JPS62236816A - Activated catalyst, catalyst added reaction mixture and curing thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to polyol/polyisocyanate coatings, and in particular to unique catalyst systems useful therein.

Vapor permeable paints are usually used.
Tivncurable coatings belong to a class of coatings formulated with aromatic hydroxy-functional polymers and multi-isocyanate crosslinkers that are cured by exposing the coated film to a steam tertiary amine catalyst. Curing chambers have been developed to economically and safely contain and handle vaporized tertiary amine catalysts.

Generally, the curing chamber is a substantially empty box through which a conveyor carrying coated substrates is passed, contacting such coated substrates with a vaporous tertiary amine produced by a conventional inert gas carrier. Long pot life system (exte
It is preferable to use aromatic hydroxy-functional polymers in cases where a single stranded pot 1ife system is required. Aliphatic hydroxy-functional resins can be used where two-part paints can be accommodated. Multi-isocyanate crosslinkers in conventional vapor permeable coatings contain at least some aromatic isocyanate groups to achieve practical cure rates.

The requirements for conventional vapor permeable curable coatings described above are modified somewhat by the vapor amine catalyzed atomization process described in U.S. Pat. No. 4,517,222. This steam catalytic atomization process can be used to simultaneously generate a paint atomize and a carrier gas carrying a catalytic amount of steam tertiary amine catalyst. The generated atomization and the steam-catalyzed amine-supported carrier gas stream are mixed and directed to a substrate to form a coating thereon. Cures quickly and does not require the use of a curing chamber.

Additionally, all aliphatic isocyanate curing agents can be used in the above spray process. However, aromatic hydroxyl groups in resins are still needed.

One drawback to the requirement for aromatic hydroxyl groups in resins is that the aromaticity is difficult to maintain in high solids paints (high 5
There are inherent limitations in the formulation of solids coatings. The same holds true for the aromaticity requirement in multi-isocyanate crosslinkers. Additionally, non-volatile solids limitations apply to the steam amine catalyst spray process described above.

Despite improvements in the field of vapor permeable curable coatings,
All aliphatic, high performance urethane finishes are also being developed. Alternatively, such urethane finishes are typically heat cured in the presence of a metal catalyst such as tin. In this case, there is a need to adapt vapor permeable coating technology to such urethane coatings which preferably utilize conventional tin catalyst systems. Such a need in the art is addressed by the present invention.

The present invention overcomes many of the limitations encountered in chamber curing and spray curing vapor cured coatings by adapting conventional urethane finishes to be applied and cured by conventional vapor cure coating techniques. It is.

In general, the novel catalysts of this invention are compatible with conventional thermoset urethane systems.

One aspect of the invention is an activated catalyst that is effective for the reaction of hydroxyl and isocyanate groups and that is activated in the presence of an amine catalyst or heat.
ble catalyst). The activated catalyst consists of the reaction product of a metal catalyst selected from tin catalysts, bismuth catalysts and mixtures thereof and a molar excess of complexing agent. The complexing agent can be selected from the group of mercapto compounds, polyphenols which have the characteristic of being able to react with isocyanate groups in the presence of a tertiary amine catalyst, and mixtures thereof.

Another aspect of the invention is a catalytic reaction mixture consisting of a polyol, a polyisocyanate, an optional solvent, and an activated catalyst as described above.
ion m1xture). Another aspect of the invention is that the polyol resin has a complexing agent functionality (complexin) that is complexed with a tin or bismuth catalyst.
The object of the present invention is to provide a catalytic reaction mixture having a high agent functionality. Furthermore, the catalytic reaction mixture consists of polyisocyanate and optionally a solvent.

Yet another aspect of the present invention is to provide a method of curing a catalytic reaction mixture for applying a coating of the catalytic reaction mixture described above to a substrate. The coating is then exposed to an amine activator or heat to cure the coating. The use of amine activators is
Allow curing to proceed at room temperature.

Yet another aspect of the invention is to apply the catalytic reaction mixture as an atomization, which atomization is mixed with an amine activator, and the mixture is applied as a coating to a substrate. The amine activator can be present in the catalytic reaction mixture as a vapor or as a liquid.

Furthermore, an aspect of the present invention is also directed to a method for improving the pot life of catalyzed reaction mixtures of polyols and polyisocyanates, where the catalyst is selected from tin catalysts, bismuth catalysts or mixtures thereof. This method uses a catalyst and
Polyphenols having the characteristic of being able to react with isocyanate groups in the presence of mercapto groups and tertiary amine activators;
and a molar excess of a complexing agent selected from the group of mixtures thereof. Furthermore, additional stability can be obtained by incorporating chelating agents.

The present invention has the following advantages. That is, it is possible to formulate catalytic reaction mixtures with extremely long and effective pot lives. Also, the reaction mixture can be rapidly cured simply by the presence of the amine activator. Also,
The catalytic reaction mixture does not require heat to achieve cure, but can be heat cured if desired.

Additionally, the catalyst system of the present invention can be used in conventional urethane coatings, especially high performance urethane finishes. The above-mentioned advantages and others can be readily ascertained by those skilled in the art from the description herein.

Conventional urethane paints, especially finishing paints, are obtained as two-part packages (two-component systems). The first pack (particularly part A) is a polyol and the second pack (part B) is a polyisocyanate. Solvent and other conventional paint additives are added to each bag by conventional techniques. Catalysts, particularly tin or other metal catalysts, can often be included in the polyol bag to suppress premature gelling of the polyisocyanate. In some cases, the catalyst package is not added to Part A or Part B until before the paint is applied.

Generally, when applying the conventional two-component paints described above, the two components are mixed prior to application by conventional roll coating, reverse roll coating, or other conventional tactile means; It can be applied by atomization technique using a double-headed spray gun. Regardless of the application technique, the two fluids are kept separate to prevent premature reactions with attendant viscosity increases that would prevent effective application. Coating paints are often baked to speed up curing and drive solvents out of the coated film.

One feature of the catalyst system of the present invention is that its use provides a long pot life. This long pot life can be achieved without the need for specially formulated resins, hardeners, etc. Alternatively, the catalytic reaction mixture can be prepared simply on dem by the presence of an amine activator in the mixture or by heating the mixture.
a'nd) J hardening or "trigger
d) Can do J.

This is important because such a combination of properties cannot be obtained by using ordinary tin mercaptide alone.

The catalyst system of the present invention is not a tin mercaptide, but is the reaction product of a tin catalyst and a complexing agent such as a molar excess of a mercapto compound, which reaction product can be formed by simply mixing at room temperature, and which can be formed by simply mixing at room temperature. The product is called a tin mercapto complex catalyst. In fact, the pot life of tin mercaptide catalyzed coatings can be extended by the addition of mercapto compounds. Although it is not clearly known whether a tin mercaptide/mercapto complex is formed, the combination of long pot life and rapid curing due to the presence of an amine activator has been experimentally confirmed.

In the above, tin catalysts and mercapto complexing agents have been described for illustrative purposes, but are not limiting.

In this regard, novel tin catalyst/mercapto complexes can be formed using a molar excess of mercapto compound relative to the tin catalyst. By molar excess of mercapto compound is meant adding enough mercapto compound to the tin catalyst such that the polyol/polyisocyanate mixture contains only the tin catalyst (i.e., no mercapto compound). It has a pot life that is at least twice as long. In general, this will affect the specific selection of tin catalyst, mercapto compound, other formulation ingredients, etc., but the molar ratio of mercapto compound to tin catalyst should be between about 2 = 1 and 500.
: Can be in the range of 1.

For this purpose, the pot life of the paint is determined by the open pot (
It is the time required for the viscosity of a paint in an open pot to double from its initial viscosity.

Without wishing to be bound by theory, the tin catalyst and mercapto compound form a complex that interferes with the tin catalyst but otherwise renders it non-reactive. The structure of the complex and reaction for its formulation is shown in FIG. As shown in FIG. 1, catalyst structure I is a common tin catalyst such as, for example, dibutyltin dibutyrate in which the ligand X is a laurate group. mercapto compound,
The initial reaction that occurs, for example, by the addition of R' SH, is the displacement of two ligands, e.g.
) Contains substitutions for U. Catalyst species (1) and (2) are both active catalyst species that promote the hydroxyl/isocyanate reaction.

By adding excess mercapto compound, an equilibrium reaction is established between catalytic species (1) and catalytic species (2). This reaction involves tin metal converting from a tetra-coordinated species to a hexa-coordinated species in coordination of the adduct mercapto group. Catalyst species■
is inert and is a novel catalytic species of the present invention. This is a catalyst-added system (ca.
Catalytic species (1) that enable the catalyzed system (catalyzed system). Also, the catalytic species 1 can be activated or triggered on demand.

Trigger that converts the catalytic species to the active form
) consists of amines or heat. The trigger is a catalyst species■.

■Or you can release the combination. Regardless of whether the active species is released, the trigger, e.g. amine or heat,
and the presence of isocyanate functionality is necessary. The isocyanate functionality reacts with a complexing agent (eg, a mercapto group) that enhances the conversion of the inactive catalyst species (1) to the active catalyst species (2) or (2).

The released or substituted mercapto group reacts with the free isocyanate group in the coating, forming a thiocarbamate bond. The thiocarbamate bond exhibits catalytic activity in the hydroxyl/isocyanate reaction. This thiocarbamate bond further promotes the hydroxyl/isocyanate reaction and also acts on the hardening of the coating film.

FIG. 1 and the above description also indicate that bismuth can be used as the active metal catalyst in the present invention. Further, as a complex forming agent, polyphenol can be used as described later.

Regarding tin catalysts, a variety of common tin catalysts can be advantageously used in the catalyst systems of the present invention and the catalytic addition reactions and mixtures of the present invention. Common tin catalysts include, for example, stannous octoate, dibutyltin dicarboxylate (e.g., dibutyltin dioctoate), tin mercaptide (e.g., diptyltin dilauryl mercaptide), stannous acetate, stannic oxide, and stannous citrate. Tin, stannous oxylate (stannous)
(us oxylate), stannous chloride, stannic chloride, tetraphenyltin, tetrabutyltin, tri-n-butyltin acetate, di-n-butyltin dilaurate, dimethyltin dichloride, and mixtures thereof. It appears that some tin catalysts and some mercaptans (or polyphenols) are unable to form the desired effective complexes due to steric hindrance. It should be noted that suitable complexes can be formed from mostly tin catalysts and mostly mercaptans (and polyphenols).

Also, a wide variety of common bismuth catalysts can be advantageously used in the present invention. As a normal bismuth catalyst,
Examples include bismuth tricarboxylates (e.g. acetate, oleate, etc.), bismuth nitrate, bismuth halides (e.g. bismuth bromide, bismuth chloride, bismuth iodide, etc.), bismuth sulfide, basic bismuth dicarboxylates (e.g. bismuth li bis-neodecanoate, etc.). bismuthly bis-neodecanoa
te), bismuth subsalicylate, bismuth subgallate, etc.), and mixtures thereof.

Regarding mercaptans, a variety of monofunctional and polyfunctional mercaptans can be advantageously used in the present invention. Typical mercaptans include, for example, trimethylol propane tri-(3-mercapto propionate), pentaerythritol tetra-(3-mercapto propionate), glycol di(3-mercapto propionate), glycol di-mercaptoacetate, and trimethylol propane. Trithioglycolate, mercapto diethyl ether, ethane
Dithiol, thiolactic acid, mercaptopropionic acid and its esters, thiophenol, thioacetic acid, 2-mercaptoethanol, 1,4-butanedithiol, 2,
3-dimercapto propatool, toluene-3,4-
Dithiol, α-α′-dimercaptopa-xyxylene salicylic acid, mercaptoacetic acid, dodecane dithiol, dosidecane dithiol, dithiophenol, di-para-chlorothiophenol, dimercaptobenzothiazole, 3,4-dimercaptotoluene, allylmercaptan, benzyl Mercaptan, 1,6-hexane dithiol, 1-octane thiol, para-
Thiocresol, 2,'3,5,6-titrafluorothiophenol, cyclohexyl mercaptan, methylthioglycolate, various mercaptopyridines, dithioerythritol, 6-ethoxy-2-mercaptobenzothiazole, d-limonene dimercaptan, etc. It includes mixtures thereof. Further useful mercaptans can be found in various catalogs of commonly available mercaptans.

- In addition to supplying functional or polyfunctional mercaptan monomers or oligomers, various resin compounds can also be added pendant (
pendant) can be synthesized or modified to obtain mercaptan or thiol groups. Various mercaptans suitable for synthesizing the mercapto-functional resin materials used to prepare the coatings of the present invention include, for example, 1,4
-butanedithiol, 2,3-dimercapto propatool, toluene-3,4-dithiol, oyohi α, α′
- Dimerkabuto p-xylene. Other suitable active mercaptan compounds include thiosalicylic acid, mercaptoacetic acid, 2-mercaptoethanol, dodecanedithiol, didodecanedithiol, dithiolphenol, di-para-chlorothiophenol, dimercaptobenzothiazole, 3°4-dimercaptotoluene. , allylmercaptan, 1,6-hexanedithiol, mercaptopropionic acid, p-thiocresol, d-limonenedimercaptan, cyclohexyl mercaptan, methylthioglycolate, mercaptopyridine, dithioerythritol, 6-ethoxy-2-mercaptobenzothiazole Examples include: Further useful mercaptans can be found in various catalogs of commonly available mercaptans.

Virtually any oligomeric, polymeric or resinous compound can be modified to provide pendant mercapcune or thiol groups. Typical resin materials containing mercaptan groups include, for example, epoxy and epoxy-modified diglycidyl ether mercaptans having a biphenol A structure.
Functional urethane resins can be derived from various aliphatic polyethylene or polypropylene glycol (diglycidyl ether) adducts and glycidyl ethers of phenolic resins. Other useful pendant mercapto group-containing polymers include condensation products of trimerized fatty acids co-reacted with trifunctional amines, such as ethylene diamine, and then reacted with 3-mercaptopropionic acid and the like. A variety of acrylic and vinyl resins can be readily modified according to the guidelines of this invention.

In this regard, any of the common hydroxyl-containing monomers, oligomers or polymers described above for use in vapor permeable coatings may be suitably modified to contain pendant mercaptan groups for use in formulating the coatings of the present invention. be able to. For example, the mercaptan-terminated acid of such polyols
Esterification (transesterification) by .

Although not exhaustive, the following description shows conventional vapor permeable curable coatings that may be suitably modified.

U.S. Pat. No. 3', 409. The '579 patent describes binder compositions of phenol-aldehyde resins (including resols, novolaks and resitols), preferably benzyl ether or polyether phenolic resins. U.S. Pat. No. 3,676,392 describes organic solvent resin compositions comprising polyether phenolic or methylol-terminated phenolic (resol) resins. U.S. Pat. No. 3,429.848 describes a composition in which silane is added to the composition described in U.S. Pat. No. 3,409,579.

U.S. Pat. No. 3,789,044 describes polyepoxide resins capped with oxybenzoic acid. U.S. Pat. No. 3,822,226 describes a curable composition of phenol reacted with an unsaturated material selected from unsaturated fatty acids, oils, fatty acid esters, butadiene homopolymers, butadiene copolymers, alcohols, and acids. Are listed. U.S. Patent No. 3,8j
No. 6,491 describes similar hydroxy-functional polymers (e.g., polyesters, etc.) capped with oxybenzoic acid.
acrylic, polyether, etc.). GB 1,369,351 describes diphenolic acid capped hydroxy or epoxy compounds. GB 1,351,881 describes the modification of polyhydroxy, polyepoxy or polycarboxy resins with reaction products of phenols and aldehydes.

U.S. Pat. No. 2,967.117 describes polyhydroxy polyesters, and U.S. Pat. No. 4,267.239 describes reacting alkyd resins with para-oxybenzoic acid. has been done. U.S. Pat. No. 4,298,658 states that 2.6
Alkyd resins modified with -dimethylol-p-cresol have been proposed.

U.S. Patent No. 4,343,839, 4,365°039
No. 4,374,167 describes polyester resins with particular application to flexible substrates. U.S. Pat. No. 4,374,181 describes a resin particularly adapted for use in reaction injection molded (RIM) urethane parts. U.S. Patent No. 4,331,78
No. 2 describes an oxybenzoic acid-epoxy adduct. U.S. Pat. No. 4,343,924 proposes stabilized phenol-functional condensation products of phenol-aldehyde reaction products.

U.S. Pat. No. 4,366,193 describes the use of 1,2-dihydroxybenzene or its derivatives in vapor permeable curable coatings. U.S. Patent No. 4,
No. 368,222 describes the unique use of vapor permeable curable coatings on surface-porous substrates of fiber-reinforced molding compositions (eg SMC). lastly,
2.3' in U.S. Pat. No. 4.3.96,647.
, describes the use of 4-trihydroxy diphenyl.

The aromatic-hydroxyl polymers or resins mentioned above, as well as many other resins, can be modified to contain mercaptan groups used in formulating the coatings of this invention.

Further, the hydroxy compound can represent a hydroxy urethane prepolymer, and as this prepolymer, a polyol or a low molecular alcohol (monomer 1 calcohol) obtained from polyester, polyether, polyurethane, polysulfide, etc. can be used. Ethylenic unsaturation can be present in the lower alcohol or polyol thereof, and if such unsaturation is required, it can be reacted to the polyol or lower alcohol by conventional reaction schemes. The usual reaction formula is lower alcohol or polyol,
For example, acrylic acid, acrylic halide, acrylic
terminal ether, acrylic or methacrylic anhydride,
Other reaction schemes for formulating hydroxyurecne prepolymers that require reaction with isocyanate-terminated acrylates, epoxy acrylates, etc. are hydroxy-acrylate monomers, hydroxy methacrylate monomers or allyl ether alcohols with e.g. maleic acid, fucuric acid, etc. , succinic acid, norboren (e
), including reactions with cyclic anhydrides such as glutaric acid and the like. Optionally, unsaturated polyol-polyesters such as ethylene oxide, propylene oxide, glycidyl acrylate, allyl glycidyl ether, α
- Can be reacted with a suitable oxirane such as olefin epoxide, butyl glycidyl ether, etc.

Additional common reactions to produce hydroxyurethane prepolymers include reacting alpha-aliphatic or aromatic substituted acrylic acids with oxirane compounds and reacting hydroxy acrylates or hydroxy methacrylates with dimercaptan compounds. . Additionally, any of the above-mentioned compounds can be further reacted with diisocyanates to form hydroxy urethane prepolymers having urethane linkages. Therefore, there is little limitation on the type of polyol used in the present invention and its synthesis.

Additional unique examples of the present invention include the modification of polyol resins to contain a few pendant mercaptan or thiol groups, such mercaptan or thiol groups being complexable with a tin catalyst. Although this is a common procedure, it has proven extremely difficult to limit the reaction, so that the resulting resin product is dominated by hydroxyl groups. Therefore, a reaction equation based on the Damman process can be used. The Damman process involves the synthesis of aliphatic polyol resins containing a small proportion of aromatic hydroxyl or mercapto groups. The basic reactions developed by the Daman process are the formation of glycidyl-functional polyols (e.g. acrylic polyols) in the first step, and the subsequent formation of mercapto compounds containing carboxyl or other functionalities with the glycidyl groups in the second step reaction. Contains the addition of For this,
The various polyol resins mentioned above can be suitably modified by the Damman process to contain a small proportion of mercaptan groups rather than a large proportion as by the synthetic techniques described above. The example describes only one resin with aliphatic (or aromatic) hydroxyl functionality, mercaptan groups, and a tin catalyst in a single molecule. Such examples illustrate the ability to formulate coatings with higher solids contents than those mentioned above.

An additional class of compounds effective in forming inert tin or bismuth catalyst complexes consists of certain classes of polyphenols that have the property of being able to react with isocyanate groups in the presence of a tertiary amine activator. In the absence of a tertiary amine catalyst, polyphenols tend not to react at all with isocyanate groups over long periods of time. Polyphenols form a hexacoordination complex with tin, as shown in catalytic species ① in Figure 1. Polyphenols that can react with isocyanate functionality in the presence of a tertiary amine activator act like mercapto groups in the presence of a tertiary amine activator. Heat also promotes the release of active tin catalyst species. Representative polyphenols that effect the formation of the novel inert tin or bismuth catalyst complexes of the present invention include cascol, pyrogallol, 3-methoxy catechol, and the like. These polyphenols are described in US Pat. No. 4,366,193.

Regarding the proportions of the catalyst system, the proportion of tin or bismuth catalyst is adjusted by the effective catalytic amount for the polyol/polyisocyanate reaction. Generally, active tin/bismuth catalyst concentration levels can range from about 0,0001 to about 1.0% by weight. Generally, the proportion of mercaptan or polyphenol is adjusted in substantial excess over the proportion of tin/bismuth catalyst. At high complexing agent/metal catalyst ratios, favorable stability (pot life) is observed, but the coating does not cure quickly. For a given complexing agent/metal catalyst ratio, higher metal catalyst levels speed up curing, but shorten pot life. The catalyst/complexing agent ratio is significantly influenced by the particular tin or bismuth catalyst, the particular mercaptan or polyphenol, polyol and polyisocyanate selection, and the desired performance requirements. However, generally catalyst/
Complexing agent molar ratios are advantageous for the catalytic reaction mixture of the present invention as described above.

The polysocyanate crosslinker bonds with the hydroxyl groups of the resin or polymer under the influence of a tin catalyst to cure the coating. Aromatic, aliphatic or mixed aromatic/aliphatic isocyanates can be used. Of course, polymerized isocyanates can be used to reduce toxic vapors of isocyanate monomers. Additionally, alcohol-modified and other modified isocyanate compositions can be used in the present invention. Preferred multi-isocyanates have about 2 to 4 isocyanate groups per molecule for use in the coatings of this invention. Suitable multi-isocyanates for use in the present invention include, for example, hexamethylene diisocyanate, 4.4'
-) Luene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethyl polyphenylisocyanate (polymerized MDI or PAPI)
, m- and p-phenylene diisocyanate bitolylene diisocyanate, triphenylmethane triisocyanate, tris-(4-isocyanatophenyl)thiophosphate, cyclohexane diisocyanate (c
HDI), bis-(isocyanatomethyl)cyclohexane (H,
, dicyclohexylmethane diisocyanate and its dimethyl derivatives, trimethylhexamethylene diisocyanate, lysine diisocyanate and its methyl ester, isophorone diisocyanate, methyl cyclohexane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmecune triisocyanate, xylylene diisocyanate and its methyl and hydrogen and mixtures thereof. Aromatic and aliphatic polyisocyanates, dimers, dimers,
Oligomers, polymers (biuret or isocyanurate derivatives) and isocyanate-functional prepolymers are packaged in preformel packages.
es) and such packages are suitable for use in the present invention.

The ratio of isocyanate equivalents of the polyisocyanate crosslinker to hydroxyl groups from the hydroxy resin material is approximately 1:1.
The ratio is preferably higher and can range from about 1:2 to about 2:1.

The proportions or isocyanate index mentioned above are often used if the paint is to be applied accurately.

As mentioned above, the solvent or vehicle can be included as part of the paint. Volatile organic solvents can include ketones and esters to minimize viscosity, although some aromatic solvents may be required, and are generally part of the volatiles contained in industrial isocyanate polymers. Typical volatile organic solvents include, for example, methyl ethyl ketone, acetone, butyl acetate, methyl aluminum ketone, methyl isobutyl ketone, and ethylene glycol monoethyl ether acetate (trade name: cellosolve acetate).
) commercially available as J). Organic solvents that can generally be used for polyisocyanate polymers include 1, for example toluene, xylene, and the like. The effective non-volatile solids content of the coating can be increased by the loading of relatively low volatility or non-volatile C (high boiling point) ester plasticizers which are retained in the majority of the cured film.

Such suitable ester plasticizers include, for example, dibutyl phthalate, di(2-elelhexyl) phthalate (D
OP), etc.

The proportion of ester plasticizer should not be more than about 5-10% by weight and should be
ance ) to avoid losses.

Additionally, the paints may contain opaque pigments and inert fillers, such as titanium dioxide, zinc oxide, clays such as kaolinite clay, silica, talc, carbon or graphite (for example in the case of conductive paints). Additionally, the paint can contain coloring pigments, anti-corrosion pigments and various additives commonly used in paints. Such additives include, for example, surfactants and flow agents.
agent), a leveling agent, a pigment dispersant, and the like. Ingredients useful in formulating paints to produce low acid value systems. Higher acid numbers reduce pot life, slow the cure of the coating, and require additional amines to be used to achieve cure.

Therefore, it is preferable to use a low acid value system.

Another class of additives optionally useful in the coatings of this invention are ketone-based chelating agents.

U.S. Pat. No. 3,635,906 discloses that the catalyst is β
It has been stated that urethane paints can improve their pot life when complexed with -dicarbonyl, α-hydroxy ketones or fused aromatic β-hydroxy ketones.

Additional ketone-based chelating agents useful in the reaction mixture according to the invention include, for example, dialkyl malonates, acetoacetates, alkyl lactates and alkyl pyruvates.

Also, although such chelating agents do not provide the same pot life as is achieved with the use of mercapto compounds or polyphenols in the present invention, the presence of such chelating agents increases the pot life of the system as explained in the examples. have the effect of Additionally, such ketone chelators do not provide inert catalyst species that can be triggered by amines or low temperature heating because ketone-based chelators do not react with isocyanate functionality under standard conditions. Also, such ketone chelators are less effective than mercaptans or phenols in complexing with tin or bismuth, as explained in the examples.

For the performance requirements encountered by the paint, the paint can be formulated to have a minimum pot life of at least 4 hours in an open pot;
Generally, they can be formulated to have a pot life of 8 hours or more, and up to 18 hours or more. Such a long pot life means that there is generally no need to reload the pot in a moving plant. Additionally, the pot life of the paint in a closed container can be longer than one day, although this will affect the formulation of the paint. After storage of the paint, the stored paint can be cut (if desired) to the application viscosity by means of a suitable solvent and retains all the excellent performance characteristics that originally possessed such paint.

The amine activator can be applied in liquid or gas phase and is preferably a tertiary amine, including tertiary amines containing substituents such as alkyl, alkanol, aryl, cycloaliphatic, and mixtures thereof. can be mentioned. Additionally, heterocyclic tertiary amines can be suitably used in the present invention.

Representative tertiary amines include, for example, triethylamine, dimethylethylamine, tetramethylethyldi'amine, trimethylamine, tributylamine, dimethylbenzylamine, dimethylcyclohexylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, pyridine, -phenylpropylpyridine, 2°4.6-collidine, quinoline, tripropylamine, isoquinoline, N-ethylmorpholine, triethylenediamine, etc., and mixtures thereof. Additionally, amine oxides and quaternary ammonium
Amines can be used. A number of proprietary tertiary amine activators are now available and can also effect the process. The amine activator is preferably a tertiary aluminum, preferably present as a vaporous tertiary amine, or the tertiary amine can be present as a liquid and function effectively and efficiently in the present invention. Additionally, primary and tertiary amines activate the tin/mercaptan catalyst complex, although primary and tertiary amines are also undesirable due to their long curing times. In addition, high hindered (h
tertiary amines are available and in some cases preferred.

Such non-tertiary amines that can be used include, for example, diisopropylamine, di-t-butylamine, dibutylamine, t-butylamine, diisopropylamine, 1.1
-dimethylpropylmine, monoethanolamine, jetanolamine, etc., and mixtures thereof.

The proportion of amine activator can be up to 6% or more;
Generally it can be less than 1% by weight, for example about 0.25-1% by volume. The proportion of amine activator can vary depending on whether the amine activator is present in liquid or gaseous state and whether the amine activator is a tertiary, primary or tertiary amine.

-1119, the proportion of liquid amine activator can be varied, but will be more concentrated than the amine activator applied as a vapor. The same is true for primary and secondary amines, which require higher levels due to their reactivity in the system.

For heating activation of the catalyst complex, the applied paint is heated at approximately 50 to 150 degrees.
baking at a temperature of 1°C or higher for about 1 to 30 minutes. Generally, the heating schedule to activate the catalyst complex is less stringent than that required to cure polyol/polyisocyanate coatings in the absence of any catalyst. Of course, even when using an amine activator, heating the coated substrate is advantageous to drive the solvent out of the coating and to allow the coated substrate to be handled quickly without causing the coating to stick. Also, such heating schedules are rather gradual in terms of temperature and time compared to common thermoset urethane systems.

A variety of substrates can be coated with the coatings of the present invention. Examples of substrates include iron, steel, aluminum, copper,
Mention may be made of metals such as galvanized steel and zinc.

Additionally, paints can be applied to wood, fiberboard, RIM (reaction injection molded urethane), SMC (sheet molding compound), vinyl,
Can be applied to acrylic or other polymeric or plastic materials, paper, etc. Since the coating cures at room temperature, there are no limitations on the use of the coating of the present invention with respect to thermal damage to heat sensitive substrates. Furthermore, flexibility in the use of the coatings of the present invention (f
lexibilit) is enhanced. However, heating the paint (eg, in the range of about 50-150°C) is often preferred to enhance solvent ejection. In practice, heating at common curing temperatures can be carried out from time to time.

Finally, the present invention is applicable to primers, intermediate wheels, and top coats with little regard to film thickness.

In practice, the present invention provides a single coating that can act as a primer and as a top coat.
(A unicoat system can be made.

The invention will be explained by way of example, but the invention is not limited thereby. In this case, unless otherwise indicated,
All percentages and proportions are by weight.

The effect of mercaptan structure on the stability of tin/mercaptan complexes was investigated to determine the viscosity (pot life) of flaming polyol/polyisocyanate paints. The paint masterbatch is mixed with TONE305 polyol (polycaprolactone triol, 100% non-volatile solids, OH value 31).
0, Union Carbide Corporation, 364
g), DESMODURN 3.990 Polyisocyanate) (hexamethylene diisocyanate trimer in ethyl acetate solvent at 90% solids, Mobai Chemical
Kompany, 481 g) and methyl amyl ketone (M
AK) solvent (300g). Dibutyltin dilaurate catalyst (trade name: rT-12)
J Catalyst, M&T Chemicals) at 0.2% by weight of tin catalyst (48:1 mercaptan:spot ratio) based on the solids content of the paint formulation. 80 g aliquots of the masterbatch were mixed with various tin/mercapcun complexes and the viscosity was measured at different time intervals (60 rpm
#2 spindle). In other tests, this formulation containing only tin catalyst at the level of tin catalyst used (
(containing no mercaptan) had a pot life of 1 hour or less, generally about 10 to 20 minutes. The results are shown in Table 1.

Table - Viscosity (cps) (hours) Mercaptan O3572255 Non-catalyzed addition 46 48 49 53
63 130 mercapto diethyl ether 4
5 49 53 52 77
G ethanediothyl 47 52 6
3 68 G thiolactic acid 52 127
425 G mercapdobu ■Pionic acid 5
0 94 158 222
G-thiophenol 44 52 54 57
96 G thioacetic acid 70 to GG 2-mercaptoethanol 46 4
8 52 52 63 13G
DP decaacetic acid 51 62 71 78
G*^G- mostly gelled G=nigel The data in the table above shows that a wide variety of mercaptans complex with the tin catalyst.

Carbonyl functionality appears to shorten the pot life of the formulation.

By complexing various tin catalysts with GDP (shown in Example I) and DE
SMOPHEN 800 polyol (polyester polyol, 100% nv solids, OH value 290, Mobai Chemical Company, 55.8g), DESMOD
URN3390 Polyisocyanate (43.2g)
, methyl amyl ketone/butyl acetate solvent (MA
A master formulation of K/BAc-1/2 volume ratio, 20 g) was evaluated.

To each of the two or three lofts of this master formulation were added the following additives as shown in Table 2: Dog-'yu Formulation No. Additive (g) 4497-
848 control DESMOPI (EN 800 (2,6
)4497-84B Control GDP (1,6)449
7-85A 10% dibutyltin acetate (1,76) in GDP 4497-84B
10% dibutyltin oxide (1,76) in GDP viscosity measurements were performed (as described in Example ■) and the results are shown in Table 3 below: Table - Main Time (cps) 4497-84880 87
169 (24:00) 4497-84
8 75 80 154 (24 hours) 4
497-85A 80 98G
4497-85B 70 102
G4497-86B 70 83
These results indicate that various forms of tin catalysts have delayed catalytic activity due to complexation with mercaptans. Formulation No. containing 10% S,'(n) octoate in GDP (1,76 g) manifesting a white precipitate that dissolves and exotherms.

Special mention is made of 4497-86A (not shown in the table above). This formulation thickened slightly, but did not gel. Although I did not attempt to verify this test, I have included it here for completeness.

Each formulation was sprayed onto glass with 0.5% by weight dimethylethanolamine (DMEOLA) catalyst by the steam injection atomization process described in U.S. Pat. Post-cure heat beta for 5 minutes. Control formulations 84A and 8
4B did not stick as a result of the post-cure heat beta. Formulation 85A.

85B and 86B did not stick as a result of the post-cure thermal beta and the amine catalyst activated the tin catalyst.

The basic formulation (polyester polyol and polyisocyanate) gives a soft cured film, so the performance properties (MEK friction, Pencil hardness, etc.) are not important. Among them, it is possible to retard the catalytic activity of the tin catalyst and activate its viscosity required by an amine activator.

- Curing of tin concentration (tin supplied from a tin/mercaptan complex) in polyol/polyisocyanate formulations was investigated for pot life (viscosity) and performance of the cured film (MEK rub). These results are shown in Table 4.

1 knee (Formulation No., (g) NGOloH(SH)=1.1 The viscosity measurement results are shown in the following Table 5 (#2 spindle, 6
0 rpm).

Skin Knee 1 Viscosity (cps) 4497-106 75 82 14
7 9.34497-105B 72
93 G 29.24
497-105A 73 96
G 31.54497-104B
68 88 G 29
．． 44497-104A 63 9!1
1 G 57.1 The data shown in the table above shows that the level of tin catalyst affects pot life, but has little effect at 6 hours. At the tin levels tested, sprayable viscosity was maintained over 6 hours (approximately 1 shift).

Each coating was steam spray cured sprayed onto glass as described in Example 1 using 0.5% by weight DMEOLA catalyst. The performance results are shown in Table 6 below.

The data in the above table shows that the amine activator activates the tin/mercaptan catalyst to effectively cure polyol/polyisocyanate paints. It shows. This data also shows that the hardening of the coating is accelerated to a certain point by the increased level of tin catalyst. This trend is reflected in the changes in viscosity at 6 hours and the MEK rubs at 1 hour with respect to the tin concentration shown in Figures 1 and 2.
).

The 104A sample was sprayed onto glass using only compressed air (no amine) and then heated at 82.2°F for 5 minutes (H'r-1). The coating was tacky.

Another sample of 104A was air sprayed onto glass (no amine), then 121. ．． Heated at 1°C for 5 minutes (HT-2). This coating was not tacky. Performance data for each sample was performed one day after application and heating.

Knee 1 Formulation 104A Air Spray Amine Spray Test 1 (T-I HT-2117-L
H'T-2 This data shows that the tin/mercaptan complex combined with the amine catalyst provides a synergistic effect on the cure of the coating as clearly shown in the 82.2'15 minute data. In fact, although the coating can be heat cured,
The catalyst system of the present invention catalyzed the mixture even further.

■ Curing of tin concentration in coatings containing highly flexible polyester polyols was investigated for dibutyltin dilaurate catalysts.

NGOloH(SH)=1.1/1.0*K-F
LEX 188 100% flexible polyester polyol
nv, OH value 235, Niing Industry
s** See Table 4 in Example ■*** The measurement results for dibutyltin dilaurate weight % viscosity in solids are shown in the following Table 9: Displayed Viscosity (cps) Formulation Initial 4 hours 1108 62
G109B 61 G109
A, 57 G108B53
[IQ8A, 46, G The short pot life is due to the resin properties of the formulations, all of which gelled within 4 hours.

The curing was measured and the results are shown as in Table 6 of Example ①.

The catalyst-free formulation did not cure when heated at 121.1°C for 5 minutes. In the catalyst system of the present invention, 82.2°C
It was cured by heating for 5 minutes. This is clear from the MEK friction at 1 hour shown in FIG.

-M Slowly curing acrylic polyols with and without mercaptans were tested to illustrate the curing of complexes and amines.

A masterbatch formulation was made from the ingredients shown in Table 11 below.

DESMODURN3390 79MA
K
40BAc
Portions of 40 masterbatches were used at different dibutyltin dilaurate catalyst levels shown in Table 12 below: JK-J
8 Controls -- 1 Product rT = 121 Diptyltin Dilaurate (See Example I) T-12/GDP/M8K "See Example ■" All formulations were sprayed under the following conditions.

AIR: Coatings were sprayed with air (amine free) and dried at ambient room temperature.

Vl(::RT: Coating as described in U.S. Pat. No. 4,517,2
No. 22 with DMEOLA catalyst and dried at ambient room temperature (VLC was Ashlan
It is a registered trademark of d0ilCo.

AIR-HTI: Coating with air (no amines)
and beta for 10 minutes at 65.5°C (150°F).

AIR-HT2: Coating with air (does not contain amine)
and beta for 10 minutes at 82.2°C (180'F).

VIC-HTI: Spray the coating on VIC-HT with DMEOLA at 65.5 (150°F).
I betaed it for 10 minutes.

VIC-HT2: Spray the coating onto the VIC-HT with DMEOLA at 82.2 (180' F).
I betaed it for 10 minutes.

VIC-HT3: Coatings were sprayed with DMEOLA as in VIC-RT and heated to 1 at 98.8 (210°F).
Bake for 0 minutes.

In the first set of tests (KI-24), the formulation contained a dilaurate catalyst (rT-12'') and no mercaptan resin. Second set of tests (Ll-L
In 24), the formulation contained the mercaptan complex shown in Table 4 of Example 2. Catalyst level is 0%, 0.02%
, 0.04% and 0.08% (all weight %)
.

The pot life was measured in the same manner as in the MEK rub at time intervals of 5 minutes, 1 hour, 4 hours and 24 hours. The coating was also tested for non-tack and the time was recorded. Control sets (Jl-J8) without tin catalyst, without mercaptan, and without amine were also tested.

Sealing JI AIR-RT >24 -- --
- - -J2 VIC-RT >24
- - - - - -J3 A
IR-HTI->24 - ----J4AI
R-)HT2>24 - - - - -
-J7 VIC-HT >24”
' ----J5 8IR-HT3>24
− − − −− −J8V
IC-HT3>24 − −− −
-- -Shohokugu J Ryomaki KI AIR-RT >4 0.75-1-20
LI AIR-RT > 4 3 -
− −, 2 to 12 VIC-RT > 4
0.75 - - - 25L2 VI
C-RT >4 3” ---20 to 3 AIR
-HTI 24 0', 75-1-35L3AI
l? -HTl>4 3-- -- 6 to 15
VIC-1 (TI<4 0.75 - -
- - 30L6VIC-HTI<4 3
- -- - 30 to 4 8IR-HT
<4 0.75 - 3
25 45L4 AIR-HT2<43 -
- 325 to 7 VIC-HT2 TP
O0,7528,407OL7 VIC-HT25-
10 minutes 3 1 8 8 45 to 5 AI
R-HT3 TFOO,,755185560L5
AIR-HT320 minutes 3 4 7.15 25 to 8
VIC-HT3 TFO0,7510308080
L8VIC-HT3TF0 3 8 30
25 60 Chang Huang Ro J Liang So ni 9 ^IR-RT >4.0.5-T T
30L9 AIR-RT >4 3.5
- - , -20KIOVIC-RT
>4 0.5 - T T
40LIOVIC-RT >4 3.5 -
---,. 30KIIAIR-HTI<4 0.
5-3 20 50LIIAJR-HTI>4
3.5 - - - - 14 to 20
VIC-HTI < 1, 0.5-”2
30 50L14VIC-HTlo, 75 3
．． 5-2 10 45 to 12. AIR-
HT2~IO,5,g t5344!5L12A
IR-1 (15 VIC on T2O, 753, 5-2835
-RT2 TFO0,512207060L15VJ
'C-1(T2 TPO3,5'12! 20
20 45 to 13AIR-, RT3 TPO0,
515406580L13AIR-RT3 TFO3
, 510102650 to 16VIG-1 (T3 TF
OO,525457575L16VIC-RT3T
FO3,530405060Ki7AIR-RT<
40.25--5 30L17 8IR-RT<4
4 - - 2 1 in 40
8VIC-RT < 4 0.25 -
-- 5 35L18VIC-RT<4
4 - - 7 40KI9
8IR-1 (TI TPOO, 254102545
L19 8IR-HTI<4 4 -
- - 45 to 22 VIC-H
TI TFOO, 256122055L22VIC-
HTlo, 5 4 - 5 15
40 to 20 8IR-HT2 TPO0,2
525205570L20 8IR-HT2<4
4 5 55 to 23
VIC-RT2 TPO0,2520325811O
L23VIC-1 (T2TFO4122025502
1AIR-RT3 TFO0,2565901001
3OL21 ＾IR-11T3TFo 4
4 5 4(1BOK24VIC-H,,T3
7FO0,25408085100''TPO means the coating does not stick from the oven (sample was cooled before testing).

*1'T means that the film was sticky.

It can be seen from the above results that the particular formulations selected exhibit low cured compositions and require low tin levels to achieve good performance from the formulations. However, when using the complex, the pot life can be extended and almost the same performance (stick-free test and MEK rub test) is obtained when using the tin catalyst alone and when using the tin/mercaptan complex. dibutyltin dilaurate levels and heating conditions. This performance was expressed as 1 for catalyst concentrations with and without mercaptans under heating conditions.
Time MEK friction and pot life data are shown in Figures 4-6.

Group ■ Advantageous embodiments of the invention include the use of resins containing hydroxyl functionality and mercapto functionality.

The addition of tin catalyst produces a unique slow-acting, autocatalytic resin that can be added to polyisocyanates to prepare unique urethane-forming coatings. The synthesis of this resin is not a normal procedure;
Preferably it is carried out by Damman synthesis. This synthesis forms a glycidyl-functional polyol (eg, an acrylic polyol) in one step and then adds a mercapto compound containing carboxyl or other functionality that reacts with the glycidyl groups of the first step reaction product.

The ingredients shown in Table 15 below were used: 15 Ethyl 3-ethoxypropionate 180 bases
Standing butyl acrylate (3 mol) 384 Glycidyl methacrylate (0.3 mol) 42.6 Hydroxyethyl methacrylate (1 mol) 130 bases - Standing di-t-butyl peroxide 5.4
Ethyl 3-ethoxypropionate 50A
The ingredients were heated to 165°C and 10% by weight of component C and 80% by weight of components C and B were added over a period of 1 hour. This mixture was maintained for 15 minutes and added 5% by weight.
Component C was added. The mixture was maintained for 1 hour and 5% by weight of component C was added. This mixture was maintained for 2 hours to produce the glycidyl-functional acrylicoboriol. The reaction mixture was then cooled to 150°C, component D was added, and the reaction mixture was maintained for 1 hour to produce a resin, which was analyzed and the results are shown in Table 16 below.

Non-volatile content 70.4% by weight OH value
95 Acid value 7.5 Water 0.35% by weight Viscosity
5.7 Stokes Gardner Color 1- Average number of molecules 2860 Average molecular weight
10,000SH16.7wt% No.200 16.7wt% No.-O
H66,6% by weight One control formulation and one inventive formulation were formulated as shown in Table 17 below: M Dish 4497-173A Resin 4497-163
64. IDesmodur N3390
25.8Ml/BAC25.0 Honkuri.

4497-172A Resin 4497-163
64. IDesmodur N339. O25,
8 MAK/BAc 25.01 Ethyl 3
- 10% dibutyltin dilaurate ("T-12") in ethoxypropionate, 0.1% by weight catalyst on non-volatile solids Each formulation was tested for pot life and then described in the examples above. The glass panel was sprayed with DMEOLA catalyst as shown in FIG.

, Dog-'-[8173A-No tin 24172A-Containing tin 27 Tests 173A 172A 1
73A 172A 173A 172ATFH-m--
NY 1 hour liver -6-,--14 MEK 21 24 22. 45B
27 Sword 10.1016. l810.14
18.18 B, 1022.20 pencil HBHH
B) IBH Refer to Table 6 in Example 1 ``'' RT-3 is the case of a panel maintained at room temperature for 72 hours.

The results in the table above show that it is possible to synthesize by blending a polyfunctional resin. The performance of the resin was not optimal in this example, as is the emphasis on curing action. Curing action was confirmed by the ability of a single resin to carry hydroxyl and methcapto functionality that complexed with the tin catalyst.

±■ Acrylic polyol 4431-160 was mixed with hydroxyacrylate (1.5m) and butyl methacrylate (2m).
,0m) and butyl acrylate (1,0m) using di-t-butyl peroxide and ethyl-3-ethoxypropionate solvent.
, acid value 1.87, n, v, solid content 71.7% by weight, water 0
．． 1%, Gardner color 1-, Stoke viscosity 10.1
cps, density 1.042g/cm'' (8,811b/
A white urethane-forming finish with an equivalent weight of 539.4° was compounded by conventional means (e.g., ball mill) from the ingredients shown in Table 19 below: Tang-Irishi Ball Millylboliol 4431-160 15
0.0 DuPont R-960TiO□ Pigment 5
00.0 Butyl acetate 200
．． 0 Leddown Polyol 4431-160 35
0.0 Ethyl 3-ethoxypropionate 50
．． ODesmodur N3390 Polyisocyanate 23.1 Butyl Acetate
A 10.0 uni common tin mercaptide catalyst was tested with the tin/mercaptan complex catalyst of the present invention. A number of mercaptans were used with common tin mercaptide catalysts to provide a detailed explanation of the invention.

4431-175A Dibutyltin dilaurate 1
48:IGDP 9 Butyl acetate 20 4431-175B Dibutyltin dilaurate I
N/A Butyl acetate 29 DP1 Butyl acetate 28 443x-i7so T-125 Tin mercaptide
1.09 N/A Butyl Acetate 29 4431-175E T-131 Tin Mercaptide
1.03 s, s:tGDP
1 Butyl acetate 28 4431-175F T-131 tin mercaptide
1.03 N/A Butyl Acetate 29 All catalyzed paints based on Paint 4431-166 and the catalyst solutions described above were prepared from the ingredients shown in the following Table 21: A component 136.5 Paint 4431-166 B component
33. IEEP/BuAc (1:1 weight)”
7.54431-177B Paint 443
1-166 A component 136.5 Paint 4431-
166 B component 33.1 Catalyst No. 1758 1.5EEP/BuAc
6.04431-177C Paint 4431-166 Eight components 136.5 Paint 44
31-166 Component B 33.1 Catalyst No. 17
5B 1.5EEP/BuAc
6. ．． 04431-181
8 Paint 4431-166 A component 136.5
Paint 4431-166 B component 33.1 Catalyst No., 175C1,5 EEP/BuAc 6
．． 04431-181B Paint 4431-166
A component 136.5 paint 4431-166 B
Component 33.1 Catalyst No. 175D
1.5EEP/BuAc
6.04431-1918 Paint 4431-
166 A component 136.5 Paint 4431-16
6 B component 33.1 Catalyst No. 175B
1.5EEP/BuAc
6.04431-19
1B Paint 4431-166 A component 136
．． 5 Paint 4431-166 B component 33.1
Catalyst No. 175F 1.51 25% F by weight in MEK added to all paints
6 drops of C-430 solution, PC-430 surfactant is a nonionic fluorocarbon surfactant, Minnes
Ota Mining & Manufacturing
Company.

"EEP is ethyl-3-ethoxypropione.

BuAc is butyl acetate.

The pot life of the catalyst-added paints shown in the table above was measured, and the results are shown in Table 22: 4431-17 Full
56 56 56-56 56 59 59 694
431-1778 56 56 59 -
59 59 64 61 Ke1shi4431
-177G 56 Kel 2--Nee 1114
431-181A 61 68121 Kel ---1-4431-181B 67
Kel 3' ------4431-1
91A 56 57 68 112 Gl) ------4431-191B 56
71176 Gel 4---1- ■ #3 spindle (at 30 rpm) 2100 cps (in 45 minutes); gel in 1 hour 330 minutes gel 42 hours and gel in 40 minutes From the above results, Sn/S ■ catalyst addition in the present invention Paint, 4431-177B, retained the superior pot life of paint 4431-177A without added catalyst, while paint 4431-177C, containing only a tin catalyst, had an extremely short pot life. By adding more mercaptan to rT-125J tin mercaptide catalyzed paint, the pot life was increased by about two times (comparison paints 4431-181A and 4431-1
81B). Many mercaptans are sold under the trade name rT-131J.
When added to tin mercaptide catalyzed paint, the pot life was approximately doubled (Comparative Bain) 4431-191
8 and 4431-191B). A long pot life was obtained when very large amounts of mercaptan were added to Paint 4431-191A. Nevertheless, the unique ability of tin mercaptide catalyzed paints to increase their pot life can be seen.

The curing response data for each catalyzed paint was 3.5
0.5 wt% DMEO at 2 kg/cm2 (50 psi)
Air atomization and VIG atomization by LA catalyst, mixing at room temperature for 2 minutes, 82.2 °C (
(180°F) for 5 minutes (see Table 11 in Example 2). These results are shown in Table 23 below.

QC Tang” Shadow Catalyst Added Paint TPO, NY,, NY Suede 1
．． 2 3,3 2,23.3 (in 5 minutes) Sword 3,34. ．． 4 3.3, 5.
4 (in 1 hour) Suode 9.11 14.12 ' 9,9
14.14 (in 24 hours) Softening Softening Softening Softening Softening Softening Softening Softening 0 Catalyzed paint 177B containing a tin/mercaptan complex according to the invention is a catalyzed paint (containing a tin catalyst but not containing a mercaptan) ), but had a long pot life. The presence of mercaptan in Comparative Catalyzed Paints 1-181A and 191A containing tin mercaptide increased pot life over catalyzed Paints 181B and 191B without mercaptan, and the softening response was promoted by the amine activator.

Therefore, the specificity of tin/mercaptan complexes with fast curing response and long pot life due to the presence of amines has been established.

For coatings that were air sprayed and then betaned, it was observed that the deactivated tin complex was released to cure the deposited paint. Heating schedule, i.e. 82.2°
C15 minutes is less stringent than required for the same paint without catalyst addition.

For example, to obtain the degree of cure for a low-beta, air-sprayed paint shown in Table 23, the same uncatalyzed paint was heated at about 250'F for about 20 minutes.
Beta'd it. As a result, it was confirmed that a fast curing response of the tin/mercaptan complex was achieved in the present invention by heat.

The versatility of the tin/mercaptan catalyst complexes of this invention is demonstrated by their suitability for use in conventional two-part urethane coatings for addition to long pot life formulations.

In this example, the IMRON817U coating was evaluated (
IMRON coating is a two-component urethane white automotive refinish finish coat (E, 1.Dupont de Nemeu
rsand Co, ). The formulations were made into 8 molds from the ingredients shown in Table 24 below. The 189S promoter was analyzed over 99!2,4-pentanedione. Solid content (0.39χ)
contained 9.8xtin and 1.9xzinc. 189
All calculated tin and zinc levels in the S promoter are 0.04xtin and 0.007xzinc. For comparison, the tin content of the catalyst solution used in 4574-44A is approximately 0.6 χ tin.

The viscosity of the formulations was measured and the results are shown in Table 25 below: Moat' - Viscosity (cps) Control 38 46 47 53 720
Gel-Tin at 4590 minutes From the results in the table above, improved pot life is achieved with the novel tin/mercapto catalyst complex compared to the tin catalyst additive formulation and the tin/ketone catalyst complex. I understand that. Also,
It can be seen that the affinity is greater for mercaptans than for ketone chelators. This result is significant because it is obtained using common commercially available paints.

0.5% by weight of each of the 5 formulations on glass I) MEOL
Sprayed with A catalyst and heated to 82.2°C (180'F) for 5 minutes. Controls were tested 5 minutes after beta and 120
Inventive formulation 155 while passing MEK double rub
E was tested with 200MEK double rub. In addition, formulations containing only tin catalysts (no mercaptans) are 200M
I had BK double friction. All five coatings passed a 200MBK double rub for 1 hour after Beta.

Inventive formulation 155E has long pot life and cure-on-demand (car-on-demand) not tested after 5 minutes.
) can be seen from the above results.

Additional tests were conducted to obtain the relationship between tin catalyst concentration and tin/mercaptan ratio for two different mercaptans, namely glycol di(3-mercaptopropionate) (GDP) and 2-mercaptoethanol (MCE). went. The basic formulation is TONE0305 polycaprolactone triol (100% n, v, solid content, OH value
310, Llinion Carbide Corp.)
, DESMODURN3390 Isocyanate (
360 parts by weight) and MAK/BAc (1:2 volume ratio)
It was blended from a solvent (231 parts by weight).

Dibutyltin dilaurate catalyst from 0.05% by weight to 0.
10% by weight, and the tin/mercaptan weight ratio was changed to 1:
Changed from 15 to 1:45. 0.0% of each formulation on glass.
Sprayed with 5 wt% DMEOLA catalyst and heated to 82.2 °C (1
80'F) for 5 minutes and tested. These results are shown in Table 26 below: Tang' L Nail I GDP 1:15 0.05
Y 19 232 G
DP 1:15 0.10Y
17 263 GDP
1:45 0.05 N 2
94 GDP 1:45
0.10 is almost 0
185 MCE b15
0.05 N 69 306
MCE 1:15 0.10Y
60 407 MCE
1:45 0.05 N 10
148 MCE 1:45 0
．． 10 Y 10 51 The results in the table above show the difficulty of the present invention in terms of Uni. For C,DP, the 5nZSH ratio should be below 1:45 at the practical level of the tin catalyst tested6 1
At low S n /S H ratios of :15, the tin catalyst level shows no benefit at increases above 0.05 wt%. However, in the case of MCE, the coating was not tack-free from the oven (TPO) at low tin catalyst levels, but was tack-free at high tin levels. all,
GDP was slightly better than MCE in the systems evaluated.

Gelation studies with liquid primary and secondary amines were conducted to illustrate the feasibility of primary and secondary amines. A masterbatch formulation of the ingredients shown in the following table was used.

1/1 Component Amount Axis) A sample of the master patch (17 g) was mixed with 3 g of a 10% by weight amine solution, and the gel time was recorded.

The results are shown in Table 28 below.

Table 28 Type of amine and solvent Gel time (min) Control (without amine) 420) Glue-N-butylamine in B-ene
254 Diethanolamine 32
2 The above results indicate that primary and secondary amines act as activators in the process to release (activate) the stabilized inert tin (or bismuth) catalyst and catalyze the curing of the paint. There is. In addition, the above results are
It has been shown that primary and secondary amines do not work, but preferred tertiary amines do. Other primary and secondary amines of Uni were tested. These amines (
Since the control) gelatinized at night, no measurement results were obtained.

Yumata bismuth/mercaptan catalyst complex with 0.62 g of Co5
cat83 bismuth catalyst (bismuth
yl) bis-neodecanoate catalyst, Co5an (
:chemicalCorp, ), 204 g of GDP and 7.34 g of N-methylpyrrolidone solvent were combined with Joncry 1500 acrylic polyol (236 g>), MAK/BACl agent (1/2 volume ratio) and bismuth/mercaptan. The formulation containing the uncomplexed bismuth catalyst (without mercaptan) had a pot life of less than 10 minutes, whereas in the present invention containing the bismuth/mercaptan catalyst complex The paint had a pot life of 4 hours or more (20 times the pot life).

The coatings of the present invention were divided into lots, air atomized with and without DMEOLA catalyst, and baked at 82.2"C or left at room ambient temperature. MEK frictional resistance measurements were carried out as follows: Shown in Table 29.

The above results demonstrate that bismuth catalysts can be complexed to improve the pot life of polyol/polyisocyanate coatings. The results also indicate that the bismuth/mercaptan catalyst complex is activated with amine catalysts and is also thermally activated.

A variety of phenolic materials were evaluated for their ability to complex with the tin and bismuth catalysts shown in the following table: ``l Valley'' 1 1 ] II Muro City II Go 1m 1 1 Place 1 1 Word II 6 II-' = Tohachi' ( ・kiW, lJ Toma The paint for each catalyst series is made from the ingredients shown in Table 31 below. Prepared.

The 4574-13.1 series was sprayed with DMEOLA catalyst and then betaed for 10 minutes at 82.2°C and tested for pot life and cure response.

4574-46 series with 29.57 mff1 (1 oz) bottle of net or 5 drops of liquid DMEOLA
The pot life was tested using The 4599 series was tested for net pot life in 20 oz bottles. If 8 drops of liquid DMEOLA were added to a double sample, a 2 mil thick coating of the 4599 series was taken and 8
Hake at 2.2° C. for 5 minutes and check the MEK friction, and the results are shown in Table 32 below.

A > 24 (hours) Wet film E
〉 3 (hours) 200 F 15 (minutes) - G 〉 3 (hours) 160 H15 (minutes) - Master I Dangel time (minutes) A 2' 2B
>500 43C73 Catalyst Gel Time MEK Friction 4599 Series (hour)A'
>4 >200B
<1>'20
0C>4 100D
<1 >2
00 order pot life data can be evaluated if the same amount of uncomplexed silver or bismuth catalyst yields a pot life (gel time) of 15 minutes or less. Therefore, adjacent (e.g. α−
Only phenolic materials with 9β-) hydroxyl groups (eg catechol, 3-methoxycatechol and pyrocatechol) could be complexed with tin and bismuth catalysts and the catalysts could be released in the presence of amines or heat. However, certain non-adjacent hydroxy compounds are described in U.S. Pat.
96647 (e.g. 2,3',4-)lyhydroxydiphenyl).

[Brief explanation of drawings]

Figure 1 is a diagram showing the reaction process to explain the formation and action of a catalytic complex by a tin catalyst and a mercapto complexing agent. Figure 3 is a graph showing MEK friction data for one hour versus catalyst concentration for the paint of Example ■, and Figure 4 is a graph showing the MEK friction data for the paint of Example ■.
Graphs showing MEK friction data at 1 hour versus medium concentration, and FIGS. It is a graph showing time data. (IS2m) (DI)h
τ-7 Dispersion residue! %) bπ-3 FT "2 Soot residue amount %) hτ-4

Claims (1)

[Claims] 1. An activated catalyst that is effective for the reaction of hydroxyl compounds and isocyanate compounds and is activated in the presence of an amine activator or heat, comprising: (a) selected from tin catalysts, bismuth catalysts and mixtures thereof; a metal catalyst; and (b) a molar excess of a complexing agent selected from (1) a mercapto compound; (2) a polyphenol having properties capable of reacting with isocyanate groups in the presence of a tertiary amine activator; and (3) mixtures thereof. An activated catalyst consisting of the reaction product of. 2. The tin catalyst is stannous acetate, stannic oxide, stannous octoate, dibutyltin dioctoate, tin mercaptide,
Stannous citrate, stannous oxylate, stannous chloride, stannic chloride, tetra-phenyltin, tetra-butyltin, tri-n-butyltin acetate, di-alkyltin dicarboxylate, dimethyltin dichloride and mixtures thereof, and the bismuth catalyst is selected from bismuth tricarboxylate, bismuth nitrate, bismuth halide,
A catalyst according to claim 1 selected from bismuth sulfide, basic bismuth dicarboxylate and mixtures thereof. 3. The catalyst according to claim 1, which contains an organic solvent. 4. The catalyst according to claim 3, wherein the organic solvent contains a keto chelating agent. 5. The molar ratio of the mercapto group from the mercapto compound or the phenol group from the polyphenol to the metal content of the metal catalyst is in the range of about 2:1 to about 500:1. catalyst. 6. The catalyst according to claim 1, wherein the hydroxyl compound and the complexing agent are the same compound. 7. The mercapto compound is trimethylolpropane tri-(3-mercaptopropionate), pentaerythritol tetra-(3-mercaptopropionate)
, glycol di(3-mercaptopropionate)
, glycol dimercaptoacetate, trimethylolpropane trithioglycolate, mercaptodiethyl ether, ethanedithiol, thiolactic acid, mercaptopropionic acid and its esters, thiophenol, thioacetic acid, 2-mercaptoethanol, 1,4-butanedithiol, 2 , 3-dimercaptopropanol, toluene-3,4-dithiol, α,α′-dimercapto-para-xylene, thiosalicylic acid, mercaptoacetic acid, dodecanedithiol, didodecanedithiol, di-thiophenol, di-para-chlorothio Phenol, dimercaptobenzothiazole, 3,4-dimercaptotoluene, allylmercaptan, benzylmercaptan, 1,6-hexanedithiol, 1-octanethiol, para-thiocresol, 2,3,5,6-tetrafluorothiophenol , cyclohexylmercaptan, methylthioglycolate, various mercaptopyridines, dithioerythritol, 6-ethoxy-2-mercaptobenzothiazole, d-limonene dimercaptan and mixtures thereof.
Catalysts as described in section. 8. The polyphenol is catechol, pyrogallol,
A catalyst according to claim 1 selected from the group consisting of 3-methoxycatechol and mixtures thereof. 9. (a) a polyol; (b) a polyisocyanate; and (c) an activated catalyst consisting of the reaction product of a metal catalyst selected from tin catalysts, bismuth catalysts and mixtures thereof; and (d) (1) a mercapto compound, A catalyzed reaction mixture consisting of (2) a polyphenol having the property of reacting with isocyanate groups in the presence of a tertiary amine activator and (3) a molar excess of a complexing agent selected from the mixture. 10. The reaction mixture of claim 9, wherein said polyol comprises an aliphatic polyol and said polyisocyanate comprises an aliphatic polyisocyanate. 11. The reaction mixture according to claim 9, which contains a volatile organic solvent. 12. The tin catalyst is stannous acetate, stannous oxide, stannous octoate, dibutyltin dioctoate, tin mercaptide, stannous citrate, stannous oxylate, stannous chloride,
stannic chloride, tetra-phenyltin, tetra-butyltin,
selected from tri-n-butyltin acetate, di-alkyltin dicarboxylate, dimethyltin dichloride and mixtures thereof, and said bismuth catalyst is selected from bismuth tricarboxylate, bismuth nitrate, bismuth halide,
A reaction mixture according to claim 9 selected from bismuth sulfide, basic bismuth dicarboxylate and mixtures thereof. 13. The reaction mixture according to claim 9, comprising an amine activator. 14. The reaction mixture of claim 13, wherein said amine activator comprises a tertiary amine. 15. The tertiary amine is a tertiary amine, dimethylethylamine, tetramethylethylenediamine, trimethylamine, tributylamine, dimethylbenzylamine, dimethylcyclohexylamine, dimethylethanolamine, diethylethanolamine, triethanolamine,
Pyridine, 4-phenylpropylpyridine, 2,4,6
- Claim 1 selected from the group consisting of collidine, quinoline, tripropylamine, isoquinoline, N-ethylmorpholine, triethylenediamine and mixtures thereof.
Reaction mixture according to item 4. 16. The reaction mixture of claim 9, wherein the proportion of metal from said metal catalyst ranges from about 0.0001 to 1.0% by weight of said reaction mixture. 17. The molar ratio of mercapto groups from the mercapto compound or phenol groups from the polyphenol to the metal content of the metal catalyst is in the range of about 2:1 to about 500:1. reaction mixture. 18. The mercapto compound can be converted into trimethylolpropane tri-(3-mercaptopropionate), pentaerythritol tetra-(3-mercaptopropionate), glycol di-(3-mercaptopropionate), glycol dimercaptoacetate, Trimethylolpropane trithioglycolate, mercapto diethyl ether, ethanedithiol, thiolactic acid, mercaptopropionic acid and its esters, thiophenol, thioacetic acid, 2-mercaptoethanol, 1,4-butanedithiol, 2,3-dimercaptopropanol , toluene-3,4-dithiol, α,α′-dimercapto-para-xylene, thiosalicylic acid, mercaptoacetic acid, dodecanedithiol, didodecanedithiol, di-thiophenol, di-para-chlorothiophenol, dimercaptobenzothiazole , 3,4-dimercaptotoluene, allylmercaptan, benzylmercaptan, 1,6-hexanedithiol, 1-octanethiol, para-thiocresol, 2,3,5,6-tetrafluorothiophenol, cyclohexylmercaptan, methylthioglyco Claim 9 selected from the group consisting of:
Reaction mixture as described in Section. 19. The reaction mixture of claim 9, wherein the polyphenol is selected from catechol, pyrogallol, 3-methoxycatechol and mixtures thereof. 20, (A) applying a catalyzed reaction mixture as a coating to a substrate, said catalyzed reaction mixture comprising a polyol, a polyisocyanate, and (a) a metal catalyst selected from tin catalysts, bismuth catalysts and mixtures thereof; and (b) ) (1) a mercapto compound; (2) a polyphenol having properties capable of reacting with isocyanate groups in the presence of a tertiary amine activator; and (3) a molar excess of a complexing agent selected from a mixture thereof. an activated catalyst; and (B) exposing the coated film to one or more amine activators or heat to cure the film. 21. Claim 20 in which one or more of the polyols or polyisocyanates are aliphatic.
The method described in section. 22. The method of claim 20, wherein the reaction mixture comprises a volatile organic solvent. 23. The method of claim 20, wherein said amine activator comprises a tertiary amine. 24. Claim 2, wherein the amine is in a vapor state
The method described in item 0. 25. The tertiary amine is a tertiary amine, dimethylethylamine, tetramethylethylenediamine, trimethylamine, tributylamine, dimethylbenzylamine, dimethylcyclohexylamine, dimethylethanolamine, diethylethanolamine, triethanolamine,
Pyridine, 4-phenylpropylpyridine, 2,4,6
24. The method of claim 23, wherein the selected from the group consisting of - collidine, quinoline, tripropylamine, isoquinoline, N-ethylmorpholine, triethylenediamine and mixtures thereof. 26. The tin catalyst is stannous acetate, stannous oxide, stannous octoate, dibutyltin dioctoate, tin mercaptide, stannous citrate, stannous oxylate, stannous chloride,
stannic chloride, tetra-phenyltin, tetra-butyltin,
selected from tri-n-butyltin acetate, di-alkyltin dicarboxylate, dimethyltin dichloride and mixtures thereof, and said bismuth catalyst is selected from bismuth tricarboxylate, bismuth nitrate, bismuth halide,
21. The method of claim 20, selected from bismuth sulfide, basic bismuth dicarboxylate and mixtures thereof. 27. The molar ratio of mercapto groups from the mercapto compound or phenol groups from the polyphenol to the metal content of the metal catalyst is in the range of about 2:1 to about 500:1. the method of. 28. The method of claim 20, wherein the proportion of metal from said metal catalyst ranges from about 0.0001 to 1.0% by weight of said reaction mixture. 29. The method according to claim 20, wherein the polyol and the mercapto compound are the same compound. 30. The method of claim 20, wherein said coating is exposed to an amine activator and then heated to a temperature in the range of about 50-150<0>C. 31. The mercapto compound is converted into trimethylolpropane tri-(3-mercaptopropionate), pentaerythritol tetra-(3-mercaptopropionate)
, glycol di(3-mercaptopropionate)
, glycol dimercaptoacetate, trimethylolpropane trithioglycolate, mercapto diethyl ether, ethanedithiol, thiolactic acid, mercaptopropionic acid and its esters, thiophenol, thioacetic acid, 2-mercaptoethanol, 1,4-butanedithiol, 2 , 3-dimercaptopropanol, toluene-
3,4-dithiol, α,α′-dimercapto-para-
Xylene, thiosalicylic acid, mercaptoacetic acid, dodecanedithiol, didodecanedithiol, di-thiophenol, di-para-chlorothiophenol, dimercaptobenzothiazole, 3,4-dimercaptotoluene, allylmercaptan, benzylmercaptan, 1,6 -hexanedithiol, 1-octanethiol, para-thiocresol, 2,3,5,6-tetrafluorothiophenol, cyclohexylmercaptan, methylthioglycolate, various mercaptopyridines, dithioerythritol, 6-ethoxy-2-mercaptobenzo Claim 2 selected from the group consisting of thiazole, d-limonene dimercaptan and mixtures thereof.
The method described in item 0. 32. The method of claim 20, wherein the polyphenol is selected from the group consisting of catechol, pyrogallol, 3-methoxycatechol and mixtures thereof. 33. The method of claim 24, wherein said vaporized amine is mixed with said atomized catalyzed reaction mixture and then coated as a film on said gas.