TW448197B - A process to make a curable composition, a curable composition, a process to cure the composition, and a catalyst and/or curing agent product for epoxy resins - Google Patents

Abstract

A composition which contains: (1) the nucleophilic addition adduct of an imidazole and an unsaturated compound, which contains more than one imidazole moiety per molecule; and (2) an epoxy resin, is characterized in that fewer than 50 equivalent percent of the imidazole moieties in the adduct are neutralized with acid. The adduct may serve as a curing catalyst in high or low-temperature curing. The composition is made and applied as a powder coating for coatings or as a matrix resin in laminates. It may be used in solvent-borne or liquid systems.

Description

448197 Printed Poly A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the Invention (1) <Invention> The present invention relates to the technology of curing catalysts for epoxy resins, especially catalysts for powder compositions. It is known to coat a substrate by applying a powder containing an epoxy resin, a curing catalyst, and a selective curing agent to a substrate. Generally, the substrate is heated and the powder is coated while it is still hot, or the powder is applied to a cold substrate and the substrate is then heated. In either case, heating causes the powder to melt and flow, while the substrate is coated and then solidified. An example of a suitable method is described in Kaufman, US Patent No. 4,358,571 (November 9, 1982), column 5, lines 5 to 49; Lee &amp; Neville's Epoxy Handbook, pages 20-15 to 20-20 (McGraw-Hill Book Co. 1967); and Tess, "Epoxy Coatings," Epoxy (2nd Edition), pp. 772-778 (Marcel Dekker Inc. 1988). For example, the coating is applied to a metal substrate by electrostatic spraying or fluidized bed, which is generally heated to 140 ° C to 240eC. Many curing catalysts are known for curing epoxy powder coatings and solvent-supported coating systems. Examples of suitable catalysts include tertiary amines and quaternary ammonium, and tertiary phosphines and quaternary scales. Known potential catalysts contain a salt containing an ammonium or phosphonium moiety and a conjugate based on a weakly nucleophilic base, such as terephthalic acid or fluoboric acid. Examples of suitable catalysts and potential catalysts include lower bases ( CrC6) -triphenyl-scaly halide and described in US Patent No. 5,202,407 (January 24, 1992) by Pham et al .; US Patent No. 4,725,652 (March 4, 1987) in Bertram et al .; Bertram EPO Patent Bulletin No. 0 328 020 A3 (August 16, 1989); US Patent No. 5,140,079 to Muskopf et al. (August 18, 1992); US paper specifications for Gan et al. Apply China National Standard (CNS) A4 Specification (210X2S &gt; 7mm) ..II .1 ^ — ^ 1--1 —0--m ^ i ^ ϋ— · (Please read the precautions on the back before filling this page ) -4-A7 B7 ^ 4819 V. Description of the invention (2) n I- II-II ^^^ 1 I --1 I -z, I----· ϊ · I (Please read the Vi on the back first (Please fill in this page again for the matters needing attention). US Patent No. 5,308,895 (May 3, 1994); US Patent No. 5,169,473 to Bertram et al. (November 8, 1992); The catalyst described in No. 4,358,571 (November 9, 1982) teaches by reacting imidazole or substituted imidazole with an acrylate, a cyclofluorene resin or an isocyanate, and then neutralizing the imidazole with a fatty acid or a dicarboxylic acid. Preparation of adduct. These adducts are used as curing agents for epoxy resins at 132 ° C (270 ° F).

Burba et al. U.S. Patent No. 5, Π5,219 (January 29, 1992) teaches: (1) reacting an imidazolyl compound with an epoxy resin to prepare an adduct; and (2) reacting the adduct with Valproic acid or its derivative reacts to protonate the amine hydrogen atom in the adduct. The resulting adduct reacts with the epoxy resin and cures at about 120 ° C. Recently, it has been desired to enable powder coatings to be applied to new substrates (such as 'wood or plastic') that are not resistant to high temperatures. General curing agents and catalysts cannot be used for this purpose 'because they are cured at too high temperatures. What is needed is a curable epoxy composition 'which does not substantially cure with the epoxy resin at ambient temperature' and which melts, flows, solidifies and solidifies with the epoxy resin without damaging the temperature of the temperature sensitive substrate Good curing of thermosetting materials. Employees of the Central Bureau of Standards of the Ministry of Economic Affairs have cooperated with consumer printing. In addition, it is desirable to cure the solvent-loaded ring gas composition at a temperature lower than the normal curing temperature, so as to protect the substrate and save time and cost when the composition is heated to a very high temperature. What is needed is a curing catalyst and a curable ring-forming composition that are stable at ambient temperature and rapidly cure at temperatures below the epoxy curing temperature to form a good curing thermosetting resin. One aspect of the present invention is a method for preparing a curable composition, which comprises the following steps: Paper ruler fine money _ § ^ TCNSTΑ4 ^ {210X 297 / ^) -5- 448】 9 7 Α7 ~ -______ B7 5 Description of the invention (3) '~~~'-(1) react imidazole with an unsaturated compound containing at least one activated double bond to form a nucleophilic addition adduct; and (2) prepare nucleophilicity The composition of addition adducts and epoxy resins is characterized in that the spurting portion of the nucleophilic addition adducts is less than equivalent% of β in the acid neutralized β before step (2). The second aspect is a curable composition containing: (1) a nucleophilic addition adduct formed by imidazole and an unsaturated compound, which contains at least one activated double bond, and the adduct contains per molecule More than one imidazole moiety; and (2) epoxy resin, the ratio of which is from 0.02 to 10 equivalents of nucleophilic addition adduct per equivalent of epoxy resin, which is characterized in that Less than 50 equivalents of the imidazole moiety is neutralized with an acid. The third aspect of the present invention is a method for curing the aforementioned composition by heating to a temperature at which the composition is cured, which is characterized in that the curing temperature is lower than 130 ° C. The fourth aspect of the present invention is a curable composition containing a nucleophilic addition adduct of (1) imidazole and an unsaturated compound printed by a consumer cooperative of employees of the Central Standards Bureau of the Ministry of Economic Affairs: and (2) An epoxy resin is characterized in that: (a) the nucleophilic addition adduct is present at a catalytic content; and (b) the composition further contains a curing agent for the epoxy resin. Other aspects of the present invention include the use of the nucleophilic addition adduct as the paper standard applicable to the Chinese National Standard (CNS) Λ4 specification (2I0X 297 mm)-6-Member of the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperation A7 _____B7 5. Description of the invention (4) Catalyst 'Use the curable composition to prepare coatings, laminates or other complexes or molded articles, and articles made therefrom. The adduct catalyzes the epoxy-epoxy curing reaction and the branching reaction. The composition of the present invention can be cured at a temperature of about 300 rpm or higher to provide a cured coating containing less foam than similar coatings used for general curing catalysts. In addition, the composition according to the second aspect of the present invention forms a stable powder coating composition which is cured at a temperature below 130 ° C to provide a low temperature powder coating for temperature sensitive applications. The present invention uses a nucleophilic addition adduct, which is prepared by reacting a salivary compound with an unsaturated compound containing at least one double bond that is activated by an adjacent electron withdrawing group. For the purposes of this application, "nucleophilic addition"

Used by March, Advanced Organic Chemistry, 4th edition, pp. 741-743 (1992). The sum compound contains one or more activated double bond moieties (Q) per molecule. The activated double bond portion (q) is preferably bonded to a general intermediate portion (A). The unsaturated compound is preferably represented by Chemical Formula I:

Chemical formula I. (A) is an intermediate portion as described later, each Q is an activated double bond portion, and η is the number of unsaturated portions bonded to the intermediate portion. The activated double bond Part (Q) contains an aliphatic carbon-carbon double bond adjacent to the activated electron withdrawing group. Examples of excessive electron-withdrawing groups include sulfonate, ketone 'esters, amines, nitrates, and sulfonate moieties. An example of a better activated double bond moiety (Q) is shown in the chemical formula ^: The paper size is applicable to the country (cns). ---- (Please read the precautions on the back before filling this page) Order 448 〖9 7 Α7 Β7 V. Description of the invention (Chemical formula Π 0 la) -OC-CR ^ CR1 0 it)

nr-c-cr ^ crS Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperation Du Yinzhuang ο (ί: ϊ 'C-crW3 where each -R1 series is an aliphatic part of an aliphatic part or an activated double bond Part of the bond to adjacent monomers. Each -R1 is more preferably nitrogen or alkynyl. The most preferred is hydrogen or methyl. The selection of each R | is steric hindrance which will not hinder the nucleophilic addition reaction. Each -R 丨 preferably contains no more than 12 carbon atoms, more preferably no more than 6 carbon atoms, and most preferably no more than 4 carbon atoms. Each activated double bond moiety (Q) is more Preferably, it contains an ester moiety, and β is more preferably an acrylate or methacrylate moiety as shown in Chemical Formula II (a). The intermediate part (A) may be a single unit or a polymer containing several repeating units or For the polymer, the selection of the middle part is not important as long as it does not interfere with the synthesis or use of the adduct. The middle part preferably contains, for example, any one or more of the following: alkyl part, aromatic Base moiety, ether bond, S-bond bond, aliphatic or phenolic hydroxyl group, glycidyl ether and / or ester moiety, acid moiety, or hydrogen atom. Preferably it does not contain epoxy resin Cured or catalyzed part such as amine, carboxylic acid, acid dentate or anhydride, thiol group or hydroxyl group. The number of the average chemical formula in the middle part is selected according to the Chinese standard of this paper. (CNS) Eight-four specifications (210X297 mm) (Please read the precautions on the back before filling out this page) Order 4 481 9 7 A7 _______B7 V. Description of the invention (6) ™ Adducts who want to soften the temperature. The number-average chemical formula preferably has a weight of 'for example' not more than about 5, and more preferably not more than about 3, and preferably at least about 200. The unsaturated compound preferably contains at least about 〇5 Activated double bond portion, more preferably at least about L0 Activated double bond portion per molecule, most preferably at least about 1.5 Activated double bond portion per molecule β The maximum number of activated double bond portions per molecule is not Important, but in most cases, it is preferably no more than about 10, more preferably no more than about 6, most preferably no more than about 4, examples of preferred unsaturated compounds include: polyacrylates and Polyf-based acrylate, unsaturated polyacetate and vinyl acetate resin Examples include acrylic vinegar and aromatic vinegar. The unsaturated compound is preferably a vinyl ester resin. The vinyl ester resin is preferably the reaction product of a new or non-new type epoxy resin and an unsaturated acid. Epoxy The resin is preferably poly (glycidyl ether), more preferably a new or non-new type of diglycidyl ether of bisphenol. The unsaturated acid is preferably acrylic acid or methacrylic acid. The reaction preferably occurs in the presence of a catalyst, such as ， 2; 4,6_tris (dimethylaminoethyl) -pan. An example of a suitable resin and its preparation method are described in the printing of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) (Fill in this page)

Messick US Patent No. 4,407,991 (October 4, 1983) and Wykowski's EPO Publication No. 0436 921 A1 (July 17, 1991) Vinyl ester resins can optionally contain unreacted epoxy resin The equivalent ratio of the vinyl ester compound to the epoxy resin portion is preferably more than 丨: 丨, more preferably at least 3: 1, more preferably at least 10: 1, and most preferably at least 20: 1. Unsaturated compounds react with imidazole to form nucleophilic addition adducts. The choice of taste azole is not important, as long as: This paper size applies the national standard rate (CNS) Λ4 specification (210X297 mm) -9-

I 448] b A7 ———---------_ V. Description of the invention (7) (1) What will be the choice? The nucleophilic addition reacts with the unsaturated compound to form an adduct; (2) The adduct is cured by epoxy-epoxy or reacted with curing agent to catalyze the curing reaction of epoxy resin. Imidazole is preferably represented by the chemical formula 化学: Chemical formula 羾 --C-R]

Each R2 is a hydrogen atom, an aliphatic portion or an aromatic portion, and each R2 is an argon or an aliphatic amine group such as a 3-aminopropyl group. Each -R2 is preferably hydrogen or alkyl. Each R2 and R3 preferably contains no more than about 12 carbon atoms', more preferably no more than about 6 carbon atoms, and most preferably no more than about 4 carbon atoms. Two R2 moieties on adjacent carbon atoms can be selectively bonded to form a ring structure, and each R3 is preferably hydrogen. Examples of suitable imidazoles include imidazole, 2-methylimidazole, 2-phenylimidazole, 2-ethylmethylimidazole, and h- (3-aminopropyl) imidazole. Employees' Cooperative Cooperation of the Central Bureau of Standards, Ministry of Economic Affairs, Du Yinhua I-11 III-Gen-[_ 1-It n τ (Please read the notes on the back before filling out this page} Miso is a better choice for unsaturated compounds The concentration of unreacted free imidazole in the adduct is minimized. The reaction mixture may contain a stoichiometric excess of imidazole, preferably the equivalent of the active double bond portion contains not more than about 1 mole of imidazole compound, The optimum is not more than about 0095 moles. The minimum concentration of imidazole in the reaction mixture is based on practical considerations, such as the desired concentration of imidazole in the final adduct. The preferred reaction mixture is activation per equivalent. The double bond part contains at least about 0.5 mol of imidazole compound, more preferably at least about 0.75 mol. This paper is widely used in China Garden Standards (CNS) M Appearance (21〇χ 297 Publication 448197 A7 _______B7__ V. Description of the invention (8) The reaction temperature is preferably at least about 50 ° C, more preferably at least about 100 ° C, and most preferably at least about 120 ° C. The transition line is not more than about 60 ° C, and more preferably not more At about 15 ° C. The reaction preferably occurs during polymerization In the presence of inhibitors, hydrofuran or hydrodecane monomethyl ether is used to prevent unsaturated resins from becoming gelatinous. Even so, 'some solutions are particularly sensitive to gel formation and require special care. Stereo hindered imidazole ( (E.g., 2-ethyl-4-methylimidazole) can react slowly and require additional stabilizers (such as' hydrofuran) in order to provide sufficient time for the reaction to occur. The adduct formed contains a / 3-imidazole moiety, which Preferably, it is represented by chemical formula IV (a), and more preferably, it is represented by chemical formula iy (b): N—-CP2 Ν ·

-Z-CHR ^ CR ^ -OC-CHR ^ CR ^ Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs -r -1. ^ 1 in I-I HI 1 J—. N I—.! Ding,- = 9 (Please read the precautions on the back before filling this page) where each Z is the electron-withdrawing group previously defined, and each — ^^ and ruler 2 have the meaning and preferred embodiment, and each imidazole Preferably it is bonded to the middle part as previously described. The preferable number of the adduct portion depends on the adduct to be used, which is similar to the preferable number of the activated double bond portion in the unsaturated ester compound as described above. Adducts are better chemical formula! Indicates that at least one of them is an imidazole moiety, and the remaining Q is an activated double bond moiety. The equivalent ratio of the oxazole moiety to the activated double bond moiety is preferably at least 1: 1, more preferably at least 2: 1 This paper size is applicable to National Standards (CNS) Α4 specifications (210X29? Mm) ~ 1-'-11-

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives A7 ----------------- B7___ V. Invention Description (9) ′ The best is at least 3: 1. All the active double bond moieties can be converted into the zo-imidazole moieties', but it is generally more practical that the equivalent ratio does not exceed 20: 1 in order to minimize the free miwa in the adduct. The adduct may optionally further contain a product of the reaction of imidazole with an epoxy moiety or other reactive group by an unsaturated compound. The softening point of the adduct is preferably high enough to make the adduct at a general storage temperature of The solids should be low enough to soften the adduct at the desired reaction temperature and solidify with the powder epoxy resin. The Mettier softening point of the adduct (determined by the test method described in the example) is preferably at least about 5 (rc, more preferably at least about 60 ° C, most preferably at least about 80 ° C. It is preferably less than 130 ° C, more preferably less than 100 ° C »The number average molecular weight of the adduct is preferably at least about 400, more preferably at least about 500. It is preferably not more than about 150,000, more preferably Not more than about 1 100. The weight average molecular weight of the adduct is preferably at least about 400, more preferably at least about 500. It is preferably not more than about 2500, more preferably not more than about 1200 »Add The melt viscosity of the compound (measured at 15 °. (Measured using an ICI Cone and a plate viscosity meter with a C-type cone) is preferably at least about 90 mPa · s, more preferably at least about 140 mPa.s, and more preferably Not more than 2000 mpa · s, more preferably not more than about 1500 mPa · s. The adduct is ideally substantially free of unbound imidazole (0% by weight), which is not associated with unsaturated compounds Reaction, but the results are generally not achieved. Preferably, not more than about 50% by weight of imidazole is non-bonded imidazole, more preferably, not more than about 30% by weight, and most preferably The minimum percentage of more than 20% by weight of β non-bonded imidazole is limited by practical considerations, such as steric hindrance. Generally, the size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -12-- ---------- See ------, 玎 (Please read the notes on the back before filling in this page} 448197 A7 B7 V. Description of the invention (10 series at least 1 weight ο /. 》 In the skill, the taste part is neutralized with organic acid before it is counted as the part of the oxygen composition. In the present invention, at least ―the substantial part of the taste and odor part is not protonated (neutral And). Preferably, at least about 50 mole% of salivary wounds are not protonated, more preferably at least about 75 mole% are not protonated, and even more preferably at least about 90 mole% are not protonated. It is preferably at least about 95 mole% unprotonated. Up to 100% is not protonated. The imidazole that is not protonated is preferably present in a free basic state. The composition of the present invention further contains a cyclofluorene resin The epoxy resin is preferably a glycidyl ether or ester compound, more preferably a glycidyl ether compound, and most preferably a new or non-new type of bisphenol. Diglycidyl hydrazone, such as bisphenol A or bisphenol F. Cyclocyanine resins can be new or non-new, but preferably are new, more preferably solid at about 25 ° C, and their cyclic equivalent (EEW) It is preferably at least about 100, more preferably at least about 200, and most preferably at least about 500. Its maximum EEW is not important / but it is preferably no more than about 2500, and more preferably no more than about 200. 〇〇, the best is not more than about 1500 »Its Mettler softening point is preferably at least about 50t, more preferably at least about 60 ° C, and most preferably at least about 65. (: Its Metuer softening point is preferably less than 130 ° C, more preferably less than about 100 ° C. Examples of suitable epoxy resins include epoxy powder-coated resins, epoxy novolac resins, high and medium Molecular weight solution epoxy resin, MDI-modified epoxy resin, glycidyl (meth) acrylate polymer or copolymer, and liquid epoxy resin and blends thereof. Specific examples of the epoxy resin used in the present invention Includes Shuangpan A, Shuangpan F, and Tetrabromobifen A. A wide range of suitable epoxy paper paper standards Common Chinese National Standard (CNS) A4 specifications (210X 297 mm) Yiyi 1 — {Read the first read first (Please fill in this note before buying)

, 1TI ί—-In I Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -13- Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs α? Η Α7 [----___ Β7 V. Description of the Invention (11) Tree Moon It is commercially available. The method of preparing others is familiar to those skilled in the art and described in various general publications such as Lee &amp; Nevdle, Epoxy Handbook, pp. 2-1 to 3-24 (McGraw-Hil 丨 Book Co. 1967). The epoxy resin may also be a novel product of a liquid epoxy resin and tetrabromobisphenol a or an epoxy-functional oxazolone containing a copolymer described in US Pat. No. 5,12,932.

The optimal ratio of the additive to the epoxy resin is generally determined by the contents of the composition and the intended use. D When the adduct is cured without a separate curing agent or crosslinking agent, the equivalent ratio is better. Each amount of epoxy resin is an adduct of at least about 0.02 equivalents, more preferably at least about 0.05 equivalents, and most preferably at least about 02 equivalents. The optimal concentration is not important, but it is preferably no more than about 10 equivalents of adduct per equivalent, more preferably no more than about 5 equivalents, more preferably no more than about 2 equivalents, most Preferably it is not more than about 1 equivalent. The weight ratio of epoxy resin to adduct is preferably at least 1:10, more preferably at least 1: 1, and most preferably at least 2: 1. The weight ratio of epoxy resin to adduct is preferably not more than 〖〇: I, more preferably no more than 5: 1, and most preferably no more than 3: 1. When the composition contains a curing agent and is cured at an elevated temperature, a smaller amount of the adduct is preferred. The equivalent ratio is preferably at least about 5 milliequivalents (meq) per equivalent of epoxy resin, more preferably at least about 201 ^ £ 1, and most preferably at least about 80 meq. The maximum concentration is not important, but is preferred The epoxy resin is not more than about 200 meq per equivalent, more preferably not more than about 50 meq, more preferably not more than about 100 meq, and most preferably not more than about 50 meq. The weight ratio of the epoxy resin to the adduct is preferably at least about 丨 parts (phr) per 100 parts of the resin. The paper method scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm).

14-4 4 8 ΐ 9 Α7 Β7- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. The description of the invention (I2) is preferably at least about 3 Phr 'and most preferably at least about 5 phr. The weight ratio of the cycloemulsion resin to the adduct is preferably not more than about 15 phr, more preferably not more than about 10 phr ', and most preferably not more than about 5 phr. Suitable curing agents for use in this composition are varied depending on the intended use of the composition. Several suitable curing agents are taught to those skilled in the art. Lee &amp; Neville, supra, 20 Examples on page -11 and Tess, supra '776-778 * Examples of suitable curing agents include dicyanodimethamine and other amines and amines' polyarginol and polyanhydrides, such as pentylmaleic anhydride. The optimal ratio of curing agent to epoxy wax depends on the curing agent and resin used. Generally, the equivalent ratio of the curing agent to the epoxy resin is preferably from 0.1: 1 to 10: 1, and most preferably from 0.2: 1 to 2: 1. Compositions containing sufficient adducts to catalyze the curing of the emulsion-epoxy may further contain a curing agent. The equivalent ratio of the adduct to the curing agent is preferably 25:75 ′, more preferably at least 50:50 ′, more preferably at least 75:25, and most preferably at least 90:10. The composition optionally contains a solvent, but is preferably It is free, and more preferably it is a powder coating composition. The solvent (if any) is preferably organic. Suitable organic solvents are known and commercially available. The choice is not important. Examples of suitable agents include: xylene, diethyl ether, acetone, toluene, alcohol, and dimethylphosphonium. The concentration of solids in the solvent is not important, but is subject to practical considerations such as the cost of 'viscosity' and the need to recover the solvent from the effluent. It is preferably between 20 and 80% by weight, and more preferably between 40 and 60% by weight in most cases. The composition may optionally contain other additives that can be used for the intended use. The paper size is applicable to the national standard (CN'S) grid (2) 0 × 29? Mm. 1 --- Γ---I I--K ^ 1-(_ I Ding (please read the notes on the back before filling this page) -15- 448197 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (U). For example, coating composition Compositions that can optionally contain: stabilizers, surfactants, and flow modifiers, fillers, colorants, and matting agents β Preparation of laminates and complexes can optionally contain stabilizers, fillers, and flow modifiers And chopped fibers. The agronomic properties of the additives in the composition other than colorants, fillers, and chopped fibers are preferably not more than about 5% by weight, and more preferably not more than about 3% by weight. Chopped fibers The concentration of fillers and pigments is preferably no more than 80% by weight, and more preferably no more than about 50% by weight. The concentration of any or the owner may be 0% by weight. By epoxy-epoxy homopolymerization The reaction cured composition is preferably cured at a temperature of at least about 80 ° C, more preferably at least about 90 ° C. The temperature is preferably at least about i00 ° C. It is preferably cured at a temperature less than i30eC, more preferably less than 120 ° C, and most preferably not more than about u cTc. But 'It can be used at temperatures of 200eC or higher. Compositions containing smaller amounts of adducts and individual curing agents are preferably cured at a temperature of at least about 120 ° C, and more preferably at least about 130. (:, The best is at least about 150 ° c. The maximum curing temperature is changed according to the desired temperature, but in most cases' the better is not more than about 250 ° C, and the better is not more than about 220 ° C. The composition of the present invention can be used for general epoxy applications, such as coating_ laminating and molding applications. For example: (a) solution coating composition can: (1) by known means such as , Spraying, painting, rolling, dipping or electrodeposition) coating on the substrate; and (2) curing by heating to an appropriate curing temperature. The paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (21〇乂 297 mm) (Please read the notes on the back before filling out this page), 1T -16 Printed by the Consumer Procurement Cooperation Department of the Central Procurement Bureau of the Ministry of Economic Affairs «48197, 1 A7 __; _— B7 V. Description of the Invention (l4) (b) The powder coating composition can be applied as follows: (1) The substrate is heated to a suitable curing temperature for the composition ; And (2) coating the compound by a known method such as electrostatic spraying or fluidized bed. It can also be applied by: (1) coating the powder on a cold substrate, Such as electrostatic coating method; and (2) heating the powder and substrate to the temperature at which the powder flows and solidifies. (C) The laminate can be prepared by: (1) impregnating the composition on a fiber base Material and heating to form a prepreg; and (2) pressing two or more prepregs together at a temperature suitable for curing the composition. (d) Molding can be prepared by: (1) injecting the composition into a mold, which can optionally contain a fibrous substrate; and (2) curing the composition by heating. Components (such as leaf springs) for automotive parts can be advantageously made from the composition of the present invention. The catalyst of the present invention may also be used for coating of an electrical laminate via a powder coating or solvent system such as described in U.S. Patent No. 5,112,932. The invention is further illustrated by the following operating examples. Operation Examples The following examples are for illustrative purposes only. They are not used to limit the specification or application paper size to the Chinese National Standard (CNS) Λ4 specification (210x297 mm (please read the precautions on the back before filling this page). Order- 17-9 A7 B7 V. Description of the invention (l5) Patentable scope. Preparation of adducts. The proportions of specific reagents and adducts used to prepare the invention are shown in the following worksheet. Addition The system was prepared using the following general procedures: (1) Optionally, new epoxy resins were prepared. DER, 33 ° (trademark of The Dow Chemical Company) liquid epoxy resin samples in the presence of new scale catalysts' Under the nitrogen atmosphere, about 14 (rc, react with bisphenol A. The amount of each reagent and the eEW of the new resin formed are shown in Table I. (In the entire table, the amount of the reagent is shown in pbw table. Except for other indications.) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs ^-n ^ im I —i ^^ il ^ i VJ .¾-ΙΦ (Please read the precautions on the back before filling this page) ( 2) Vinyl ester resin is prepared. The new tree of step (〗) Or DER · * 33〇 The liquid epoxy resin sample is heated to 80.00 to 10000c, and a fixed working gas is foamed through the resin. About 500 ppm of hydrogen is added as an inhibitor and Acrylic acid or methacrylic acid was added. ANCAMINE K54 catalyst was added at 75 ppptn and the temperature was raised to about 120 ° C. When the residual epoxy concentration was about 7 or 8%, the second 750 ppm was added. ANCAMINE K54 catalyst is added. When the residual epoxy reaches the concentration shown in Table I, the reaction is interrupted and the temperature is reduced. The air flow is reduced and the vinyl ester resin is purged with nitrogen. The reagent and the vinyl acetate resin The residual epoxy content is shown in Table I. (3) The imidazole adduct of the vinyl ester resin is formed. The spit shown in Table I is added in several portions during a period of about 15 minutes to form a mildly formed product. External heat. After that, the temperature was slowly raised to 140 ° C in 15 minutes, and the mixture was heated in HOT: 60 minutes. The product was recovered and cooled. The residual paper in the adduct was scaled to China National Sample Rate (CNS) A4 Specifications (210X 297 cm) Μ48ί97 A! B7 V. Description of the invention (l6) It is measured by HPLC. (4) Mettler softening point is measured using the following method, which is published by the Dow Chemical Company's RPM-108C method, which is a deformation of ASTM D 3104. The softening point in PRM-108C is The temperature at which the epoxy resin suspended in a cylinder with a hole at the bottom of 6.35 mm flowing 19 mm downward when flowing at a linear rate when heated in air was a temperature of 19 mm. The sample was ground to a size of less than 5 mm. Samples with 6.35mm holes in the bottom are placed on aluminum foil on a hot plate at 150 ° C (for low molecular weight samples) or 200t (for high molecular weight samples). The granule sample is added to the 枉 until it is filled with molten foaming free resin. 枉 and the aluminum foil are removed from the plate and cooled; then, the aluminum foil is peeled off and excess resin is removed from the outside of the 枉. The mule was placed in Mettler Instruments' FP5 / 53 softening point device. This device contains a furnace and a beam. When the sample flows out of the ladle, the beam is disturbed. The flame temperature is set at 20 ° C below the expected melting temperature of the sample and the sample is left for at least 30 seconds for equilibration. Then, the temperature rises by 2 ° C per minute until the droplets formed under the holes destroy the light beam. (5) Melt viscosity is measured using ICI Cone and Plate Viscometer with C cone at about 150 ° C. The average molecular weight was determined by gas chromatography. The properties of the reagents and adducts are shown in Table I. For the purposes of Table I, "Im" means imidazole, "2-ΜΓ means 2-fluorenimidazole, and" 2-Phi "means 2-phenyl Imidazole, and "2E4MI" means 2-ethyl-4-fluorenylimidazole. This paper size applies to China National Standard (CN'S) A4 specification (210X 297 male; t) -19- b 8 4 4

7 7 AB V. Description of the invention (Π) Table I Adduct 1 2 3 4 5 6 Liquid epoxy resin (pbw) 559 539 48.94 55.10 46.5 48.46 Shuangpan A (pbw)-57.8--5.2 Epoxy equivalent 180 240 180 180 180 240 Methyl acrylic acid (pbw)-209.7 22.82 21.17-Acrylic acid (pbw) 210---18.27 15.78 Residual epoxy (%) 0.6 1.0 1.0 3.6 &lt; 1 1,5 Choice of imidazole 2 -MI 2 capture 2Ε4ΜΪ 2-MI 2-Phi 2-Phi Saliva volume (pbw) 231 193,4 28.23 23.73 35.27 30.56 Residual imidazole (%) 1.2 5.7 16.3 5.9 6 · 1 6.2 Softening point (° c) 78 71 , 9 65.8 76.9 82.1 89.4 Melt viscosity (mPa. S @ 150 ° C) 370 190 110 360 270 600 Μπ-726 704 658 612 516 Mw-908 777 742 878 1070 Μ,-1177 878 846 1101 1857 Polydispersity- 1.25 L10 1.13 1.43 2.07 Table I (continued) ----: ------ I ------ 1T (Please read the notes on the back before filling {&quot; this page] Central Standard of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperative Printing Adduct 1 7 8 9 10 11 12 Liquid Epoxy Resin (pbw) 54.97 52.77 55.21 55.00 56.89 539.1 Double Age A (pbw)-Book 11.25-11.59-Epoxy equivalent 180 180 320 180 320 1 60 Methylpropionic acid (pbw) 25.63 24.61 17.59 235.8 Acrylic acid (pbw)--2L57 15.10-Residual epoxy (%) L0 1.0 1.17 0.95 0,85 1.46 Selection of imidazole Im 2-MI 2-MI 2- MI 2-MI 2-MI Amount of bee smell (pbw) 19.4 22.62 15.95 23.43 16.42 225.1 Residual imidazole (%) 4.6 4.7 6.1 1.2 0.6 4.1 Softening point (° c) 62.8 69,3 84,2 77.9 92.6 72 Viscosity (mPa * s @ 150 ° C) 160 140 680 370 1520 1400 · Mn 576 529 1060 790 1139-Mw 639 579 1716 972 1920-Μ, 699 625 2675 1284 3088-Polydispersity 1.11 1.09 L62 1.23 1.69-&gt; Measured at 120 ° c. The paper size applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) -20- 448197 Printed by Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs &quot; A7 B7 V. Description of the invention (18) Example 1- The laminated adduct 12 was dissolved in methyl ethyl ketone to a solid concentration of 65%. A mixture of 10 grams of adduct solution and 125 grams of DER / 691 A80 epoxy resin solution was impregnated in a 15 cm x 15 cm square woven E glass 7628 sheet (woven E glass 7628 is available from Inter Glass) «The impregnated flakes are heated in a hot air circulating oven at 8 ° C for 4 minutes to evaporate the solvent. The resulting prepreg contains 60 to 65% resin. A 50% prepreg is placed in Between two pieces of copper foil and pressurized at 1 UTC and a pressure of 0.2 bar for 20 minutes. The formed laminate had a glass transition temperature of 69 ° C. The experiment was repeated using 12 g of the adduct solution. The formed laminate It has a glass transition temperature of about 99 ° C. The two-layer laminate has a good appearance. Example 2-16 Powder-coated epoxy resin A was prepared by stirring in a nitrogen atmosphere at 100 ° C, First mix 6830 grams of 0_ £ .11 / 330 liquid epoxy resin and 3170 grams of ER_grade bisphenol A with a new catalyst of 500 ppm. Second, heat the mixture to 140 ° C. Second, at 140. (: reaction About 2 hours, until the resin viscosity is about 5,000 mPa · s at 120 ° C-Secondly, by adding para- The methyl ester of methanesulfonic acid quenched the catalyst. Second, it was stirred for 30 minutes, and then cooled and solidified. The target EEW of the resin was about 1000. Epoxy resin B was prepared by the same procedure, but 6, 6% by weight of DEN * 438 (trademark of the Dow Chemical Company) epoxy novolac resin is added to the reaction mixture immediately after the methyl ester of p-toluenesulfonic acid. This paper size applies Chinese national standards ( CNS) Α4 size (210X297 meal) (Please read the precautions on the back before filling this page)

1T -21-448ί 97 Α7 Β7 Employees of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China F. Cooperative cooperatives' printing 5. Description of the invention (19) Two 70 grams of DEH, 5 (trademark of Dow Chemical Company) phenol hardener The sample was melted under a nitrogen atmosphere of 14 t. 30 g of the adduct were mixed into the first sample (hardener eight) and 30 g of the adduct was mixed into the second sample (hardener B). The mixture was stirred for 15 minutes and then cooled to room temperature. The epoxy resin, hardener, and additives shown in Table II are mixed into the laboratory mixer in the ratio shown in Table π at 420 rpm and within 2 minutes. The mixture was melt extruded in a twin screw extruder at 65eC and 300 rpm. The extrudate is cooled, sliced, ground and sieved to produce a powder. The powder was applied to a steel plate 'using electrostatic spraying and the steel plate was placed in a furnace at 110. 〇, I20 ° C and 130 ° C for 20 minutes. The coatings were tested for: Flow-by visual inspection and comparison with high temperature powder coated samples. As a result, 0 = poor and 4 = excellent. Burnability-Use Erichsen's test. Impact resistance-using ASTM D2794-84 test method, using 4 pounds (1.8 kg) heavy coating on the carrier surface, its diameter is 1/2 inch (1.25 cm) "test system measures the force that can be applied without damage Number of in-lbs (Nm) »Gloss at 20 ° reflection angle-using DIN 55 990 test method. All tests were repeated using powders that had been aged for six days at 35 ° C. All results are shown in Table II. (Please read the notes on the back before filling out this page), 1T This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -22- 3 f 9 7 A7 B7 V. Description of the invention (2) Table 2 Sample 2 3 4 5 6 7 8 9 10 Epoxy resin A (pbw) 532.8 532.8 532.8 532.8 532.8 532.8--Epoxy resin B (pbw)------461.3 461.3 461.3 Hardener A (pbw ) 59.2 59.2 59.2 59.2 59.2 59.2---Hardener B (pbw)-----80 80 80 MODAFLOW MFIII (pbw) 8.0 8.0 8.0 8.0 8.0 8.0 8.1 8.1 8.1 Titanium Dioxide (pbw) 400 400 400 400 400 400 405.4 405.4 405.4 Aging: (days) 0 0 0 6 6 6 0 0 0 Application to eC 110 120 130 110 120 130 110 120 130 Flow 2 2.5 3 1.5 2.5 3 3 3'5 4 Erichsen Trial (mm)-8.3 8.9-8.0 8.3 8 7 Impact resistance (British pair-broken) (Nm)-160 (18.1) 160 (18.1) 160 (18.1) 160 (18.1) 140 (15.8) 160 (18.1) Gloss (%)-101 100- 96 98-92 93 ί ---.------ Yu (Please read the notes on the back before filling out this page) Table π (trace) Order of the Central Laboratories of the Ministry of Economic Affairs Printed samples 11 1 2 13 14 15 16 Epoxy resin A (pbw)------Epoxy resin B (pbw) 461.3 461.3 461.3 461.3 461.3 461.3 Hardener A (pbw)-----Hardening wound B (pbw)-80 80 80 80 80 80 MODAFLOW MFK (pbw) 8,1 8.1 8.1 8.1 8.1 8.1 Chlorine Dioxide (pbw) 405.4 405.4 405.4 405.4 405.4 405.4 Aging: (days) 7 7 7 14 14 14 Yu. C Application 110 120 130 110 120 130 Flow 2 3 3 1 2 3 Erichsen Test (mm)----6.3 7.4 Impact resistance (British broken) (Nm)--160 (18.1) 160 (18.1) Gloss (% ) 92 93-90 93 This paper size applies to China National Standards (CNS) A4 (2Ι0χ 297 public love) -23- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 4 8 / c 1 ^ A7 B7 V. Invention Explanation (21) Example 17 A diacetamide modified phenol hardener was prepared in the following manner: (1) 32.8 parts by weight (pbw) of liquid epoxy resin and 62.7 pbw of bisphenol under nitrogen at 100 ° C A mix; (2) add 4.5 pbw of diethanolamine that has been melted at 50 ° C; and (3) after exotherm reaches 180 ° C, cool to 15 (TC and hold for 30 minutes) 90 pbw obtained from Example 1 The adduct is mixed with 10 pbw of a novolak phenol resin having a hydroxyl equivalent weight of about 104 under nitrogen atmosphere at i400 ° C. The resulting hardener composition has a MetUer softening point of about 831 and is at The melt viscosity at 120 ° C is 3840 mPa. S. The powder coating composition is prepared in accordance with the procedures of patent application Nos. 2 to 16. It contains: 10.9 pbw Diethanolamine modified phenol hardener, 3.5 pbw hardener composition containing adduct, 24.9 pbw of DER * 672U epoxy resin, 30.7 pbw of D.E_R · * 642U epoxy resin, 5 pbw titanium dioxide , 22 pbw of BaS04, 2 pbw of mica, and 1 pbw of MODAFLOW MIII II flow modifier. The composition was coated on a 6 mm steel plate using an electrostatic sprayer, which had been preheated to 245 ° C. Coating The material was cured at 245 ° C for 2.5 minutes. The powder was also manually applied to a glass plate (which had been preheated to 235 ° C) and cured for about 2 minutes. The plate was observed through a microscope and was substantially free of bubbles. Example 18 Using the procedure of Example 17, adduct 8 was melt blended with a phenol novolac resin having about 104 hydroxyl equivalents at 140 ° C. The weight ratio of the adduct to the novolac resin was 90:10. When complete, the blend has a softening point of 86.7 ° C, and a melt viscosity of 440 mPa · s at 150 ° C. At 120 ° C, the paper size applies the Chinese National Standard (CNS) Α4 specification (21〇χ29? 公 漦) ) (Please read the notes on the back before filling this page)

'1T -24- 448 A7 B7 V. Explanation of the invention (22) The melt viscosity is 3360 mPa · s. The powder composition contains: 636.8 pbw of DER / 661E epoxy resin; 55.2 pbw of blend; 300 pbw of KRONOS 2310 (available from Kronos) titanium dioxide; and 8.0 pbw of MODAFLOW MFIII (available from Monsanto) Flow Modifier * It was prepared using the procedure of Example 2-16. The composition was coated on a steel plate as described in Examples 2 to 16 and cured at 120 ° C and 110 ° C for 20 minutes. It was also coated and cured at 100 ° C for 30, 45, 60, and 75 minutes. The coatings were tested as in Examples 2 to 16. The results are shown in Table III. All plates resisted the abrasion of 200 acetone without visible damage. Form ΠΙ (Please read the notes on the back before filling out this page).

’1T Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs Time (minutes) Temperature rc &gt; Thickness (#m) 20. Gloss 60. Gloss Erichsen Cavity (mm) Impact in-lbs. (Nm) 20 110 566 100 103 3.8 110 (11) 20 120 56 99 103 4.6 90 (10) 30 100 59 97 102 5.6 30 (3) 45 100 53 100 101 4,6 50 (6) 60 100 59 99 101 6.0 · 50 (6) 75 100 67 99 101 4.1 40 (5) This paper size is applicable to China National Standard (CNS) A4 specification (2) 〇X 297 mm )

Claims (1)

Scope of patent application No. 861 1 8400 Patent Reexamination Application Patent Range Amendment, where the adduct does not exceed, and the adduct does not exceed 丨 Amendment i Correction Date: 1990.05. 1. A preparation-curable A composition method comprising the following steps: (1) reacting an imidazole with an unsaturated compound containing at least one activated double bond to form a nucleophilic addition containing more than one imidazole moiety per molecule An adduct; and (2) preparing a composition containing the nucleophilic addition adduct and an epoxy resin, characterized in that less than 50 equivalents of the nucleophilic addition adduct % Of imidazole was neutralized by acid before step (2); wherein the adduct had a Mettler softening point of at least 5CTC, and measured at 15CTC Melt viscosity of at least 90 mPa's. 2. As in the method of applying for item 1 of the patent scope, 25% of the imidazole is neutralized by the acid. 3. As in the method of claim 2 of the patent application, 10% of the imidazole is neutralized by the acid. 4. · If the method in the scope of the patent application is applied for item 3, more than 5% of the taste is neutralized by the acid. 5. · If the method in the scope of the patent application is applied in item 4, it is the "unsaturated flavorazole", 2-f Any one of imidazole, 2-ethyl-4_f-imidazole, 2-benzylimidazole, or N- (3-aminopropyl) odor. 6. A curable composition comprising: The nucleophilicity and cost of papers composed of -㈣ and -unsaturated compounds are applicable to the Chinese standard "CNS" A4 (21〇X 297 public love) ------: ----- ^- ------ Order --------- ^ (please read the note i on the back of the page first and then fill out this page &gt; 6. The scope of the patent application adduct, the adduct containing more than one imidazole moiety per molecule; and (2) epoxy resin, the ratio of which is 0.05 to 10 equivalents per equivalent of epoxy resin. The nucleophilic addition adduct is characterized in that less than 50 equivalent% of the imidazole in the addition # is neutralized by the acid, wherein the adduct has a Mitteler softening point of at least 5 CTC, Well at 150. Melt viscosity of at least 90 mPa.s as measured at 0 °. . A method for curing a composition such as the second item in the patent application, which is characterized by heating the composition to its curing temperature, which is lower than 13 × :. 8_ The method of claim 7 in the patent scope, wherein the curable composition is a powder coating composition. 9. A curable composition comprising: (a) an epoxy resin; (b) a curing agent for the epoxy resin in an equivalent ratio of 0.05 to 10 equivalents of the curing agent per equivalent of the epoxy resin; and ( c)-a catalytic amount of catalyst, which is used in the reaction of the epoxy resin and the curing agent I is characterized by a rhenium catalyst-a nucleophilic addition addition of-imidazole and an unsaturated compound The adduct has less than 50 equivalents of the imidazole moiety neutralized by the acid; wherein the adduct has a Mithion softening point of at least 50 C 'and measured at 15 CTC ( (Please read the notes on the back before filling in this page) I nn ^ -r &quot; J_ HP Μ 层 Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -27- 4481S7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Melt viscosity of at least 90 mPa.s. 10. The curable composition according to item 9 of the application, wherein the concentration of the adduct is 5 to 200 milliequivalents per equivalent of epoxy resin. 11. A catalyst and / or curing agent product for an epoxy resin, comprising the reaction product of an imidazole and an unsaturated compound containing at least one activated double bond to form a prodrug containing more than one imidazole moiety per molecule A nuclear addition adduct; wherein the adduct has a METTLER softening point of at least 50T: and a melt viscosity of at least 90 mPa's measured at 150 ° C. 12. As a product of the scope of application for patent No. 11, wherein the Mik has the following formula: wherein each R1 is a hydrogen atom, an aliphatic portion or an aromatic portion; each R2 is a hydrogen atom, a lipid individually A family moiety or an aromatic moiety; and each R3 is hydrogen or an aliphatic amine group. 13. If the product of item 11 of the patent application 'wherein the unsaturated compound has the following formula: A-(-Q) n where A is a polymerization including a single unit, an aggregate or a plurality of repeating units In the middle part of the compound, each Q is an activated double bond part 'and n is the number of unsaturated parts bound to the middle part. 14. The product according to item 11 of the application, wherein the unsaturated compound is an aromatic unsaturated compound. 15, such as the scope of patent application! The product of item 丨, wherein the unsaturated compound is a vinyl ester resin. --III —.----- install ----- 1 · Order ·! ------ ^ (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -28- 97 A8 B8 CS D8 Application scope 16. The product according to item 11 of the application scope, wherein the unsaturated compound is a vinyl ester resin containing an unsaturated epoxy moiety. 1 7. The product according to item 16 of the scope of patent application, wherein the ratio of the vinyl ester portion to the epoxy portion is greater than 1: 1 to at least 20: 1. --- :! 1,-1 --- Outfit ------ 1 Order i! · '^ (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs ^ 29- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Year pi: Application date_No. Category ^ / 〇〇 (The above sheds are filled by the Bureau) 448197 A4 C4 Yunnong Patent Specification Tingyue Invention—Name New Chinese Method for preparing curable composition, curable composition, method for curing the composition, and catalyst and / or curing agent product of epoxy resin English A 1U ΜΑΚ 1ι A CURADLii A CURABLE COMPOSITION, A PROCESS TO CURE THE COMPOSITION, AND A CATALYST AND / OR CURING AGENT PRODUCT FOR EPOXY RESINS Name (1) Joseph Gan (2) Gabrielle * Bardini (3) Crow E. Huffman Nationality (1) France (2) United Kingdom (3) German costume inventor residence, residence (1) 100 Streisburg, Porigan Road, France (2) Sasbach, Germany No. 5 Den Chilzger Road (3) No. 24, Bollinger-Weinberger Kopping, Germany Name (Name) American Dow Chemical International Co., Ltd. Central Consumer Affairs Bureau, Ministry of Economic Affairs, Consumer Cooperatives, Printed Nationality Residence, Domicile (Office) Representative Name United States Midland, Michigan • Albert Road, USA Stevens Center No. 2030 Steven S. Glass This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) line 4481 97 A5 B5 IV. Abstract of Chinese invention (the name of the method for preparing T-cured composition, Curable composition ~, a method for curing the composition, and epoxy resin) a catalyst and / or curing agent product of the composition 'comprising: (1) a nucleophilic addition adduct of an imidazole and an unsaturated compound , Which contains more than one imidazole moiety per molecule; and (2) epoxy resins are characterized by less than 50 equivalents in the adduct. After the imidazole moiety is neutralized, the adduct can be used as high or low temperature Cured curing catalyst. The composition is used as a coating for powder coating or as a substrate resin in laminates. * It can be used in solvents or liquid systems. Ministry of Economic Affairs t 夬 标 隼Abstract of the English invention printed by Linggong Consumer Cooperatives contains: (1) the nucleophilic addition adduct of an imidazole and an unsaturated compound, which contains more than one imidazole moiety per molecule; and (2) an epoxy resin, is characterized in that fewer than 50 equivalent percent of the imidazole moieties in the adduct are neutralized with acid. The adduct may serve as a curing catalyst in high or low-temperature curing. The composition is made and applied as a powder coating for coatings or as a matrix resin in laminates. It may be used in solvent-borne or liquid systems. ----: --- ^ ---- i ------, order ----- 0 (Please read the notes on the back before filling in this section) Paper size Applicable to China National Standards (CNS) A4 (210X297 mm) No. 861 1 8400 Patent Reexamination Application Patent Range Amendment, where the adduct does not exceed, and the adduct does not exceed 丨 Amendment i Correction Date: 1990.05. 1. A preparation-curable A composition method comprising the following steps: (1) reacting an imidazole with an unsaturated compound containing at least one activated double bond to form a nucleophilic addition containing more than one imidazole moiety per molecule An adduct; and (2) preparing a composition containing the nucleophilic addition adduct and an epoxy resin, characterized in that less than 50 equivalents of the nucleophilic addition adduct % Of imidazole was neutralized by acid before step (2); wherein the adduct had a Mettler softening point of at least 5CTC, and measured at 15CTC Melt viscosity of at least 90 mPa's. 2. As in the method of applying for item 1 of the patent scope, 25% of the imidazole is neutralized by the acid. 3. As in the method of claim 2 of the patent application, 10% of the imidazole is neutralized by the acid. 4. · If the method in the scope of the patent application is applied for item 3, more than 5% of the taste is neutralized by the acid. 5. · If the method in the scope of the patent application is applied in item 4, it is the "unsaturated flavorazole", 2-f Any one of imidazole, 2-ethyl-4_f-imidazole, 2-benzylimidazole, or N- (3-aminopropyl) odor. 6. A curable composition comprising: The nucleophilicity and cost of papers composed of -㈣ and -unsaturated compounds are applicable to the Chinese standard "CNS" A4 (21〇X 297 public love) ------: ----- ^- ------ Order --------- ^ (please read the note i on the back of the page first and then fill out this page &gt;