TW500781B - Curable coating compositions - Google Patents

Abstract

The invention relates to an ambient temperature curable coating composition comprising a film-forming epoxy resin, a curing agent for the epoxy resin that contains an average of at least two thiol groups per molecule and a catalyst for the curing reaction, wherein the composition contains a fugitive retarder for the curing reaction which inhibits curing of the composition in the bulk but which leaves the curable composition when the composition is applied as a coating on a substrate. Further, the invention relates to the use of these coating compositions, in particular to their use as primer coatings for steel in shipbuilding or structural steel used in buildings, bridges or oil rigs.

Description

500781 Case No. 88119558 Amendment V. Description of the invention (1) The present invention relates to a coating composition that can be cured at ambient temperature. Such compositions usually contain a film-forming resin, a curing agent for the resin, and a catalyst for the curing reaction, optionally combined with a solvent pigment and a filler. The resin and curing agent are often packaged separately 'and mixed temporarily before the coating is applied to the substrate, especially if the coating is to be rapidly cured. The pot life, that is, the time during which the viscosity of the coating increases beyond the sprayable consistency, is generally required to be as long as possible and the time required for the coating to cure on the substrate is as short as possible. The indication of pot life can also be obtained from the time required to double the viscosity of the reaction system or the time at which reaction fever begins within a large number of reactions. Ambient temperature-curing coatings are especially used to coat large structures that are difficult to heat, such as ships, buildings, bridges, industrial plants, and oil production facilities, regardless of whether they are under maintenance during construction. The ambient temperature of the coating can vary from below 0 to more than 25 ° C, depending on the season and location. The coating must have a fairly long pot life, such as more than 1 hour at 25 ° C but cured on the substrate for less than one day, preferably less than 8 hours, and can even walk on it without damage to the coating at 0 ° C. A surrounding temperature curable coating composition according to the present invention contains a film-forming resin, a curing agent of the resin and a curing reaction catalyst, and is characterized in that the composition contains a short-acting retarder of the curing reaction to inhibit a large amount of the composition from curing but when When applied as a coating on a substrate, a curable composition remains. "Film-forming" means that a resin can form a continuous layer when applied to a substrate. The most widely used film-forming resin in some ambient-temperature-curing coatings is epoxy. Based on epoxy resins, for example, published in US-A- 4, 8 35, 24 1 and US-A-4, 051, 195 and McGraw-Hi 1 1 1 9 67 by H. Lee & KK Neville, "Handbook of Epoxy Resins "in Chapters 23 and 24. The epoxy resin is a preferable resin for the coating composition of the present invention. The epoxy resin can generally be any epoxy resin described in the above Le e & Ne v i 1 1 e book.

O: \ 60 \ 60892.ptc Page 6 500781 Case No. 88119558 Month Revision V. Description of the Invention (2) A glycidyl epoxy resin containing glycidyl ether or ester group. The epoxy resin can be, for example, a bis-glycidyl ether, such as bis-A or bis-F diglycidyl ether or a bis-glycidyl glycidyl ether. Such glycidyl ethers derived from bisphenols generally have a functionality of 2 or less, such as 1.5 to 2. The epoxy resin can optionally be a polyglycidyl glycidyl ether such as an epoxy dialdehyde resin, or an aliphatic or cycloaliphatic di- or polyglycidyl ether. Examples of cycloaliphatic glycidyl ethers are bisphenol hydrogenated glycidyl esters, such as 2,2-bis (4-glycidyloxycyclohexyl) propane (hydrogenated bisphenol A diglycidyl ether) or hydrogenated bisphenol condensation shrinkage Glyceryl ethers. Examples of glycidyl group-containing epoxy resins are glycidyl esters of ethylenically unsaturated carboxylic acids such as glyceryl isobutyrate or glycidyl acrylate homopolymers or copolymers, or diglycidyl dimer fatty acids Polyglycidyl esters of S or aromatic polyacids. Epoxidized oils can also be used. Epoxy compounds without added heteroatoms such as diepoxy octane or epoxidized polybutadiene. A preferred curing agent for epoxy resins in the coating composition of the present invention is a compound containing at least a dithiol group per molecule. Examples of polythiol-cured epoxy resin coatings are EP-A-0, 1 2 9, 3 94, GB-A-1, 5 1 3, 7 6 9 and US-A- 3, 5 5 3, 2 8 3 instructions. The polythiol used in the coating composition according to the present invention can contain, for example, an average of at least 2, preferably at least 3, or 6 or 8 or more thiol groups per molecule. Generally, a random curing resin or curing agent should contain more than 2 functional groups per molecule. Polythiols with a functionality of at least 3 are more suitable for most epoxy resins, although dithiols can be used with highly functional epoxy resins such as epoxy novolac and methacrylic acid dehydrated glyceride polymers. Examples of such polythiols are thiol-substituted carboxylic acids such as mercaptoacetic acid or fluorenylpropionic acid and polyols such as trimethylolpropane, pentaerythritol, glycerol, trihydroxymethylethane, ethylene glycol, 1,4-

O: \ 60 \ 60892.ptc Page 7 500781 Case No. 88119558 Amended 5. Description of the invention (3) Butyl glycol, dipentaerythritol, anthocyanin or mannitol esters, such as trimethylolpropane tri ( Mercaptoacetate) or pentaerythritol tetrakis (3-mercaptopropionate) are commercially available. Other examples of polythiols are cyclopentanedithiol, 1,2-ethanedithiol, dipentenedithiol, M ethylcyclohexanethiol, 1,6-hexanedithiol, bis (thioglycol) Sulfurated, 1,8-diwei 1,3,5-trioxo-2, 4 1,4-dithiol. Hexane and dithiol, such as weyl alcohol and polyglycerol, undergo long-term contact with salt. For some applications, salt epoxide is used in the range of 1: 1 to 2: 1. It is expected that polythiol can be used to partially blend the surroundings. The coating life is generally slow and the epoxy resin is dry for a long time. The coating composition contains a solid catalyst mono-tertiary amine, an alkylamine such as 2,4-bismethyl) phenol, and N, N-J such as difluorenyl. Coca amine epoxy resin weight catalyst. They can be used with 3--3-dioxo-octane, 1,2,3-propane-trithiol, 6,6-trithiol, dimethylthiodiazole or aromatic thiols such as polymerized polysulfides Alcohols can be prepared by, for example, 1,2,4-trivinyl ring reactions. Polyurethanes based on urethanes can be derived from reactions of example isocyanates. The coating may be water or acid water, for example, on a hull having a cathodic anticorrosive effect, it is preferable that it does not contain a saponifiable carboxylic acid ester group. The ratio of bases in the coating composition is generally in the range of 1: 5 to 5: 1, preferably in the range of, and most preferably in the range of 0.8: 1 to 1.2: 1. In some cases deer. Alternatively, the thiol-functional substance (etc.) may be mixed with other types of once-cured epoxide agents, so long as the influence of time is not otherwise damaged. The curing reaction between thiols does not have a catalyst at ambient temperature, especially if the ambient temperature is lower than 20 ° C, so the catalyst of the chemical reaction of the present invention. The epoxy thiol curing reaction is preferably most preferably an amine containing at least one aromatic ring per molecule, such as monoaryl (dimethylaminomethyl) phenol, 2, 4, 6-tris (diamidodimethylformamide T) An amine, or pyridine, although an aliphatic amine or diazobicyclooctane (triethylenediamine) can be used. The catalyst generally has a base of 0.1 to 10%. A secondary or even primary amine is the ring of choice The oxyresin reaction is then incorporated into the cross-link circuit.

O: \ 60 \ 60892.ptc Page 8 500781 Case No. 88119558 Month, Revision V. Description of Invention (4) This type of catalyst can be used at a higher level as long as it does not interfere with the pot life and drying time. Examples of other catalysts that can be used are other Lewis salt catalysts or Lewis acid catalysts or organic metal compounds or organotin and other metal salts. The short-acting blocker is preferably a volatile compound, usually a volatile liquid organic compound. When the composition is applied as a coating on a substrate, it evaporates to leave a curable composition. Volatile compounds have a vapor pressure of at least 1 m m H g at 25 ° C, preferably solvents for film-forming resins, curing agents and / or catalysts. Short-acting blockers can optionally be a compound that is applied to the substrate of the composition by means other than evaporation to achieve effects on the curable composition, such as adhesion to the substrate or some other component of the coating or separation by phase. A volatile solvent suitable as a short-acting blocker may generally be any volatile solvent that is not a Η-bond donor. For example, a volatile compound suitable as a retarder for a catalytic epoxy polythiol coating composition is a volatile hydrocarbon, especially if it has no real quality volatile alcohol solvents or other polar solvents such as primary or secondary amines- Bond donors (usually compounds containing active hydrogen, that is, elements containing rhenium attached to carbon) have solute hydrogen bond acidity, and ΣαΗ2 is greater than 0.1 as described by M.Η. Abraham in Chemical Society Reviews 1993, pp. 73-83 . The hydrocarbon is preferably an aromatic hydrocarbon such as xylene, ethylbenzene or trioxane, although aliphatic hydrocarbons such as heptane, isooctane and petroleum solvents can be used. Aromatics have the advantage of being a better solvent for epoxy resins and curing agents. Mixing with such solvents is also possible. Other short-acting blockers are Η-bond acceptors, volatile solvents, with a dissolving agent hydrogen bonding salinity Σ10,000Η2 greater than 0.2 and a solute hydrogen bonding acidity less than 0.1. See the introduction of Abraham, such as ether, Esters, ketones, or N, N-dithiotetraamine. Examples of short-acting blockers may be a volatile compound containing at least one ether and / or ester group such as butyl acetate, dibutyl ether, diethyl ether, ethoxypropyl acetate or

O: \ 60 \ 60892.ptc Page 9 500781 _ Case No. 88119558_ Year Month ___ V. Description of the invention (5) Butoxy ethyl acetate, or a cyclic ether such as dioxane, as long as its ether or ester does not contain Free alcohol group or another hydrazone-bond donor. Examples of short-acting blockers are monoketones such as methyl ethyl fluorenone (2-butanone), methyl isobutyl fluorenone or methyl isoamyl ketone. Short-acting blockers may also be, for example, alkyl carbonates such as diethyl carbonate or propylene carbonate. Short-acting blockers can be another volatile N, N-dioxetamine, such as N, N-dimethytamine or N, N-methytamide, but containing rhenium attached to nitrogen Amidine is a hydrazone-bond donor that reduces rather than extends its pot life. The short-acting retarder may be a mixture of different types of short-acting retarders. Examples are aromatic hydrocarbons such as xylene and an ether, ester or ketone solvent such as butyl acetate, methoxypropyl acetate or methyl isobutyl ketone. Nitroalkane or volatile siloxane can also be used if it shows initial miscibility with the curable composition. Although epoxy resin coatings are commonly used in solvent blends containing aromatic hydrocarbons such as xylene, hydrocarbons are not commonly used as the only volatile organic solvents. Often used as a solvent blend with an alcohol such as n-butanol or isobutanol or an ether alcohol such as butoxyethanol. Such blends generally contain xylene and alcohol in volume ratios ranging from 1: 1 to 3: 1. The coating composition of the present invention containing a hydrocarbon such as dibenzobenzene as a short-acting retarder is generally not more than 20% by volume based on the total solvent base of any fluorene-bond donor such as alcohol or amidine volatile organic compound. Although the coating composition containing a europium-bond acceptor such as an ether, an ester or a ketone of the present invention can contain up to 30% or 40% by volume of a volatile organic europium-bond donor, it preferably contains less than 10% europium- The key donor is preferably absent. In the case of tertiary amine catalyst-containing epoxy polythiol coatings, a typical solvent blend of xylene and n-butanol in a volume ratio of 3: 1 can be used at a temperature of 0 ° C and 25 ° C for 8 hours. Internal curing, but an unacceptably short shelf life of less than half an hour at 25 ° C. If butanol is removed, the composition can be quickly cured at both 0 ° C and 25 ° C, and the shelf life is at least 1 hour at 25 ° C.

O: \ 60 \ 60892.ptc Page 10 500781 ___Case No. 88119558_Year Month Amendment V. Description of the Invention (6) It is intended to be used for manual mixing and 2—packaging coating applied by traditional spray equipment. Generally, the viscosity of the coating composition for spray coating should be in the range of 0.5 to 10 poises, preferably less than 6 poises. If all solvents are removed, the pot life will become unacceptable. In other words, the solvent-free composition based on liquid epoxy resin, liquid polythiol, and catalyst will gel at 25 ° C in less than half an hour. Into pieces. It is also possible to use a solvent containing both the H-bond acceptor and the H-bond donor digroup, but only as a blend with other Η-bond acceptor solvents. Because the properties of the η-bond donor are generally better than the Η-bond acceptor . It is also possible to use tautomeric solvents such as ethyl acetoacetate, as the enol form of this is generally not a significant tautomer. It was found that the solvents or solvent mixtures can be used as short-acting blockers in accordance with the formula: 2 9. 3 7Γ-2 72. 2 a + 77. 9 β > 0 In the formula: 7Γ series solvent 7Γ% dipolarity -Polarizable parameters such as those described by Abraham in Chemical Society Reviews 1993 on pages 73 to 83. The 7Γ of the solvent mixture is equal to the sum of the 7Γ values of the individual solvents contained in the mixture, weighted by their equal volume fractions. The solvent π value not included in Abraham's text can be estimated by comparing similar solvents listed in the text. α is the parameter of solvent hydrogen bond acidity ΣαΣ2 * Μ · Η · Abraham in

Chemical Society Reviews 1993, pages 73-83. The α of the solvent mixture is equal to the sum of the α values of the individual solvents contained in the mixture weighted by their volume fractions. Solvents not present in Abraham's text; values can be estimated by comparing similar solvents listed in the text. The parameter Σ ^ Η2 of the hydrogen bonding degree of the solvent is as described by M.H. Abraham in Chemical Society Reviews 1993, pages 73 to 83. Dissolve

O: \ 60 \ 60892.ptc Page 11 500781 _ Case No. 88119558 V. Description of the invention (7) Year Month The modifier mixture / 3 is equal to the sum of the individual solvents contained in the mixture weighted by their volume fractions. Solvent call values that are not present in Abraham's text can be estimated by comparing similar solvents listed in the text. As long as the short-acting blocker can extend the pot life, it can generally use 5-50% of the weight of the coating composition. For example, for a catalytic epoxy polythiol coating, a volatile hydrocarbon such as xylene used as a retarder is preferably 10 to 40% by weight of the coating composition, preferably 15-25%, a volatile ester, ester or Ketones should be used in similar amounts. The short-acting blocker can optionally be a short-acting volatile acid that can form an amine salt with a tertiary amine catalyst, for example. The acid is preferably a carboxylic acid such as acetic acid. The molar ratio of the acid to the amine catalyst is 0.1: 1 to 10: 1, preferably 1: 1 to 6: 1.

However, it has been found that not all solvents meeting the above formula are used as short-acting retarders. For example, due to their function as catalysts, the presence of these compounds accelerates the reaction. As pointed out above, amines can be used as catalysts for the reaction between epoxy resins and curing agents with an average of at least 2 thiol groups per molecule. Therefore, these compounds are not considered short-acting blockers. Examples of compounds that meet the above formula but are not considered short-acting blockers due to their accelerated curing reactions are exemplified by piperidine, N-tepipidine, N-tepipyrrole, pyrazine, 2-methylpyrazine And pyrimidine.

In principle, any short-acting retarder can be used in a coating composition which can be cured at ambient temperature according to the invention. However, it was found that various problems were encountered when the short-acting blocker contained only toluene. It was found that toluene in these compositions was not a suitable solvent for the most desirable form of epoxy resin and was too volatile. The toluene flash point requires special equipment to handle these coating compositions in a safe manner. These defects are generally not manifested in a solvent mixture containing toluene as one component and a sufficient amount of one or more other components. The coating composition of the present invention can be exemplified as a shipbuilding or building, a bridge or an oil.

O: \ 60 \ 60892.ptc Page 12 500781 Case No. 88119558 Month Revision V. Description of the invention (8) Anticorrosive primer coating composition coated with structural steel for derrick. The film-forming resin and the curing agent are usually stored separately, and applied to the substrate together as a coating shortly after mixing. The catalyst should also be stored separately from the resin. For example, the epoxy resin component and the polythiol component can be applied after mixing in a container for 1 or 2 hours. The extended pot life granted by short-acting blockers is a particular advantage of this system. The resin and curing agent can be alternately mixed and applied in a double-feed sprayer; the coating of the present invention has the advantage that the same coating can be mixed and applied using any procedure. The coating composition of the present invention is particularly suitable for curing at ambient temperature, such as below 40 ° C, especially below 25 ° C, including cold climates, where the ambient temperature is below 10 t or even below 0 ° C up to -5 ° C or -1 0 ° C. The coating hardens quickly at 10 ° C. Normally at 0 ° C, a 200 μm coating film can be trampled for 24 hours, and it will not dig through the film 8 hours after ordinary coating. The composition of the present invention cures and hardens faster than epoxy resin compositions based on conventional primary amine curing agents. The coating of the present invention may contain an anticorrosive pigment such as metallic zinc, zinc phosphate, wollastonite or a complex molybdate or phosphonate, a barrier pigment such as mica iron flakes, glass flakes, aluminum flakes or mica and / or a Filler pigments such as iron oxide, barite, talc calcium carbonate or titanium dioxide. The coating may also contain other coating additives such as wetting agents, thixotropic gums, reactive diluents such as monoepoxides or a flow control agent. Pigments and other additives can often be mixed and stored with epoxy resins or with curing agents or with both. Other additives that may be included include diluents and tougheners, so long as the properties of these materials do not impair the pot life and drying properties of the composition. The invention can be illustrated with reference to the following examples. These examples are intended to illustrate the invention but are not intended to be interpreted to limit its scope in any way. Example 1

O: \ 60 \ 60892.ptc Page 13 500781 Case No. 88119558 Rev. V. Description of the invention (9) Epoxide equivalent based on a mixture of bisphenol A and bisphenol F (EPikote 232, from Shell Chemicals) The liquid epoxy resin of 176 was mixed with 2,4,6-tris (dimethylamine methyl) phenol (Ancamine K54, from Air Products) catalyst and xylene in the amounts shown in Table 1. This composition is mixed with pentaerythritol tetrakis (3-Weiylpropionate) (CAS 757-23-7 from Dow Chemicals) and xylene to obtain an epoxy-p-thiol group in a ratio of 1: 1; within each component The amount of xylene is 20% by weight. Dihydroxybenzene does not contain hydroxyl groups or other hydrazone-bonds to body solvents. The obtained uncolored coating composition samples were stored in paint cans at different temperatures, and the viscosity was measured multiple times with a flat-bottomed cone viscometer. Viscosity is measured at 25 ° C. The time it takes for a coating composition to double in viscosity is taken as a pot life assessment, although in most cases the uncolored composition still has a sufficiently low viscosity for spray applications even after the viscosity is doubled. Uncolored coating composition samples were applied to a 200 / zm wet thickness steel substrate and allowed to dry at different temperatures. Record the time when the coating dries and cures to a hard surface that does not stick to the touch ("touch dry"), as the coating cures until the entire thickness of the coating is hard ("hard dry"). The obtained results are shown in the following Table 1: Table 1 The amount of catalyst film T (° C) when the coating is applied in the pot life is 2 times the initial viscosity and touches dry_ hard dry (¾% by weight of oxygen resin) (poise) time time Time 2.0 0 0.645 2 hours 30 minutes 2 hours 20 minutes 3 hours 15 minutes 1.14 15 0.625 1 hour 44 minutes 1 hour 25 minutes 1 hour 55 minutes 1.7 25 0.643 (55 minutes 1 hour 35 minutes 1 hour 45 minutes as shown in Figure 1 It is shown that the coating composition of Example 1 has a temperature of about 1 hour even at 25 ° C.

O: \ 60 \ 60892.ptc Page 14 Case No. 8811Q55S V. Description of the invention (10) Revision $ The sufficient period of application with spray coating, even if it is dried and cured to a hard coating layer within 4 hours during the process. Therefore, it can be used at any temperature within the range of 0 to 25 t for curing at ambient temperature without the need for special coating equipment. _ For comparison, a mixture of xylene and butanol in a 3: 1 weight ratio was used to replace the coating composition of toluene at 25. (: It only takes 21 minutes to double the viscosity after storage ', and the coating composition using a mixture of xylene and butanol of 1 ·· 1 will only need 37 minutes to gel at 25 ° C. The xylene is simply omitted The coating compound is doubled in viscosity at 25 ° C in just 2 2 minutes. An epoxy resin paint is prepared from the following components: Sulfur A epoxy resin (Araldite GY250, 24.17kg Jp ex · Ciba Chemicals) 2 Benzene 10.42kg pigment (talc, heavy-crystal and iron oxide) 48.94kg thixotropic gum 0.55kg tris (dimethylaminofluorenyl) phenol 0. 24kg pentaerythritol tetrakis (3-fluorenylpropionic acid il) 15.52kg ( CAS no · 757-23-7, ex. Dow Chemicals) The paint thus produced has a viscosity of 3.5 poise at 23 ° C, a dry film of PVC 30%, and a solvent content volume ratio of 20%. A 20 liter test of this paint The samples are stored at 2 3 ° C, and can still be sprayed after 1 hour. Part of the mixture is sprayed on 1 2Π X 6 π (3 0. 4 8 cm X 15.24cm) steel sheet, and allowed to cure at 0 C. One 150 // m dry thickness film 7 After 7 hours and 10 minutes, the film can walk without cracking. For comparison, the epoxy resin paint according to this example (to reduce the amount of dimethylbenzyl and contain a little butanol) When the agent) with one diprimary amine as curing agent when the inner vessel surface coating weeks

O: \ 60 \ 60892.ptc Page 15 500781 __ 皇 号 88119558_ year month day — five, description of the invention (11) keep the temperature at 0 ° C is not dry and solidified enough to walk on it without digging holes . ', Example 3-An epoxy phenolic resin having an average of 3.6 epoxy groups per molecule (D0w

Chemicals (DEN 438) and 1.8% by weight of 2, 4, 6 to tris (dimethylamine methyl) based (Ancamine K54 by Air Products) mixed with di-benzene and then mixed with ethyl cyclohexanedithiol The curing agent is made into a coating composition containing 20% by weight of xylene. This coating composition has a pot life (viscosity doubling time) of 1 hour and 23 minutes at 25 ° C. This coating cures to a hard coating at 0 ° C. Example 4 Example 1 was repeated using the only bisphenol A-based epoxy resin with a cyclic epoxy equivalent of 190 sold by Ciba Chemicals under the trademark Araldite GY250. The test conditions are the same as those described in Example 1. The obtained results are shown in Table 2 below. Table 2 Application period S coating film catalyst amount T (° C) Initial viscosity doubled Viscosity touch dry hard (weight% of epoxy resin) (Poise ) Time Time Time 1.0 0 0.713 2 hours 40 minutes 4 hours 30 minutes 5 hours 15 1.0 15 0.803 1 / J, hours 37 minutes 1 hour 30 minutes 2 hours 1.0 25 0.738 1 < hours 31 minutes 1 hour 1 hour as shown in Table 2 As shown, the coating composition of Example 4 has a sufficient pot life at 25 ° C, and it hardens into a hard coating layer at less than 6 hours even at 0 ° C. Examples 5 to 1 4

O: \ 60 \ 60892.ptc Page 16 500781 ---____ Case No. 88119558 _ Year 5. Description of the invention (12) 1 ^ .00 g Araldite GY 250 epoxy resin produced by Ciba Chemicals and 6.42 g pentaerythritol (3 -Mercaptopropionate) (Dow Chemicals outlet CAS 757-23-No. 7) '〇 · ΐ 7 g 2,4,6-tris (dimethylamine methyl) anion (Ancamine K54 by Air Products) and 4.24 g The solvents shown in Table 3 below are mixed. Examples A to G use volatile solvent-based H-bond donors which are not effective short-acting blockers of the present invention. Xylene was used in Example 5 and H- ^ acceptor was used in Examples 6 to 5. The acceptor was a short-acting blocker suitable for the present invention. Example 12 demonstrates the effect of mixing a η-bond to give a solvent to a Η-bond acceptor. Example 丨 3 represents a tautomeric solvent, showing that ketones and ester groups attached to the same fluorenyl group are not as good as long-distance groups, etc.

effective. Example 14 shows the Η-bond acceptor effect with acidic characteristics. The result is a weak acceleration of the response. Resin for each example. The curing agent, catalyst and volatile solvent mixtures were stored in batches, and the time to start exotherm was measured.

O: \ 60 \ 60892.ptc P.17 500781 Case No. 88Π9558 _Ά Revision V. Description of the invention (13) Table 3 Example of the time when the solvent starts to generate heat (minutes) π a β Z1 A amine 1 1.30 0.62 0.60 -83.9j B methanol 2 0.44 0.43 0.47 -67.5 C ethanol 7 0.42 0.37 0.48. ^ -51.0 D butanol ethylhexanol 8 0.42 0.37 0.48 -51.0 E 13 0.392 0.372 0.482 -51.9 F f 26 0.582 0.402 0.802 -29.6 G 2- Methoxypropanol 38 0.49 0.15 0.02 -24.9 5 chloroform 67 0.52 0.00 0.16 27.7 6 xylene 92 0.25 0.00 0.45 42.4 7 dioxan 110 0.65 0.00 0.51 58.8 8 methyl isobutyl fluorenone 113 0.60 0.00 0.45 52.6 9 acetic acid Butanol 133 0.70 0.00 0.51 60.2 10 2-Butanone 136 0.75 0.00 0.64 71.8 11 158 1.31 0.00 0.74 96.0 12 13 1,4-dioxane N, N-dimethomethylamine methyl isobutyl fluorenone: 73 78 * 0.59 0.09 0.50 31.3j 14 Butanone (3: 1) Acetyl t-butyrate Schottyl ethane 60 0.95 / f 0.02 0.33 48.1 1) Z = 29.3 7Γ-272.2 α + 77.9 ^ 2) Estimated value The time to start exotherm is related to the pot life. The solvents of Examples 6 to 13 can be used in place of xylene as the short-acting blocker in the compositions of Examples 1 to 6, and can give at least the same pot life. The coatings containing the short-acting retarders of Examples 6 to 13 had a hard drying time similar to that of equivalent coatings containing an equivalent amount of xylene. As a control, a solvent-free composition had an exothermic onset period of 18 minutes. Example 1 5 Add 173 g of M-based ethanol in 445 ml of butyl acetate

O: \ 60 \ 60892.ptc P.18 500781 Case No. 88119558 Month, Revision V. Description of the invention (14) De s m d du r N 3 3 0 0 Polyisocyanate is used to synthesize a polythiol crosslinker. The mixture was heated to 70 ° C in the presence of an acid catalyst. Isocyanate group consumption stopped in 2 hours. The product has a thiol equivalent of 2 9 8. This material is used as a 62% by weight solution in butyl acetate. Mix 3.38 g of polythiol solution with 1.74 g of liquid bisphenol A epoxy equivalent 190 (Araldite GY250 by Ciba Chemicals) and 30 mg of 2,4,6_tris (diamidomethyl) yl group ( Ancamine K54 by Air Products). After coating, a 150 μm dry film was obtained within 90 minutes at 25 ° C. Mix 15 g polythiol solution with 14 · 2 g of the same liquid epoxy resin, 5 g of xylene and 0 · 28 g of 2,4,6-tris (dimethylaminomethyl) phenol (Anc by Air Products) a mine K54). No peak exotherm was observed even after 25 hours at 25 ° C, which is a good indication of the pot life of this composition. Example 1 6 10 g equivalent of 190 liquid bisphenol A epoxy resin (Araldite GY25 0 produced by Ciba Chemicals) and 2.29 g of ethylcyclohexyl dithiol, 3.47 g of pentaerythritol tetramercaptopropionate and 0.17 g of 2, 4 , 6-Tris (dimethylamine methyl) phenol (Anc amine K54 by Air Products). Dioxin equivalent to 20% by weight of each component was also added. This mixture produced an exothermic onset time of 115 minutes and a spike exotherm of 123 minutes. Example 1 7 27.15 g equivalent of 190 liquid bisphenol A epoxy resin (Araldite GY250 by Ciba Chemicals) and 16.97 g of pentaerythritol tetraweilyl propionate, 0.49 g of m-diphenylenediamine and 0.46 g of 2 , 4, 6-Tris (diamidomethyl) phenol (Ancamine K54 by Air Products) in a solvent-free formulation

O: \ 60 \ 60892.ptc Page 19 500781 Case No. 88119558 ¥ _Ά Revision V. Description of the invention (15). Touch dry within 45 minutes when applied as a 150 / zm film at 23 ° C. The formula is the same, but half the thiol equivalent is replaced by m-xylylenediamine with the same number of N-fluorene analogues to make a solution of 80% solids in methyl isobutyl fluorenone at 25 ° C to obtain an initial exothermic time of 8 8 minutes. ❿

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Claims (1)

500781 Notice No. 88119558 1, ▼ !! Patent Liwei Correction 1. One of the alcohol groups of Shuyuezhi is coated by A 2. The touch 3. The tertiary 4. The compound is steamed 5. The short 6. The short 7. The short 8. The short 9. The short One week, one person and solid short-acting resistance layering when benzene alone is applied according to the application system, one is based on amine application, and the solvent is concurrent while the remaining is based on application efficiency blocking, based on application efficiency blocking, based on application efficiency blocking, and based on application efficiency blocking. An epoxy coating composition for chemical reaction of solid epoxy resin, including a film-forming epoxy curing agent which contains at least an average disulfide catalyst per molecule, characterized in that the composition contains a curing reaction batch composition which is cured but when the composition is in The composition on the substrate, provided that the short-acting blocker, non-blocking agent, inhibits the composition, leaving a large amount of solids. A curable coating composition according to item 1 of the patent, wherein tertiary amine. The patent scope contains at least one patent scope. The short-acting retardation non-Η-bond gives a curing range of hydrocarbons. The special agent is available. The special agent is required. The special agent is included. The special agent is included. The curable coating composition of the item, wherein the aromatic ring. The curable coating composition according to any one of items 1 to 3 is a volatilization of a film-forming resin and / or a curing agent, and the composition is applied when the composition is applied as a layer on a substrate. The curable coating composition according to item 4, wherein the curable coating composition according to item 5 is an aromatic hydrocarbon. The curable coating composition according to item 4 of the invention, wherein one is a Η-bond acceptor. The curable coating composition according to claim 7, wherein at least one ether and / or ester group. The curable coating composition according to item 7 is a ketone. O: \ 60 \ 60892.ptc page 22 500781 _ case number 88119558_ year month date_ί ± ^ _ VI. Patent application scope _ 1 0. Curable coating composition according to item 7 of the patent application scope, where the The short-acting blocker is mono-N, N-dioxetamine. 1 1. The curable coating composition according to any one of claims 1 to 3 and 5 to 10 in the scope of the patent application, wherein the solvent meets the formula 2 9. 3 7Γ-2 7 2. 2 α + 77. 9 cold > 0, where: • The dipolar-polarizable parameters of 7Γ-based solvents 7Γ Η2 are such as M. Η. Abraham in Chemical Society Reviews 1993 pages 73-83 stated that the ττ of the solvent mixture is equal to the individual solvents contained in the mixture The sum of the 7Γ values weighted by their equal volume fractions, 〇: is the parameter of the solvent hydrogen bond acidity 161: 112 as described in .11. 8 1 ^ 3118111 on Chemical Society Reviews 1993 pages 73-83, α of the solvent 0 mixture It is equal to the sum of the alpha values of the individual solvents contained in the mixture, weighted by their volume fractions, and the parameter Σ / 3/3 of the hydrogen bonding salinity of the cold solvent, such as 1 H. Abraham, Chemical Society Reviews 1993, pages 73-83. / 9 is equal to the sum of the / 3 values of the individual solvents contained in the mixture weighted by their volume fraction *. The calling values of solvents not shown in Abraham's text can be estimated by comparing them with similar solvents listed in the text. 12. The curable coating composition according to any one of claims 1 to 3 and 5 to 10, wherein the content of the short-acting retarder is 15-25% by weight of the coating composition. 13. The curable coating composition according to any one of claims 1 to 3 and 5 to 10 of the scope of patent application, which is used as a steel anticorrosive coating. 1 4 · A curable coating composition according to item 13 of the scope of patent application, which O: \ 60 \ 60892.ptc Page 23 500781 Case No. 88119558 Revised O: \ 60 \ 60892.ptc Page 24