formula (I): Wherein the group X represents a lactam, an oxime, an imide or a triazole in the form of XH, and a method for producing an N-alkyl or N-arylcarbamoyl derivative. In particular, the invention relates to the production of blocked isocyanates by a process without isocyanates. The present invention also relates to the use of the N-alkyl or N-arylcarbamoyl derivative produced by the method of the present invention in a paint.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a method for producing an N-alkyl or N-arylcarbamoyl derivative, particularly a blocked isocyanate. A blocked isocyanate is a compound that contains an isocyanate with a blocking agent.

BACKGROUND ART Blocked isocyanates are used in the production of polyurethanes and polyureas. The blocked isocyanate can be stably mixed with the polyol, for example, at temperatures up to 150 ° C. As the temperature increases, the blocking agent is released from the isocyanate groups, so that the released isocyanate can react with the polyol present to form a polyurethane.

A method for producing an N-alkyl or N-arylcarbamoyl derivative is disclosed in DE-A-27.
12931. In the method, an isocyanate is contacted with caprolactam. As a result, caprolactam-blocked isocyanate is formed.

[0004] A disadvantage of the process disclosed in DE-A-2712931 is that the reaction with isocyanates involves a safety hazard.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a more secure method.

[0006] The purpose of this is to convert amines to the following general formula:

[0007]

Embedded image

Wherein the group X is in the form of XH and is contacted with a carbonic acid derivative of the formula lactam, oxime, imide or triazole.

In the method of the present invention, there is no isocyanate in the reaction mixture.

An advantage of the process of the present invention is that during the formation of the blocked isocyanate, there is no longer any free isocyanate.

Since the known reaction disclosed in DE-A-2712931 does not proceed quantitatively, small amounts of free isocyanate are present in the reaction mixture. To reduce the vapor pressure of this free isocyanate, the isocyanate is often trimerized by increasing the temperature before contacting the isocyanate with the lactam. This is particularly the case for isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI). The advantage and significance of the fact that free isocyanate is not present in the reaction mixture in the process according to the invention is that it is not necessary to carry out the above-mentioned trimerization reaction.

A further advantage of the method of the present invention is that it is used to prepare N-alkyl or N-aryl carbamoyl derivatives where the nitrogen is secondary and the derivative is a lactam, oxime, imide or triazole. Is to get. These are compounds that cannot be prepared by known isocyanate routes.

In the context of the present invention, the amine may be a mono-, di-, tri-, polyamine or a mixture thereof. Examples of the di- and triamines include diaminooctane, diaminononane, diaminododecane, trisaminononane, diaminodixydecane, diaminodioxododecane, bishexamethylene trisamine, and Jeffamine. Other suitable amines are oligomers as binary reaction products. Examples of the oligomer include hexamethylene diamine, adipic acid, urea, carbonyl biscaprolactamate (CBC),
Reaction products with one or two caprolactam molecules, and the like.

The advantage of the process according to the invention for producing blocked isocyanates based on oligomeric amines is that the group (X) leaving during the reaction of the carbonate derivative with the amine is easily removed as XH from the reaction mixture. The fact is that you can. This means
In contrast to the removal of the triethylamine salts released in the production of blocked isocyanates based on phosgene and triethylamine.

Contacting the amine with the carbonic acid derivative can be carried out in a solvent, if desired. Preferably, this is done by dissolving the carbonate derivative of formula I in a suitable first solvent. Suitable solvents are generally aprotic solvents such as esters, ethers, cyclic carbonates, cyclic amides, hydrocarbons and the like. Subsequently, the amine dissolved in the second solvent is slowly added to the solution of the carbonate derivative with constant stirring. The second solvent is preferably also selected from the group of the same aprotic solvents. Preferably, the first and second solvents are the same.

After adding the dissolved amine, the mixture is stirred for a while at a temperature between room temperature and 150 ° C. When the temperature exceeds 150 ° C., the blocking agent can be easily eliminated. Preferably, after stirring at a temperature of 50 ° C to 100 ° C, the N-alkyl or N-arylcarbamoyl derivative formed can be separated from the reaction mixture by a known method.

The products obtained by the process of the invention can be applied very widely in technically different fields, ie both in thermosetting and thermoplastic applications. Examples thereof include, for example, powder coating compositions, coating systems based on water or solvents, coating systems for cans or coils, inks, toners, film-forming agents for sizing glass fibers,
Examples include an adhesive, a hot melt, and a rubber composition.

The unmodified or partially modified polymers of the present invention can generally be used in powder coating compositions, can or coil coating compositions, and solvent-based coating compositions.

In a preferred embodiment of the present invention, the product obtained by the method of the present invention can be used as a crosslinking agent in a thermosetting powder coating composition.

Thermosetting powder coatings have better chemical resistance than thermoplastic powder coatings. As a result, there has been a longstanding effort to develop crosslinkers and polymers for thermoset powder coatings. There are still attempts to find binder compositions for thermosetting powder coatings with good flowability, good storage stability and good reactivity. Binder compositions for thermosetting powder coatings generally contain more than 50% by weight of polymer and less than 50% by weight of crosslinker.

The products obtained according to the invention can be used in powder coating compositions as crosslinking agents in combination with hydroxyl-functional polymers.

The hydroxyl-functional polymer is preferably a polyester, a polyacrylate, or a mixture of both. Preferably, the polyester has a hydroxyl number of 20-100 mg KOH / g of resin and an acid number of less than 10 mg KOH / g of resin. Preferably, the polyacrylate has a hydroxyl number of 40-150 mg KOH / g of resin and an acid number of less than 20 mg KOH / g of resin.

The weight ratio of the hydroxyl group containing polymer to the crosslinker is from about 95: 5 to about 5
0:50, preferably 93: 7 to 70:30. This ratio depends, among other factors, on the hydroxyl number of the polymer.

The hydroxyl functional polymer can be extruded, for example, by extrusion at a temperature of about 100 ° C.
It can be mixed with a blocked crosslinker. Curing, for example, at about 130 ° C.
It occurs at a temperature of from about to about 170C (e.g., for about 10 to 40 minutes), preferably at a temperature above about 150C.

For example, fillers, catalysts, curing agents, flow agents and / or stabilizers, and, if desired, additives such as pigments can be added to the coating system, preferably before extrusion.

[0026] Suitable polyesters can be obtained from carboxylic acids or their equivalents by conventional manufacturing methods. It is preferred to use mainly aromatic carboxylic acids.
Examples thereof include, for example, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, etc.
Also, as long as available, equivalents such as the anhydrides, acid chlorides or lower alkyl esters are mentioned. Generally, the carboxylic acid component will have at least 50
% By weight, preferably at least 70% by weight, of isophthalic acid and / or terephthalic acid.

[0027] Preferably, the diol component of the polyester is an aliphatic diol. Examples thereof include, for example, ethylene glycol, propane-1,2-diol, propane-1
, 3-diol, butane-1,2-diol, butane-1,4-diol, butane-1,3
-Diol, 2,2-dimethylpropanediol-1,3 (= neopentyl glycol
), Hexane-1,6-diol, 2,2- [bis (2-hydroxyethoxy)] phenylpropane, and a small amount of polyols such as glycerol, hexanetriol, pentaerythritol, sorbitol, trimethylolethane, Trimethylolpropane, tris (2-hydroxy) isocyanurate and the like can be used as the alcohol. An epoxy compound can be used instead of the diol and the polyol, respectively. The alcohol component preferably contains at least 50 mol% of neopentyl glycol.

Furthermore, the applied polycarboxylic acid can be a cycloaliphatic and / or acyclic polycarboxylic acid. Examples thereof include, for example, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexanehydroendomethylenetetrahydrophthalic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, adipic acid,
Succinic acid, maleic acid and the like can be mentioned. The amount of cycloaliphatic and / or acyclic polycarboxylic acid can be up to about 30 mol%, preferably up to about 20 mol%, based on the total carboxylic acid. Hydroxycarboxylic acids and / or lactones, if desired, can also be used. For example, 1
2-hydroxystearic acid, ε-caprolactone, hydroxypivalic acid ester of neopentyl glycol and the like. During the preparation, the monocarboxylic acid can also be added in small amounts, for example in amounts of less than 5% by weight. For example,
For example, benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid, saturated aliphatic monocarboxylic acid and the like can be mentioned.

The polyester can be produced by an ester reaction or a transesterification reaction known to those skilled in the art. If desired, conventional catalysts can be used. Examples include dibutyltin oxide, tetrabutyl titanate, and the like. The production conditions and the COOH / OH ratio depend on the desired hydroxyl number and acid number, for example, from about 20 to about 100 mg KOH / g of resin and about 1
It is selected so as to obtain a polyester resin having an acid number of less than 0 mg KOH / g resin.

Preferably, the polyester is a dicarboxylic acid of about 40 to 100 mol% isophthalic acid and about 0 to 60 mol% terephthalic acid, wherein the total amount of isophthalic acid and terephthalic acid is 100 mol% ) As the base material. Preferably, the amount of isophthalic acid is greater than 60 mol%.

If desired, the polyester can also be based on more than two dicarboxylic acids.

The hydroxyl-functional acrylic resin can be based on, for example, hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl (meth) acrylate and the like. This resin, for example, (meth) acrylic acid, (meth)
An alkyl ester of acrylic acid or the like can be used as a base material. Examples thereof include, for example, ethyl (meth) acrylate, isopropyl (meth) acrylate,
n-butyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (
(Meth) acrylate, ethylhexyl (meth) acrylate and / or cyclohexyl (meth) acrylate. For example, a vinyl compound such as styrene can be used.

The glass transition temperature (Tg) of the product obtained by the process of the invention is between 10 ° C. and 150 ° C., preferably between 50 ° C. and 110 ° C., depending on the raw materials and molecular weights chosen.

When the products of the present invention are used in combination with a hydroxyl-functional polymer in a binder composition, for example, good flow and good chemical resistance, bubble formation on the surface with a layer thickness of at least 120 μm or less It combines the highly desirable properties such as the desired gloss, high resistance to boiling water and salt spray, high scratch resistance, good mechanical properties, and good color stability of powder coatings without the need to .

The production of common thermosetting powder coatings and the chemical reaction that cures the powder coating to form a cured coating is described in Powder Coatings, Chemistry of Misev. and Technology) (1991, John Wiley), pp. 42-54, 148, and 22.
It is described on pages 4-226. Thermoset binder compositions are generally defined as the resinous portion of a powder coating consisting of a polymer and a crosslinker.

If desired, customary additives such as, for example, pigments, fillers, defoamers, flow agents, stabilizers and the like can be used in the binder compositions and powder coating systems according to the invention. Suitable pigments include, for example, inorganic pigments such as titanium dioxide, zinc sulfide, iron oxide and chromium oxide, and organic pigments such as azo compounds. Suitable fillers include, for example, metal oxides, silicates, carbonates, sulfates, and the like.

Examples of the stabilizer include primary and / or secondary antioxidants and UV stabilizers such as quinone, a phenol compound (having a substituent having a steric hindrance), a phosphonite (ester), Phosphates (esters), thioethers, HALS compounds (hindered amine light stabilizers) and the like can be used.

Examples of the defoaming agent include benzoin, cyclohexane dimethanol bisbenzoate and the like. Examples of the fluidizing agent include polyalkyl acrylate, fluorohydrocarbon, and silicone oil. Other suitable additives include, for example, additives that improve tribocharging, such as tertiary amines having a sterically hindered substituent described in EP-B-371528.

The powder coating of the present invention can be applied by a usual method, for example, after spraying the powder coating on a grounded support, and then exposing the coating to heat at an appropriate temperature for a sufficient time. It can be applied by curing the film. The applied powder coating can be heated, for example, in a gas oven or an electric oven, or using infrared rays.

[0040] Thermosetting powder coating compositions for industrial use are, in a general sense, Powder Coatings, Chemistry and Technology.
Technology), Misev, pp. 141-173 (1991).

The composition of the present invention can be used, for example, in powder coatings for supports such as metals, woods, and plastics. Such paints are also suitable for the automotive industry as painted parts and decorative articles.

For example, “Resins and Curing Agents for Thermosetting Powder Coatings (Resins and curing agents for ther
mosetting powder coatings) '' (Kapilow and Sammel,
Vol. 59, July 1987, pages 39-47, Journal of Coatings Technology, solvent or water based paints are thermosetting powders. Not for paints, but for powder paints, it must meet requirements that do not apply to "liquid" paints, such as those relating to the melting point, rheological properties, reactivity, stability, etc. of the binder. Provided that the molecular weight, viscosity and glass transition temperature of the hydroxyl-functional polymers are more compatible with the choice of monomers, these polymers can surprisingly be used in combination with the crosslinkers of the present invention in a solvent or water based It can also be used as a raw material compound in a prepared paint.

In a further preferred embodiment of the present invention, the product obtained by the process of the present invention is applied as a crosslinking agent in a binder system for coil paints or can paints.

[0044] Suitable binding systems for these applications are hydroxyl-functional polymers such as polyesters, polyacrylates and the like. Suitable solvents in these applications are esters or hydrocarbons. Catalysts that can be used in coil paints or can paints are:
Known from polyurethane chemistry. Examples of the catalyst include a tin catalyst.

Coil coatings are described, for example, by Joseph E. Gaske, “Coil Coatings” (Federation of Society for Coatings Technology). for
Coatings Technology), February 1987, pp. 7-19).

Curing conditions and additives can be selected depending on the desired peak metal temperature (PMT) and the nature and thickness of the support. The curing time is generally about 250 ° C.
At a temperature of 400 ° C. and a PMT of 204 ° -249 ° C., the time can be about 20 to about 70 seconds.

Suitable supports include, for example, steel, tinned steel, aluminum, and the like.

The coil paint of the present invention is suitable for use as a primer or a top coat. For example, paints for household equipment such as refrigerators, freezers, microwave ovens, ovens, boilers, paints for trailer houses, wall coverings It can be used as a paint for materials.

The resin composition of the present invention gives good results also in the can coating industry where the desired layer thickness is generally thin and the curing conditions differ from those in making coil coatings.

[0050] Can coatings are described, for example, in "Organic Coatings-Science and Technology" by ZW Wicks et al.
ngs-Science and Technology), Volume 2: Applications, Properties and Performance "(
Wiley-Interscience, 1994, 284-
290) can be obtained.

The curing conditions and additives can be selected depending on the desired use and the nature and thickness of the support. Curing times generally range from a few seconds to tens of minutes at a temperature of about 100C to about 220C.

Suitable supports include, for example, steel, tin-plated steel (ETP, electrolytic tinplate), chrome-plated steel (ECCS, electrolytic chromium-chromium oxide steel), aluminum and the like.

The paints of the present invention are suitable for use as interior and exterior paints, such as beer cans, other beverage cans (“two-piece and three-piece”), spray cans, can ends (can end), pipes and tubes, drums, cigar boxes, canned fish (so-called "drawn-redrawn (DRD)", "draw-wall
It can be used as a paint for iron-and-draw (draw-wall ironed); They can be used in colored or uncolored compositions.

The use of exterior coatings is important mainly from a decorative point of view, which gives the support a suitable appearance for sale. It protects the metal from corrosion and the coating also serves as a label.

Interior coatings are primarily intended to protect the contents of the can on the one hand from the effects of metals and on the other hand to protect the metals from the contents of the can.

The type of monomer, crosslinker and curing conditions to be used in preparing the polyester can be selected depending on the desired application.

The system of the present invention can be used for colored and uncolored compositions.

If desired, customary additives such as pigments, fillers, stabilizers, dispersants, glidants, defoamers and the like can be added to the binder system according to the invention.

Hereinafter, the present invention will be described with reference to the following examples.

Example 1 Preparation of caprolactam-blocked tetramethylene diisocyanate

[0061]

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[0062] 54.4 g (0.2 mol) of carbonyl-bis-caprolactam were dissolved in 200 ml of ethyl acetate at 78 ° C. In 20 minutes, 88 g (0.1 mol) of 1,4-diaminebutane dissolved in 20 ml of ethyl acetate were added dropwise. A white suspension formed. After 4 hours, the reaction was stopped. The white product was filtered off. The caprolactam present was removed by sublimation in a vacuum oven at 60 ° C. A white solid of caprolactam-blocked tetramethylene diisocyanate was obtained in 80% yield.

Example 2 Preparation of caprolactam-blocked tris (isocyanatoethyl) amine

[0064]

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75.6 g (0.3 mol) of carbonyl-bis-caprolactam were dissolved in 200 ml of ethyl acetate at 78 ° C. In 20 minutes, tris (2-
Amine ethyl) 14.6 g (0.1 mol) amine was added dropwise. This clear suspension is
Stirred at 8 ° C. overnight. The solution was washed three times with 250 ml of water (containing a small amount of NaCl) to remove the caprolactam. The solution was was dried with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. Caprolactam
-Blocked tris (isocyanatoethyl) amine was found to be a colored oil and was obtained in 99% yield.

Example 3 Production of N, N-dibutyl-N- (caprolactamatecarboxylamine)

[0067]

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2.5 g (10 mmol) of carbonyl-bis-caprolactam (CBC) was added at 160 ° C.
To 10 ml (60 mmol) of dibutylamine. The coloring solution was stirred at 160 ° C. overnight. The whole was cooled. 150 ml of ethyl acetate was added to the solution. The solution was then extracted three times with 150 ml of water (buffer pH = 5). Ethyl acetate was removed on a rotary evaporator. It can be seen that dibutylamine was still present in the product. This was distilled off. N, N-Dibutyl-N- (caprolactamatecarboxyl) amine was an oil. Purity was 80%. The yield based on CBC was 99%.

Example 4 Preparation of Caprolactam-Blocked Hexamethylene Diisocyanate

[0070]

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151.2 g (0.6 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In 15 minutes, 34.8 g (0.3 mol) of 1,6-diaminehexane dissolved in 40 ml of ethyl acetate were added dropwise. The clear suspension was stirred at 78 ° C. overnight. The solution was washed four times with 250 ml of water (containing a small amount of NaCl),
The caprolactam was removed. The solution was was dried with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. After recrystallization in ethyl acetate, caprolactam-blocked hexamethylene diisocyanate was obtained as a white solid in 85% yield.

Example 5 Preparation of caprolactam-blocked octamethylene diisocyanate

[0073]

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252 g (1.0 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In 15 minutes, 75.1 g (0.5 mol) of 1,8-diamineoctane dissolved in 150 ml of ethyl acetate were added dropwise. The clear solution is added at 78 ° C for 2 hours.
Stirred for hours. The solution was washed three times with 500 ml of water (containing a small amount of NaCl) to remove the caprolactam. The clear solution was cooled to 5 ° C. The product crystallized out and was filtered off (yield = 47%). The solution was concentrated to 100 ml and cooled to 5 ° C. Again, the product crystallized out (yield = 38%). The product was filtered off. Subsequently,
The solution was concentrated to 50 ml. The product crystallized out again and was filtered off (yield = 6%).

Each product was dried at 40 ° C. in vacuo. Caprolactam-blocked octamethylene diisocyanate was found to be a white solid. Overall yield is 91
%Met.

Example 6 Caprolactam-blocked 1,8-diisocyanato, 4- (isocyanatomethyl)
Nonan production

[0077]

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302.4 g (1.2 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In one hour, 69.3 g (0.4 mol) of triaminononane dissolved in 100 ml of ethyl acetate were added dropwise. The reaction was monitored by TLC. After 3 hours, the clear solution is cooled to room temperature and 500 ml of water (containing a small amount of NaCl)
Extracted times. Then dried solution with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. The product was dried at 75 ° C. in vacuum. Caprolactam-blocked 1,8-diisocyanato, 4- (isocyanatomethyl) nonane was obtained as pure, slightly colored oil (yield = 99%).
.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] July 14, 2000 (2000.7.14)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image Wherein the group X represents a lactam, an oxime, an imide or a triazole in the form of XH at a temperature of from room temperature to 150 ° C.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Detailed description of the invention

[Correction method] Change

[Correction contents]

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a method for producing an N-alkyl or N-arylcarbamoyl derivative, particularly a blocked isocyanate. A blocked isocyanate is a compound that contains an isocyanate with a blocking agent.

BACKGROUND ART Blocked isocyanates are used in the production of polyurethanes and polyureas. The blocked isocyanate can be stably mixed with the polyol, for example, at temperatures up to 150 ° C. As the temperature increases, the blocking agent is released from the isocyanate groups, so that the released isocyanate can react with the polyol present to form a polyurethane.

A method for producing blocked isocyanates is described in GB-A-1415730. GB-A-1415730 describes a method of reacting N- (1-chloro-1-alkenyl) -carbonate with an amine to form a blocked isocyanate.

A method for producing an N-alkyl or N-arylcarbamoyl derivative is disclosed in DE-A-27.
12931. In the method, an isocyanate is contacted with caprolactam. As a result, caprolactam-blocked isocyanate is formed.

[0005] A disadvantage of the process disclosed in DE-A-2712931 is that the reaction with isocyanates involves a safety hazard.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a more secure method.

[0007] The purpose of this is to convert amines to the general formula

[0008]

Embedded image

Wherein the group X is in the form of XH and is contacted with a carbonic acid derivative of the formula lactam, oxime, imide or triazole.

In the method of the present invention, there is no isocyanate in the reaction mixture.

[0011] An advantage of the process of the present invention is that during the formation of the blocked isocyanate, free isocyanate is no longer present.

Since the known reaction disclosed in DE-A-2712931 does not proceed quantitatively, small amounts of free isocyanate are present in the reaction mixture. To reduce the vapor pressure of this free isocyanate, the isocyanate is often trimerized by increasing the temperature before contacting the isocyanate with the lactam. This is particularly the case for isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI). The advantage and significance of the fact that free isocyanate is not present in the reaction mixture in the process according to the invention is that it is not necessary to carry out the above-mentioned trimerization reaction.

A further advantage of the method of the present invention is that it can be used to prepare N-alkyl or N-aryl carbamoyl derivatives where the nitrogen is secondary and the derivative is a lactam, oxime, imide or triazole. Is to get. These are compounds that cannot be prepared by known isocyanate routes.

In the context of the present invention, the amine may be a mono-, di-, tri-, polyamine or a mixture thereof. Examples of the di- and triamines include diaminooctane, diaminononane, diaminododecane, trisaminononane, diaminodixydecane, diaminodioxododecane, bishexamethylene trisamine, and Jeffamine. Other suitable amines are oligomers as binary reaction products. Examples of the oligomer include hexamethylene diamine, adipic acid, urea, carbonyl biscaprolactamate (CBC),
Reaction products with one or two caprolactam molecules, and the like.

The advantage of the process according to the invention for producing blocked isocyanates on the basis of oligomeric amines is that the group (X) leaving during the reaction of the carbonate derivative with the amine is easily removed as XH from the reaction mixture. The fact is that you can. This means
In contrast to the removal of the triethylamine salts released in the production of blocked isocyanates based on phosgene and triethylamine.

The contacting of the amine with the carbonic acid derivative can be carried out in a solvent, if desired. Preferably, this is done by dissolving the carbonate derivative of formula I in a suitable first solvent. Suitable solvents are generally aprotic solvents such as esters, ethers, cyclic carbonates, cyclic amides, hydrocarbons and the like. Subsequently, the amine dissolved in the second solvent is slowly added to the solution of the carbonate derivative with constant stirring. The second solvent is preferably also selected from the group of the same aprotic solvents. Preferably, the first and second solvents are the same.

After the addition of the dissolved amine, the mixture is stirred for a while at a temperature between room temperature and 150 ° C. When the temperature exceeds 150 ° C., the blocking agent can be easily eliminated. Preferably, after stirring at a temperature of 50 ° C to 100 ° C, the N-alkyl or N-arylcarbamoyl derivative formed can be separated from the reaction mixture by a known method.

The products obtained by the process according to the invention can be applied very widely in technically different fields, ie both in thermosetting and thermoplastic applications. Examples thereof include, for example, powder coating compositions, coating systems based on water or solvents, coating systems for cans or coils, inks, toners, film-forming agents for sizing glass fibers,
Examples include an adhesive, a hot melt, and a rubber composition.

The unmodified or partially modified polymers of the present invention can generally be used in powder coating compositions, can or coil coating compositions, and solvent-based coating compositions.

In a preferred embodiment of the present invention, the product obtained by the method of the present invention can be used as a crosslinking agent in a thermosetting powder coating composition.

Thermosetting powder coatings have better chemical resistance than thermoplastic powder coatings. As a result, there has been a longstanding effort to develop crosslinkers and polymers for thermoset powder coatings. There are still attempts to find binder compositions for thermosetting powder coatings with good flowability, good storage stability and good reactivity. Binder compositions for thermosetting powder coatings generally contain more than 50% by weight of polymer and less than 50% by weight of crosslinker.

The products obtained according to the invention can be used in powder coating compositions as crosslinking agents in combination with hydroxyl-functional polymers.

The hydroxyl-functional polymer is preferably a polyester, a polyacrylate, or a mixture of both. Preferably, the polyester has a hydroxyl number of 20-100 mg KOH / g of resin and an acid number of less than 10 mg KOH / g of resin. Preferably, the polyacrylate has a hydroxyl number of 40-150 mg KOH / g of resin and an acid number of less than 20 mg KOH / g of resin.

The weight ratio of the hydroxyl group containing polymer to the crosslinker is from about 95: 5 to about 5
0:50, preferably 93: 7 to 70:30. This ratio depends, among other factors, on the hydroxyl number of the polymer.

The hydroxyl-functional polymer is, for example, extruded at a temperature of about 100 ° C.
It can be mixed with a blocked crosslinker. Curing, for example, at about 130 ° C.
It occurs at a temperature of from about to about 170C (e.g., for about 10 to 40 minutes), preferably at a temperature above about 150C.

For example, fillers, catalysts, curing agents, flow agents and / or stabilizers, and, if desired, additives such as pigments, can be added to the coating system, preferably prior to extrusion.

[0027] Suitable polyesters can be obtained from carboxylic acids or their equivalents by conventional manufacturing methods. It is preferred to use mainly aromatic carboxylic acids.
Examples thereof include, for example, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 3,6-dichlorophthalic acid, tetrachlorophthalic acid, etc.
Also, as long as available, equivalents such as the anhydrides, acid chlorides or lower alkyl esters are mentioned. Generally, the carboxylic acid component will have at least 50
% By weight, preferably at least 70% by weight, of isophthalic acid and / or terephthalic acid.

Preferably, the diol component of the polyester is an aliphatic diol. Examples thereof include, for example, ethylene glycol, propane-1,2-diol, propane-1
, 3-diol, butane-1,2-diol, butane-1,4-diol, butane-1,3
-Diol, 2,2-dimethylpropanediol-1,3 (= neopentyl glycol
), Hexane-1,6-diol, 2,2- [bis (2-hydroxyethoxy)] phenylpropane, and a small amount of polyols such as glycerol, hexanetriol, pentaerythritol, sorbitol, trimethylolethane, Trimethylolpropane, tris (2-hydroxy) isocyanurate and the like can be used as the alcohol. An epoxy compound can be used instead of the diol and the polyol, respectively. The alcohol component preferably contains at least 50 mol% of neopentyl glycol.

Furthermore, the applied polycarboxylic acid can be a cycloaliphatic and / or acyclic polycarboxylic acid. Examples thereof include, for example, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexanehydroendomethylenetetrahydrophthalic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, adipic acid,
Succinic acid, maleic acid and the like can be mentioned. The amount of cycloaliphatic and / or acyclic polycarboxylic acid can be up to about 30 mol%, preferably up to about 20 mol%, based on the total carboxylic acid. Hydroxycarboxylic acids and / or lactones, if desired, can also be used. For example, 1
2-hydroxystearic acid, ε-caprolactone, hydroxypivalic acid ester of neopentyl glycol and the like. During the preparation, the monocarboxylic acid can also be added in small amounts, for example in amounts of less than 5% by weight. For example,
For example, benzoic acid, tert-butylbenzoic acid, hexahydrobenzoic acid, saturated aliphatic monocarboxylic acid and the like can be mentioned.

[0030] Polyesters can be produced by esterification or transesterification reactions known to those skilled in the art. If desired, conventional catalysts can be used. Examples include dibutyltin oxide, tetrabutyl titanate, and the like. The production conditions and the COOH / OH ratio depend on the desired hydroxyl number and acid number, e.g.
It is selected so as to obtain a polyester resin having an acid number of less than 0 mg KOH / g resin.

Preferably, the polyester is a dicarboxylic acid of about 40 to 100 mole% isophthalic acid and about 0 to 60 mole% terephthalic acid, wherein the total amount of isophthalic acid and terephthalic acid is 100 mole% ) As the base material. Preferably, the amount of isophthalic acid is greater than 60 mol%.

If desired, the polyester can also be based on more than two dicarboxylic acids.

The hydroxyl-functional acrylic resin can be based on, for example, hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl (meth) acrylate, and the like. This resin, for example, (meth) acrylic acid, (meth)
An alkyl ester of acrylic acid or the like can be used as a base material. Examples thereof include, for example, ethyl (meth) acrylate, isopropyl (meth) acrylate,
n-butyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (
(Meth) acrylate, ethylhexyl (meth) acrylate and / or cyclohexyl (meth) acrylate. For example, a vinyl compound such as styrene can be used.

The glass transition temperature (Tg) of the product obtained by the process of the invention is between 10 ° C. and 150 ° C., preferably between 50 ° C. and 110 ° C., depending on the raw materials and the molecular weight chosen.

When the products of the invention are used in combination with a hydroxyl-functional polymer in a binder composition, for example, good flowability and good chemical resistance, bubble formation on the surface with a layer thickness of at least 120 μm or less It combines the highly desirable properties such as the desired gloss, high resistance to boiling water and salt spray, high scratch resistance, good mechanical properties, and good color stability of powder coatings without the need to .

The production of common thermosetting powder coatings and the chemical reaction that cures the powder coating to form a cured coating is described in Powder Coatings, Chemistry of Misev. and Technology) (1991, John Wiley), pp. 42-54, 148, and 22.
It is described on pages 4-226. Thermoset binder compositions are generally defined as the resinous portion of a powder coating consisting of a polymer and a crosslinker.

If desired, customary additives such as, for example, pigments, fillers, defoamers, flow agents, stabilizers and the like can be used in the binder compositions and powder coating systems according to the invention. Suitable pigments include, for example, inorganic pigments such as titanium dioxide, zinc sulfide, iron oxide and chromium oxide, and organic pigments such as azo compounds. Suitable fillers include, for example, metal oxides, silicates, carbonates, sulfates, and the like.

Examples of the stabilizer include primary and / or secondary antioxidants and UV stabilizers such as quinone, phenol compounds (having a substituent having a steric hindrance), phosphonite (ester), Phosphates (esters), thioethers, HALS compounds (hindered amine light stabilizers) and the like can be used.

Examples of the defoaming agent include benzoin, cyclohexane dimethanol bisbenzoate and the like. Examples of the fluidizing agent include polyalkyl acrylate, fluorohydrocarbon, and silicone oil. Other suitable additives include, for example, additives that improve tribocharging, such as tertiary amines having a sterically hindered substituent described in EP-B-371528.

The powder coating of the present invention can be applied by a usual method, for example, after spraying the powder coating on a grounded support, and then exposing the coating to heat at an appropriate temperature for a sufficient time. It can be applied by curing the film. The applied powder coating can be heated, for example, in a gas oven or an electric oven, or using infrared rays.

[0041] Thermosetting powder coating compositions for industrial use are, in a general sense, powder coatings, Chemistry and Technology.
Technology), Misev, pp. 141-173 (1991).

The composition of the present invention can be used, for example, in powder coatings for supports such as metals, woods, and plastics. Such paints are also suitable for the automotive industry as painted parts and decorative articles.

For example, “Resins and curing agents for therr.
mosetting powder coatings) '' (Kapilow and Sammel,
Vol. 59, July 1987, pages 39-47, Journal of Coatings Technology, solvent or water based paints are thermosetting powders. Not for paints, but for powder paints, it must meet requirements that do not apply to "liquid" paints, such as those relating to the melting point, rheological properties, reactivity, stability, etc. of the binder. Provided that the molecular weight, viscosity and glass transition temperature of the hydroxyl-functional polymers are more compatible with the choice of monomers, these polymers can surprisingly be used in combination with the crosslinkers of the present invention in a solvent or water based It can also be used as a raw material compound in a prepared paint.

In a further preferred embodiment of the present invention, the product obtained by the process of the present invention is applied as a crosslinking agent in a binder system for coil paints or can paints.

Suitable binding systems for these applications are hydroxyl-functional polymers such as polyesters, polyacrylates and the like. Suitable solvents in these applications are esters or hydrocarbons. Catalysts that can be used in coil paints or can paints are:
Known from polyurethane chemistry. Examples of the catalyst include a tin catalyst.

Coil coatings are available, for example, from Joseph E. Gaske's “Coil Coatings” (Federation of Society for Coatings Technology). for
Coatings Technology), February 1987, pp. 7-19).

Curing conditions and additives can be selected depending on the desired peak metal temperature (PMT) and the nature and thickness of the support. The curing time is generally about 250 ° C.
At a temperature of 400 ° C. and a PMT of 204 ° -249 ° C., the time can be about 20 to about 70 seconds.

[0048] Suitable supports include, for example, steel, tinned steel, aluminum, and the like.

The coil paint of the present invention is suitable for use as a primer or a top coat. For example, paints for household equipment such as refrigerators, freezers, microwave ovens, ovens, boilers, paints for trailer houses, wall exteriors It can be used as a paint for materials.

The resin composition of the present invention gives good results also in the can coating industry where the desired layer thickness is generally thin and the curing conditions are different from those in making coil coatings.

[0051] Can coatings are described, for example, in "Organic Coatings-Science and Technology" by ZW Wicks et al.
ngs-Science and Technology), Volume 2: Applications, Properties and Performance "(
Wiley-Interscience, 1994, 284-
290) can be obtained.

The curing conditions and additives can be selected depending on the desired use and the nature and thickness of the support. Curing times generally range from a few seconds to tens of minutes at a temperature of about 100C to about 220C.

Suitable supports include, for example, steel, tin-plated steel (ETP, electrolytic tinplate), chromium-plated steel (ECCS, electrolytic chromium-chromium oxide steel), aluminum, and the like.

The paints of the present invention are suitable for use as interior and exterior paints, for example, beer cans, other beverage cans (“two-piece and three-piece”), spray cans, can ends (can end), pipes and tubes, drums, cigar boxes, canned fish (so-called "drawn-redrawn (DRD)", "draw-wall
It can be used as a paint for iron-and-draw (draw-wall ironed); They can be used in colored or uncolored compositions.

The use of exterior coatings is important primarily from a decorative point of view, which gives the support a suitable appearance for sale. It protects the metal from corrosion and the coating also serves as a label.

Interior paints are primarily intended to protect the contents of the can on the one hand from the effects of metals and on the other hand to protect the metals from the contents of the can.

The type of monomer, crosslinker and curing conditions to be used in preparing the polyester can be selected depending on the desired application.

The system of the present invention can be used for colored and uncolored compositions.

If desired, customary additives such as pigments, fillers, stabilizers, dispersants, glidants, defoamers and the like can be added to the binder system according to the invention.

Hereinafter, the present invention will be described based on the following examples.

Example 1 Preparation of caprolactam-blocked tetramethylene diisocyanate

[0062]

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54.4 g (0.2 mol) of carbonyl-bis-caprolactam were dissolved in 200 ml of ethyl acetate at 78 ° C. In 20 minutes, 88 g (0.1 mol) of 1,4-diaminebutane dissolved in 20 ml of ethyl acetate were added dropwise. A white suspension formed. After 4 hours, the reaction was stopped. The white product was filtered off. The caprolactam present was removed by sublimation in a vacuum oven at 60 ° C. A white solid of caprolactam-blocked tetramethylene diisocyanate was obtained in 80% yield.

Example 2 Preparation of Caprolactam-Blocked Tris (isocyanatoethyl) amine

[0065]

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75.6 g (0.3 mol) of carbonyl-bis-caprolactam were dissolved in 200 ml of ethyl acetate at 78 ° C. In 20 minutes, tris (2-
Amine ethyl) 14.6 g (0.1 mol) amine was added dropwise. This clear suspension is
Stirred at 8 ° C. overnight. The solution was washed three times with 250 ml of water (containing a small amount of NaCl) to remove the caprolactam. The solution was was dried with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. Caprolactam
-Blocked tris (isocyanatoethyl) amine was found to be a colored oil and was obtained in 99% yield.

Example 3 Production of N, N-dibutyl-N- (caprolactamatecarboxylamine)

[0068]

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2.5 g (10 mmol) of carbonyl-bis-caprolactam (CBC) was added at 160 ° C.
To 10 ml (60 mmol) of dibutylamine. The coloring solution was stirred at 160 ° C. overnight. The whole was cooled. 150 ml of ethyl acetate was added to the solution. The solution was then extracted three times with 150 ml of water (buffer pH = 5). Ethyl acetate was removed on a rotary evaporator. It can be seen that dibutylamine was still present in the product. This was distilled off. N, N-Dibutyl-N- (caprolactamatecarboxyl) amine was an oil. Purity was 80%. The yield based on CBC was 99%.

Example 4 Preparation of Caprolactam-Blocked Hexamethylene Diisocyanate

[0071]

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151.2 g (0.6 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In 15 minutes, 34.8 g (0.3 mol) of 1,6-diaminehexane dissolved in 40 ml of ethyl acetate were added dropwise. The clear suspension was stirred at 78 ° C. overnight. The solution was washed four times with 250 ml of water (containing a small amount of NaCl),
The caprolactam was removed. The solution was was dried with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. After recrystallization in ethyl acetate, caprolactam-blocked hexamethylene diisocyanate was obtained as a white solid in 85% yield.

Example 5 Preparation of caprolactam-blocked octamethylene diisocyanate

[0074]

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252 g (1.0 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In 15 minutes, 75.1 g (0.5 mol) of 1,8-diamineoctane dissolved in 150 ml of ethyl acetate were added dropwise. The clear solution is added at 78 ° C for 2 hours.
Stirred for hours. The solution was washed three times with 500 ml of water (containing a small amount of NaCl) to remove the caprolactam. The clear solution was cooled to 5 ° C. The product crystallized out and was filtered off (yield = 47%). The solution was concentrated to 100 ml and cooled to 5 ° C. Again, the product crystallized out (yield = 38%). The product was filtered off. Subsequently,
The solution was concentrated to 50 ml. The product crystallized out again and was filtered off (yield = 6%).

Each product was dried at 40 ° C. in vacuum. Caprolactam-blocked octamethylene diisocyanate was found to be a white solid. Overall yield is 91
%Met.

Example 6 Caprolactam-blocked 1,8-diisocyanato, 4- (isocyanatomethyl)
Nonan production

[0078]

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302.4 g (1.2 mol) of carbonyl-bis-caprolactam were dissolved in 400 ml of ethyl acetate at 78 ° C. In one hour, 69.3 g (0.4 mol) of triaminononane dissolved in 100 ml of ethyl acetate were added dropwise. The reaction was monitored by TLC. After 3 hours, the clear solution is cooled to room temperature and 500 ml of water (containing a small amount of NaCl)
Extracted times. Then dried solution with NaSO _4. The NaSO ₄ was filtered off and the ethyl acetate was removed on a rotary evaporator. The product was dried at 75 ° C. in vacuum. Caprolactam-blocked 1,8-diisocyanato, 4- (isocyanatomethyl) nonane was obtained as pure, slightly colored oil (yield = 99%).
.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Invention Bartolomeus Johannes Margareta Plum Netherlands, Nuel-6235 Argyle Ulestraten, Klein Berghemmer Wech 52nd F term (reference) 4C034 DE11 4J038 DG111 DG191 DG301 JB22 JB23 JB26 JB34 KA03 MA02 MA07 MA09 NA09

Claims (4)

[Claims] 1. A method for producing an N-alkyl or N-arylcarbamoyl derivative, wherein an amine is represented by the general formula: Wherein the group X is in the form of XH and represents a lactam, oxime, imide or triazole. 2. The method according to claim 1, wherein the group X represents a lactam in the form of XH. 3. Use of the product obtained according to claim 1 or 2 in a coating composition. 4. A binder composition for a coating composition comprising the product obtained by the method according to claim 1.