TW200835708A - Soluble polymers with high conversion of acid from aromatic epoxy resins and diacids and crosslinked coatings prepared therefrom - Google Patents

Abstract

An uncrosslinked, soluble, epoxy terminated high molecular weight epoxy ester resin having an acid number of less than about 5 comprising the reaction product of a low molecular weight epoxy resin and a dicarboxylic acid; and a coating produced from the uncrosslinked, soluble, epoxy terminated high molecular weight epoxy ester resin.

Description

200835708 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a solvent-free high-molecular-weight epoxy ester resin which has been uncrosslinked from a low molecular weight aromatic epoxy resin and a diterpenic acid. A soluble high molecular weight epoxy ester resin is advantageously used to prepare a crosslinked coating from the oxygen generating resin.先前 【 【Prior Art】 保护 Protective coatings for metals are one of the first applications of epoxy resins, and their use as internal coatings for metal food and beverage containers is one of the largest markets. Typically, internal protective coatings for metal food and beverage containers are made from high molecular weight epoxy resins. Moreover, typically high molecular weight epoxy resins are prepared by reacting a low molecular weight epoxy resin such as diglycidyl ether of bisphenol 1 with a hydroxyl containing monomer such as bisphenolphthalein. The cyclic reaction product of bisphenol hydrazine and bisphenol a diglycidyl ether, also known as = cyclodimer, often precipitates from the coating solution, causing processing equipment: • wood' with productivity loss and waste produce. The food and beverage can industry is looking for a technology that can reduce or eliminate such problems from the manufacture of epoxy thermoset internal container coatings. A class SiL class represents a broad class of potentially effective materials that can be used in the reaction with low molecular weight epoxy resins to produce higher molecular weight epoxy ester resins. However, according to the known methods for preparing high molecular weight epoxy resins, the use of dicarboxylic acids leads to the formation of crosslinked insoluble polymers. What is needed in the industry is a method of reacting a dicarboxylic acid as a comonomer with an epoxy resin monomer, resulting in a non-crosslinked soluble epoxy functional polymerization. 5 200835708 0 There are many known methods for the use of dicarboxylic acid. Acids and epoxies, such as U.S. Patent No. 4,722,981, U.S. Patent Publication No. 2,128,428 A1, and European Patent Publication No. 0501575 A2. However, the use of monocarboxylic acids as comonomers is not indicated in U.S. Patent No. 4,722,981 and U.S. Patent No. 2,128,428, the disclosure of which is incorporated herein by reference. As a catalyst, it is not used as a comonomer. Therefore, the method disclosed in the above-mentioned prior art does not produce an uncrosslinked soluble high molecular weight epoxy ester resin terminated with an epoxy group. A number of other known methods are used to illustrate the use of diepoxides and dicarboxylic acids, such as those disclosed in U.S. Patent Nos. 5,962,621, 5,8,2,163, and 5,780,582. However, such documents do not disclose hydroxy-functional polyesters terminated with an epoxy group. Other literature, such as Suzuki, Akira; Kameyama, Atsushi; Nishikubo, Tadatomi, Kobunshi Ronbunshu (1996), 53(9), 522-529; Alvey5 Francis B.? Journal of Polymer Science, and Dusek, K, Matejka, L Advances in Chemistry Series 1984, 208, 15 teaches the synthesis of high molecular weight polyesters from epoxy resins and dicarboxylic acids. However, the methods disclosed in these documents use an equimolar amount of epoxide and diveric acid. Thus, the resin product obtained by these known methods: (1) does not have epoxy functionality, ( 2) including a large amount of unreacted dicarboxylic acid, or (3) undergoing gelation. U.S. Patent Nos. 4,829, M1 and 45,302,574; and Canada 6 200835708 Patent No. 1091690 - address m - do not use epoxy resin and carboxylic acid reactions, but the temple literature does not show The ring is a molecular weight epoxy ester resin. Synergy and other literature may be sister--, the purpose of the use of dicarboxylic acid, but the use of dicarboxylic acid as a co-monomer to break the end of the uncrosslinked eight P table preparation ^%虱The base < j / conjugated ruthenium molecular weight epoxy resin, for example, U.S. Patent No. 3,864,316 jin η, 〆, 旎 and 4, 474, 935, discloses the preparation of chlorination, that is, non-aromatic ring bombardment, and the coating number is disclosed for preparation. a method comprising _ taking I, 171, 820 " a methyl group-based functional polyester; and WO 0001779 A1 discloses a right 俨 取 method, and, 虱 _ polyester block copolymer and A coating composition of a crosslinking agent, wherein the ring sentence is MSk. In the middle of the private, vinegar after the #polymer all have acid function hope to hunt from the low molecular weight of the pain of the # 徂 一 inserted ^ Xiang private clothing milk resin and dicarboxylic acid reaction; the father's soluble epoxy is the end of the high A molecular weight epoxy vinegar resin in which the uncrosslinked soluble epoxy groups are terminal:::; The amount of the epoxy vinegar resin can then be reacted with a crosslinking agent to form a coating. - Knife [Summary of the Invention] =_点_ The uncrosslinked soluble ring 2 of Xinlai is a terminal high molecular weight epoxy ester resin having an epoxy group terminal and a few acid group conversion ratio of ruthenium. In a specific example, the uncrosslinked soluble lacquer base of the present invention is a high molecular weight epoxy ester resin based on a low molecular weight linalyl epoxy resin and a diterpenic acid. Produced by reaction. Because of the epoxy resin's ability to use the resin, it can be used as a precursor for epoxy thermosets, including 7 200835708 by coating with a crosslinking agent. For example, _Lu resin (Chongdu HCresoles) cross-linking another aspect of the invention, the novel epoxy vinegar coated reed, m has the nature of the balance of the resin and various types of sputum; ^ hunting by the above soluble high The molecular weight of the epoxy vinegar is mainly formed by::: reaction. The novel epoxy S coating is for use in the interior of food or beverage cans and/or can ends. [Continuous application method]

The present invention includes a novel composition comprising a product having an epoxy terminal and a south (tetra) acid group conversion or a low acid value. The present invention: = a high molecular weight epoxy vinegar resin which is prepared by reacting a low molecular weight epoxy resin with a dicarboxylic acid to form a terminal, and a soluble epoxy group having a reactive epoxy group as a terminal: in the epoxy functionality of the resin They are used as rigid conductors for epoxy thermosets, including coatings that are crosslinked with a soluble phenolic resin. The present invention is a high molecular weight oxyacetate resin composition which is not crosslinked and has a soluble epoxy group as a terminal. It is referred to herein as a solid epoxy ester resin/7 or a seer® to distinguish the present invention. Epoxy resins and well-known, solid epoxy resins derived from low molecular weight epoxy resins and bisphenol A, or SER/. v. Uncrosslinked 〃 means that the composition has a defined viscosity and no significant gelatinous reaction product. Coulomb means that the composition is dissolved in a suitable organic solvent. By high molecular weight 〃 means that the composition has a molecular weight of at least about 2 times, preferably at least about 3 times, of the starting epoxy resin. , acid value " means the amount of ruthenium (in milligrams (mg)) necessary to neutralize 1 gram (g) of the sample according to the procedure described in ASTM D 1639-83. 8 200835708 ''High carboxylic acid group conversion rate" means that the _ moiety and the intermediate of the dicarboxylic acid are completely reacted qualitatively, as measured by the acid value of the composition, such that the acid value is less than about 5. " The epoxy resins of the present invention can be prepared by a variety of methods, including, for example, the method described in U.S. Patent Application Serial No. 65, the entire disclosure of which is incorporated herein by reference. in.

For example, in U.S. Patent Application Serial No. 05,280, the method of reacting a low molecular weight epoxy resin with a dicarboxylic acid as needed in the presence of another difunctional monomer such as money A, the reaction It is carried out in a solution in the presence of a catalyst at a reaction temperature of up to about 22 (rc) to form the uncrosslinked soluble high molecular weight epoxy ester resin of the present invention. Preferably, the dicarboxylic acid and epoxy resin group The reaction is carried out in solution and in the presence of an inert reaction diluent. The reactive diluent is preferably used as an epoxy resin or a solvent miscible with it. The soluble monomer can be used to the appropriate degree of inertia and at atmospheric pressure. At low atmospheric pressure or superatmospheric pressure, it can be heated to the reaction range of the field and does not interfere with any inert organic solvent in which the carboxylic acid moiety reacts with the epoxide moiety. Substantially desirable solvents without impurities, impurities 曰IV low catalytic enthalpy Reactivity such as hydrogen peroxide or unaltered transition metal ions. Examples of suitable solvents include „Bite, triethylamine or mixtures thereof; Ν_pyrrolidone (ΝΜΡ) 'benzoic acid A Vinegar, benzoic acid ethyl vinegar, benzoic acid 1 butyl vinegar, cyclopentanone 'cyclohexanone, cycloheptanone, cyclooctanone, ?-hexyl pyrrolidone; and ethers or hydroxy ethers, such as dioxane, digan Alcohol dioxime ether, triol dioxime ether, diethylene glycol ethyl ether, diethylene glycol methyl ether 'dipropylene glycol oxime ether, 9 200835708 propylene diacetate, propylene glycol phenyl ether, propylene glycol methyl ether acetate, propylene glycol methyl scale And tripropylene glycol methyl ether; toluene, mesitylene, xylene, benzene, dipropylene glycol monomethyl ether acetate, halogenated solvent, such as dichlorobenzene, propylene carbonate, naphthene, butyrolactone, dimethyl Ethyl amide, dimethyl decylamine, esters such as ethyl acetate or butyl acetate and mixtures thereof. Other suitable diluents are organic compounds which are inert to the reactants at the reaction temperature, for example ' Various glycol ethers, such as ethylene glycol scales, ethylene glycol or propylene glycol monomethyl ether and esters thereof, such as ethylene glycol monoethyl ether acetate; ketones such as methyl isobutyl ketone, methyl ethyl Ketones and acetonides; and aromatic hydrocarbons such as methyl benzene, cyclohexane or mixtures thereof. The agent is cyclohexanone and propylene glycol methyl ether acetate. The solvent is usually used in an amount of from about 5 to about 300% based on the total weight of all the reactants. If the obtained resin product is coated When used for the purpose, the solvent is typically retained in the reaction mixture. Alternatively, the solvent is removed by any method, & steaming or the like.

The monomer concentration used in the first and eighth w " beetle is based on various factors, including special monomers, solvent and desired polymer. Typically, a monomer that uses 0. 60: i 〇 to 〇 95: i 〇 carboxylic acid to epoxy stoichiometric ratio. The low-division Lactobacillus sinensis used in the present invention comprises a polyepoxide which is a combination of more than one % of the emulsion groups of the parent molecule, that is, the parent molecule has more than one ^ 1U Alkoxy groups. The sputum is a saturated or unsaturated aromatic poly-, Λ.. clothing emulsion, if necessary, the vertical is replaced by thermal interference substances, such as halogen atoms, hydroxyl, ... soil, ether and analog . 10 200835708 ''Low Molecular Weight'' Epoxy Resin ～ and an aromatic epoxy scavenger having a number average molecular weight (Μη),; 10,000, preferably less than about 〇〇〇, More preferably, it is less than about, and it is generally useful in the present invention that the epoxy resin precursor in the low knife has an average molecular weight of from about 200 to about 10 Å. Preferably, 攸, scoop 2 〇〇 to about 8,000, and more preferably from about 250 to about 4,0 。. The preferred low molecular weight cyclic sorghum eucalyptus is a liquid polyepoxide comprising, for example, a liquid epoxy propyl arm of the polyhydric phenol & More preferably, 2,2-bis(4-_1 |, a a, having an average molecular weight of between about 340 and about 900 及 and between % and/or 500 equivalent of an oxide equivalent. Another 1 匕 base) propane epoxy propyl polyether. It is especially preferred to have an average score of + about 340 to about 900, and an oxide equivalent of between about 170 and about 5 Å and containing from about 1 to about Epoxypropyl poly-type of 2,2•bis(4-hydroxyphenyl)propane of about 1. 0 weight or more of saponifiable chlorine. As used herein, the term epoxide and the average molecular weight of the weight of each polyepoxide molecule per epoxide divided by the average number of oxirane groups present in the molecule is 0. The diepoxides used in the practice of the present invention include diglycidyl ethers of dihydric phenols, such as in U.S. Patent Nos. 5,246,751, 5,115, 〇75, 5,089,588, 4,480,082 and U.S. Patent No. 4,438,254, the entire disclosure of which is incorporated herein by reference in its entirety, in its entirety, in Incorporate this article by reference. Other suitable diepoxides include commercially available DER·16300 and 6〇〇 series epoxy resins and 11 200835708 commercially available from The Dow Chemical Company as α-Gan-* '--epoxypropyloxy An epoxy resin based on isopropylidene-bisphenol. Preferred oxides are those having an epoxy equivalent weight of from about 1 Torr to about 4,000. The most bauxite, the diepoxide is the di-epoxypropyl ether of bisphenol A, 4,4 is the base of the enzyme, 4,4-oxydiphenol, 4,4,·dihydroxybenzophenone , stupid phenol, hydroquinone, 9 9, · bishydroxyphenyl), 4,4,-dihydroxybiphenyl or 4,4,-dihydroxy-meta-'-- Diethylene propyl esters of dicarboxylic acids previously described. These aromatic bis-epoxides tend to be more reactive toward dicarboxylic acids than non-aromatic monoepoxides and are therefore more prone to cross-linking or gelation. In the present invention, it is surprising that the uncrosslinked soluble resin product is prepared using the aromatic bisoxide. 4 The amount of epoxy resin used is entangled according to the target molecular weight and epoxy functionality. The epoxy resin is used from about 3 〇 to % 85% by weight based on the weight of the reactants. More preferably, it is from about 40% by weight to about 75% by weight, and most preferably from about 45% by weight to about 3% by weight. ^ = The carboxylic acid used in the present invention may be, for example, saturated, unsaturated, and oligo-% aliphatic, aromatic or heterocyclic. Examples of such acids include, in particular, succinic acid, glutaric acid, adipic acid (AA), pimelic acid, suberic acid, cadaveric acid, oxalic acid, rosin acid, maleic acid, aconitic acid. , f 酉夂 (ehl〇rendle aeid), phthalic acid (pA), p-xylene: one (PA), isophthalic acid (IPA), 2,6-naphthalene diteric acid, 3, 4, -biphenylcarboxy-mes 4,4-diphenyldicarboxylic acid, malonic acid, hydrazine and cyclohexanedicarboxylic acid, 1,10, fluorene dioxime _ ring s夂m dodecanedicarboxylic acid, 13-cyclohexanedicarboxylic acid (1,3 CIIDA) 'l4·cyclohexanedicarboxylic acid (1,4-CHDA), tartaric acid, 12 200835708 払J齩 and serotonic acid. More preferred carboxylic acids include terephthalic acid, isophthalic acid, adipic acid, and mixtures thereof. The amount of carboxylic acid used in the invention can be varied in a wide range. The amount used in the present invention is about 1% by weight to about 50% by weight based on the weight of the reactants. More preferably from about 5% by weight to about 45% by weight, and most preferably from about 1% by weight to about 4% by weight - ▲ a reaction mixture of a low molecular weight epoxide and a carboxylic acid may optionally be in a difunctional monomer For example, a compound containing a hydroxyl group or a thiol group, such as a phenol or a thiophenol: is carried out below. Preferably, the optionally hydroxyl group-containing compound is one having at least one of a group attached to an aromatic nucleus. The lysole may be substituted or unsubstituted with a single or polyphenolic phenol. The poly(4) group can be obtained by condensing mono- or polyphenols with formaldehyde. Preferably, the preferred phenol is a polyhydric phenol having from 2 to 6 OH groups and up to 30 stone anti-atoms, including the following formulae:

Wherein X is a polyvalent member or group, and each R is independently selected from the group consisting of hydrogen, halogen 2 and a hydrocarbon group. Preferred groups represented by X are oxygen, sulfur, _s〇..., : a divalent hydrocarbon group having up to 1 carbon atom and a group containing oxygen, hydrazine, sulfur or nitrogen. Preferably, the age is 2,2-bis(4-hydroxyphenyl)propane (double hops, each of which is reversed) and X is isopropylidene. VIII 13 200835708 can be used in the practice of the present invention. Preferred dihydric phenols for preparing the resin of the present invention include 4,4,-isopropylidene bisphenol (bisphenol A), 4,4, di-diphenylethyl decane, 3,3'- Dihydroxydiphenyldiethylmethane, 3,4,-dihydroxydiphenyl-mercaptopropylmethane, bisphenol, 4,4'-dihydroxy-diphenyl, 4,4,-dihydroxydiphenyl Cyanomethane, 4,4,-dihydroxybiphenyl, 4,4, dihydroxybenzophenone, 4,4, dihydroxydiphenyl sulfide, 4,4,-dihydroxydiphenyl milling, 2, 6-Dihydroxynaphthalene, 1,4, dihydroxynaphthalene, phenol, resorcinol, o-diphenol, m-xylenol, p-quinol, chlorophenol, nitrophenol, hydroquinone, 2, 2-bis(4-hydroxyphenyl) propyl compound 2,2-bis(4-hydroxyphenyl)pentane, catechol, bisphenol, such as tetrabromobisphenol quinone and in the US patent Other dihydric phenols listed in 3,395,118, 4,43,254 and 4,480,082, which are incorporated herein by reference. a mixture of dihydric phenols. Among these dihydric phenols, bisphenol A, hydroquinone and mixtures thereof are preferred. The amount of phenol used in the present invention is based on the molecular weight of the phenol, the epoxide The molecular weight, the target equivalent of SEER, and the degree of branching. Generally, it is used in an amount of from about 1% by weight to about 6% by weight based on the weight of the reactants, more preferably from about 5% by weight to About 5% by weight, and most preferably from about 20% by weight to about 45% by weight. In general, the reaction of a low molecular weight epoxy resin with a dicarboxylic acid requires a catalyst or any material capable of catalyzing the reaction. In the case of an oxy resin, the dicarboxylic acid and the epoxy resin component are present in a catalyst for the reaction between the carboxylic acid group of the dicarboxylic acid and the epoxy group of the epoxy resin, and are sufficient to form a desired Contact under resin conditions. Catalysts useful in the present invention include, but are not limited to, phosphines, amines, 14 200835708 quaternary ammonium and pin salts, such as tetraethylammonium chloride, tetraethylammonium bromide, iodide Tetraethylammonium, diethylammonium hydroxide, tetrachloride Ammonium, tetra(n-butyl)ammonium bromide (ΊΈΑΒ), molybdenum tetra(n-butyl)ammonium, tetra(n-butyl)ammonium hydroxide, tetrakis(n-octyl)ammonium chloride, brominated tetra N-octyl)ammonium, tetrakis(n-octyl)phosphonium iodide, tetrakis(n-octyl)ammonium hydroxide, methyl chloroformate (n-octyl)ammonium chloride, bis(tetraphenylphosphinoalkyl) chloride Ammonium, ethyl acetate tri-p-tolyl scale/acetate complex, ethyl triphenyl scale/acetate complex, N-methylmorpholine, _ 2_phenylimidazole or combinations thereof and The analogs described in U.S. Patent Nos. 5,208,317, 5,109,099, and U.S. Patent No. 4,981,926, the disclosures of which are incorporated herein by reference. The most preferred catalysts include tetrabutylammonium bromide (TBPB), tetraethylammonium bromide, tetraethylammonium hydroxide, ethyltrimethylamine acetate, ethyltriphenyl scale and N-methyl acetate. Porphyrin, 2-Phenylimidazole (2-Phlm) Ruthenium Although any material capable of catalyzing the reaction can be used, a preferred catalyst is a phosphonium salt catalyst. Preferred phosphonium salt catalysts include scale or money salt catalysts. More preferred ruthenium salt catalysts include tetrabutylammonium bromide, tetrabutyl bromide (TBPB), ethyltriphenyl sulfonate iodide, tetraphenyl bromide and ruthenium bromide (n-butyl) ammonium and Corresponding chloride, iodide, bromide, acetate, formate, phosphate, borate, trifluoroacetate, oxalate and bicarbonate are best optimized for desertification of tetrabutyl scale (TBPB). The amount of catalyst used depends on the molecular weight of the catalyst, the activity of the catalyst, and the rate at which polymerization is desired. The catalyzed J used in the process of the present invention can be varied within a wide range as long as a catalytic amount is present. In general, the amount of the catalyst used in the present invention falls within the range of 50 from 1 scoop of 0·〇〇ι% to about ίο%, preferably from about 0 · 0 01. From about 0% to about 2%, more preferably from about 2% to about 2%, and most preferably from about 0.03% to about 1% by weight of the reactants. The epoxy resin composition of the present invention can be formed by the low molecular weight aromatic non-oxygen and dicarboxylic acid in the presence of a catalyst and in the presence of a solvent to form an uncrosslinked soluble high molecular weight epoxy ester. It is prepared by reacting under the conditions of a resin. _ Rain molecular weight "epoxy" means an epoxy resin product having a number average molecular weight (Μη); 〇'(10)0, preferably less than about 1 〇, 〇〇〇, and more preferably less than about 8,000. Usually, In the present invention, the amount of J-oxyl resin in the polymer has an average number of from about 1,000 to about 20,000, more preferably from about 1, 〇Q 〇 to about 1 〇, (9) 〇, and more preferably. The ground is from about 1,2 Torr to about 8,0. The reaction for preparing the SEER of the present invention can be carried out using a batch-man method or a continuous process carried out in a reaction extruder, as in the European patent Ep. • described in 0193 809. The process of the invention can be carried out in an open vessel or in a pressurer or in an injection molding machine. The conditions most favorable for the polymerization are determined by various factors, including The specific reactants, the solvent used and the catalyst used. Usually, the reaction is carried out in a non-oxidizing atmosphere such as nitrogen or other inert gas s. It is desirable to use an inert organic solvent for the reactants to ensure uniformity. Reaction mixture and adjustment in these Exothermic reaction under the conditions. The reaction conditions used in the method of the present invention may be changed. The time and temperature which are most advantageous for use are based on the specific monomers used, especially the reactivity of the 16 200835708, etc. The polymer and the organic liquid are varied. However, the optimum rate for the reaction to form the polymerization is generally from a reaction temperature in the range of from about 5 to about 3 Torr, from about atmospheric pressure to about 15 psig. The reaction is carried out under the reaction pressure of the range and from about 30 minutes to about 24 hours. The reaction of the bad oxygen resin with the carboxylic acid is advantageously carried out at elevated temperature. The reaction temperature is preferably from about 6 (rc to about 22). 〇t 'better from about i〇(rc

Up to about 150 c, and most preferably from about 120 ° C to about 140 ° C. The reaction time is preferably from about i hours to about 24 hours, and most preferably from about 2 hours to about 8 hours. Sustained reaction, i to achieve the desired conversion rate, which is determined by the acid conversion of the resin measured by acid number (AN) titration, and at the target molecular weight or blame of the resin, here Stop the reaction effectively at the point. In a specific example, the reaction is usually carried out by reacting at about 1 〇 (rc to about 120 ° C, and taking t / 1 for 5 ♦ bad emulsion with diruthenic acid and allowing The reaction is carried out for about 1 hour 聋 $ % 1 士至至 , , , 2 日 忪 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 放 :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: The product of the special product, r: 乂, having a epoxide equivalent of between about 600 and about 4, _, is a polyester resin product of the end ^0士约0.60至〇95哲甘i物5, will be "between about 170: tick and each ole with epoxide ^.,," 酴 between the two 酴: 环氧The reaction of the present invention can be carried out in a step-by-step process in which a liquid aromatic epoxy resin (LER), a dicarboxylic acid is reacted with a catalyst, and before the gelation, the desired epoxy reaction product is obtained. Termination of the reaction. Alternatively - if a difunctional monomer, such as a binary, is used as desired, the liquid aromatic epoxy resin can be reacted with the binary reaction. Dioxanoic acid may then be added to the reaction mixture; or the reaction may be first reacted with diremediation followed by addition of the binary to the reaction mixture; and prior to gelation, _ when the reaction product includes the target epoxy equivalent The reaction is terminated at a point in time. During polymer synthesis, the polymer is recovered from the reaction mixture by conventional methods. For example, a reaction mixture containing a polymer that becomes a sink can be transitioned to remove the solid polymer. The solid monomer is washed with water, sterol and other solvents which are non-solvent for the polymer, but which are good solvents for impurities. The polymer can also be poured into the non-solvent of the polymer by pouring the reaction mixture into a polymer. In addition, the precipitated product is collected and separated. In addition, the product polymer can be separated by vacuum distillation, wiped film to remove the solvent. Tan citrus - the epoxy ester resin of the present invention can be various rings Oxygen curing agents, such as phenols, private 'tannic acid', and resin and needles are cured with via groups or epoxy groups. The resin of the present invention can be polymerized with a hardener such as an amine. , a carboxyl-terminated polymer, a phenol-terminated polymer, an amine, a carboxylic acid or a phenol, or a resol phenolic polymer. This ♦ uses the medium! = SEE " for various industrial applications. Medium or other epoxy, laminated and composite layers. Industrial coatings are applied to the surface of the substrate to protect the coating (coating) and are typically cured or crosslinked, 18 200835708 to form a decorative The continuous film and the protective substrate. The protective coating generally comprises 3 organic polymeric binders, pigments and various coating additives, wherein the polymerization station, the "agent acts as a fluid vehicle for the pigment and imparts rheological properties to the fluid coating. Once cured Or when cross-linked, the polymeric binder hardens and functions as a binder for the pigment and provides adhesion of the dried coating film to the substrate. The pigment can be organic or inorganic, and in addition to its durability and hardness, it can provide opacity and color. The manufacture of protective coatings includes the preparation of poly

Adhesives, mixed component materials, pigments ground in polymeric binders and become thinner than commercial standards. Preparation of a bonding agent as described herein according to ASTM 4147-99 may include a wide variety of other additives, such as hardening: 'dye, pigment and flow modifier, flame retardant, auto-extinguish Examples of agents, dry agents, and all types of added flame retardants used herein for their known purposes include: monoammonium phosphate, diammonium phosphate, and trihydrate. The second additive may be in liquid or particulate form as long as the binder is still solid. A liquid coating composition comprising the tree 0 of the present invention and a suitable pigment, catalyst and additive can be obtained with any desired particle size and without any adverse effect of the binder. The coatings from the eight pieces of Gutian have a surprisingly good combination of properties. Depending on the choice of the polymer, the crosslinking agent, and the catalysis: the composition and the amount of the component, it is possible to obtain, for example, a good visibility of the fluid, high scratch resistance, good mechanical properties, and good 19 200835708 Composition of t, t long and good color stability. The water-dispersible coating composition containing the resin of the present invention is highly desirable for can coatings and coil coating compositions. In order to provide a further understanding of the present invention, including its representative advantages, the following embodiments are presented. The various terms, abbreviations and nomenclature used in the materials used in the following examples are explained as follows: "EEW" represents epoxy equivalent. 10, AN, and represent the acid value. D.E.R.TM3 31 ( EEW= 188) > D.E.R. 3 83 ( EEW= 180)

And D.E.R. 354LV (EEW=170) is a liquid aromatic epoxy resin (LER). D.E.R. 661 (EEW=534), D.E.R. 667 (EEW = 1 850) and D.E.R. 669E (EEW=3290) are solid epoxy resins (SER). These products are commercially available from The Dow Chemical Company. , A1 " is a catalyst from Morton Chemical Company (70% by weight of n-Bu4POAc / HOAc in decyl alcohol). TBAB, TBPB, 2-Phlm, TPA, AA, PA, 1,4-CHDA, 1,3-CHDA, diglyme, cyclohexanone, DowanolTM PMA (PMA), Dowanol PM (PM) and Di(propylene glycol) methyl ether acetate (DPMA) is a commercially available chemical from Aldrich. The isophthalic acid (IPA) is a commercially available acid from Aldrich or MB Biomecidals, Inc.

Methylon 75 108 is a methylol phenyl allyl ether commercially available from Occidental Chemical Co. 20 200835708. Superphosphoric acid (105%), methyl ethyl ketone (ΜΕκ), lactic acid, and 2-butoxyethanol (DowanolTM EB) are commercially available chemicals from Aldrich Chemical c〇. HPLC 〃 represents high pressure liquid chromatography. HPLC grade water, acetonitrile (ACN) and tetrahydrofuran (THF) are commercially available chemicals from EMD. BYK-310 Shiyang Oxygen Surfactant is a product from Byk Chemie. Various standard test methods and procedures for measuring certain properties in the examples are as follows: Epoxide equivalent (EEW) titration is based on equivalent The steps of ASTM D-1652-97 are completed. The acid number (AN) analysis was carried out according to the procedure equivalent to ASTM D 1639-83. Cyclic dimer analysis is performed by using a water/ACN gradient elution procedure

HPLC of the Agilent 1100 LC system was completed. The average number of tens of analyses was done using the viscotek GPC analysis system. The following examples are for illustrative purposes and are not intended to limit the scope of the invention. All parts and percentages are by weight unless otherwise indicated. 1 — The solution resin of the rouge product advanced reaction was carried out using the following procedure: 7-class 21 D.E.R. 661 of Model 200835708 - The preparation of AA SEER is described below. Add 100 grams (g) DER 661 SER (previously dried under 18 hours for 18 hours), 9.22 grams of AA and 11 gram grams of diethylene glycol dimethyl scales with mechanical stirrer, condenser, heating A 1 liter (L) resin kettle with a thermocouple connected to a programmable controller. The reactor was filled with n2 while heating to 110 with gentle mixing, at which time 〇77 g of TBAB in 1 〇 1 # (mL) diglyme was added. (view all at about 60 ° C)

The solids of the fractions were dissolved. The reaction mixture was maintained at about 112 for a period of 32 Torr. During this time, samples were occasionally taken for EEw titration. The results of this Example 1 are shown in Table 1 below. Example 2 - Preparation of Resin Product Example 2 was carried out in addition to (10) grams of adipic acid (AA) as described in the above Examples. In addition to use

Comparative Example A Comparative Example A is as in the above example! As described above, 26.7 grams of bisphenol A, 32 7 grams of adipic acid, hydrazine: gram DER 331 epoxy resin and 公16 grams of A· catalyst were used at the reaction temperature, but without using a solvent, as shown in the table. The one shown in 1. - meaning

_Comparative Example B Comparative Example B is as in the above, using 24.3 grams of bisphenol A, 29.8 grams of hexamethylene, 15 在 at the inverse _·- -V w 丨 / J , / temperature 〇 DER 331 epoxy resin and 〇 15 g A] catalysis

Field, ~ rabbit 丨 > T...' but not > Under the bath, as shown in Table 1. Comparative Example C 22 200835708 Comparative Example c used 33.3 grams of adipic acid, 150.0 grams of DER·331 epoxy resin and 0·14 g of A at the reaction temperature as described in the above Examples. -1 Catalyst, but not using a solvent, as shown in Table 1.

Comparative Example 比较D Comparative Example D, Part 1 is as described in Example 1 above, using 33. 3 grams of adipic acid, 150.0 grams of DER 331 epoxy resin and 0 · 1 4 at the reaction temperature. The gram of the A-1 catalyst was carried out without using a solvent as shown in Table 1. Part 2 of Comparative Example D was carried out using the product from Part 1 and 26.1 g of bisphenol a and 〇 16 g of A-1 catalyst at the reaction temperature, as shown in Table 1. Table I. Reaction of liquid epoxy resin (LER) or solid epoxy resin (SER) with aa Example reactants Catalyst conditions Target actual EEW Example 1 DER 661 + AA TBAB 110〇C, 50 % in diethylene glycol Dimethyl ether in 1800 1592 Example 2 DER 661 + AA TBAB 110〇C, 50 % in diethylene glycol dimethyl ether 3200 3115 I comparative real LER + A-1 130-180〇C _1800 — gel 23 200835708

Example A BA+ AA --______ Comparative Real LER + A-1 130-180〇C —------ 1150 ——————— Gel Example B BA+ AA --_____ Comparative Real LER + A-1 160°C ---——__ 530 ----- Gel Example C AA Comparative Real LER + A-ι 130°C ——~·-__ 530 --- 533 Example D-AA Part 1 -------Comparative Real Comparison " 1 ----A-1 160 °C ——~~~·---_ 1800 -----~ Gel Example D - Example D - Part 2 Part 1 + zhang & /nl -> BA 3 ΐΑ ί 3-20 - The chelating product The SEER resin was prepared using two methods. In both methods, the "uneven sentence" is generated at the beginning of the inverse (four), when the used double-handed (DCA) ^ is heated completely, _ becomes a clear solution. Regular sampling will be performed, = EEW A AN Changes. When the advanced reaction is over, allow the yam liquid ~. 卩 to below 90 C and then quickly transfer to the glass jar. LER, DCA, solvent and catalysis (4) to the population with reflux condensation H, N2, and The air-driven motor connection is disturbed, the rod and the thermocouple and the heating sleeve connected to the temperature controller are in the milliliter glass. The reaction mixture is heated to a specified temperature in a small A i hour and then maintained at a constant temperature until The target EER is reached. In the method A, the reaction takes a period of time between the time of the desired solution temperature and the time after the desired EEW of 24 200835708 is reached. ^LER, DCA and part of the solvent (about 9% by weight) were added to a 5 cc glass resin jar equipped with Method A as above. The reaction mixture was heated to the specified temperature in less than 1 hour. Then the catalyst and the remaining solvent were added. (about 10 weights ) Or dissolved in the remaining solvent (~ 10 wt%) catalyst. The solution is maintained at a specified temperature, the EER until it reaches the target. The reaction time-based catalyst is added from time to time to reach the target EEW.

The reaction conditions for preparing the resin are shown in Table II, and the results of the analysis of the product of Shushu are shown in Table III. Table II. Reaction conditions for preparing rouge LER DCA Solvents >1 Tanning agent C Warming DE (g) Acid (g) Catalyst (g) Example a Rd (°C) 3 383 200.03 IPA 79.30 II Glycol TBPB 1.9700 110 Diterpene ether 4 354LV 200.00 IPA 84.70 Diethylene glycol TBPB 2.0100 110 Diethylene ether 5 354LV 200.08 IPA 90.40 Diethylene glycol TBPB 2.0500 110 Diterpenoid scale 6 383 199.97 IPA 84.90 PMA TBPB 2.0108 1 1 Π 7 383 200.00 IPA 84.88 PMA TBPB 2.0100 i 1 U 140 8 383 25.07 IPA 10.61 Diethylene glycol TBPB 0.2493 160 — A scale 25 200835708

9 —---- 383 200.06 ΤΡΑ 84.91 PMA TBPB 2.0100 140 10 383 200.01 PA 84.91 PMA TBPB 2.0111 140 11 Ι_183 24.96 IPA 10.58 PMA TBPB 0.1252 140 12 60.05 IPA 25.51 PMA TBPB 0.1492 140 13 __183 179.98 IPA 76.39 Cyclohexanone TBPB 1.8074 140 14 383 64.98 IPA 27.59 DPMA TBPB 0.0640 180 15b 383 121.87 1,4- 53.50 PMA TBPB 1.2353 140 CHD ---- A Use Method A and 50% by weight of solvent unless otherwise stated.

/ mixture · 1 8 wt%. The weight % of the e catalyst is based on the amount of lER, DCa and the catalyst. The weight % of the solution is based on the total amount of the reaction system, i.e., LER, DCA, catalyst, and solvent. dD E R• Epoxy resin type. Table Π (continued) · Reaction conditions for preparing the resin Example 3 I, ER DCA Solvent d 7. Seven doses c Temperature (°C) DERd (g) Acid (g) Catalyst (g) 16 383 200.02 IPA 84.89 PMA TBPB 2.0123 140 17 331 199.97 IPA 81.19 Cyclohexanone TBPB 1.9805 140 18 383 200.00 IPA 79.40 Cyclohexanone 2-Phlm 0.1975 140 19 383 200.02 TPA 42.45 PMA TBPB 2.0100 140 20 383 180.01 IPA 76.40 Cyclohexanone TBPB 1.8080 140 a Use Method A And 50% by weight of solvent unless otherwise stated. b Solvent · · 18% by weight. The weight % of the e catalyst is based on the amount of LER, DCA, and chemistry. The weight % of the solution is based on the total amount of the reaction system, system, LER, DCA, catalyst and solvent. dDER• Epoxy steam moon type. Table IIL SEER EEW, AN and Μ Implementation time LER acid ------ EEW ~ AN -----Ί Λ / Γ ^ Example a (minutes) Actual Μ 3 365 383 IPA 1,800 1,736 —~~ ~— 0.2 0 Q AC\ 4 500 354LV IPA 1,800 1,754 0.2 ^ 5 〇U 3 6 1 S 5 470 354LV IPA 3,200 2,869 0.2 7 1 RA 6 515 383 IPA 3,2〇〇3,265 0.1 / 5丄o 4 fi〇〇7 85 383 IPA 3,200 3,612 0.1 6 671 8 30 383 IPA 3,20〇3,354 0.1 ^ \j / x ^ 1 1 Q 9 160 383 TPA 3,200 3,440 <0.1 J 5丄丄7 4 440 10 67 383 PA 3,20〇3,607 0.5 7,25 1 11 149 383 IPA 3,200 3,156 1.6 5,191 12 285 383 IPA 3,200 3,234 1.2 6,194 13 45 383 IPA 3,200 3,628 0.1 14 83 383 IPA 3,20〇4,110 0.1 1 , 778 15 78 383 1,4- CHDA 3,200 3,167 0.6 3,732 16 45 383 IPA 3,200 3,570 1 EEW and AN are measured after the entire resin solution has cooled to ambient temperature' unless otherwise stated. b A small amount of sample (often < 20 grams) was taken from the bulk solution and used for EEW and AN analysis. 27 200835708 Table 111 f continued) · SEER EEW, AN and Μη

The aEEW and tether are measured after the overall resin solution has cooled to ambient temperature unless otherwise noted. b A small amount of sample (often < 2 gram) was taken from the bulk solution and used for EEW and AN analysis. The results in Tables I-III show that an uncrosslinked soluble high molecular weight epoxy ester resin having the desired properties is obtained. A comparative example of a steel sheet of commercially available L-type, T4CA, surface 5 无 of tin-free steel (TFS - a sheet of single-reduced electrolyte chromium coated) is used in this embodiment. The metal substrate in the example. The coating formulation was taken to the TFS panel and cured according to the procedure described in ASTM 4147_99 to give a coating thickness of 〇2〇+/_〇〇2 mil. The coated panels were subjected to a mek resistance test according to ASTM D 54() 2_93, a maximum double wear (DR) quantity test before coating failure, and a wedge-shaped f flexibility test according to ASTM D 328i-84. The pasteurization resistance of the lactic acid is immersed in a vial containing 2% by weight of lactic acid and a wedge-shaped curved plate sample heated at 3G for 12 minutes in TC (Dm. The completion of the coating is described using the grading system described in the following list 28 200835708 0 A. Table A. Grading of the grading system of the pasteurization resistance test

There are no red stains or bubbles on the curved or flat section. There is no red stain on the flat section or the bubbles are red-stained on the flat section, but there are no bubbles on the flat section. There are some small bubbles on the flat. The red dyed coating on the section with many large bubbles destroys all test lines and is repeated here and is reported as the average of the results. The properties of some of the coatings prepared in Examples 3-20 were measured and the results of the 5 Hai specific examples are shown in the following table iv.

29 200835708 Table IV. Properties of resin coatings cured with phenolic resin hardener and H3P04 catalyst at 205 °c for 10 minutes Examples Resin hardener (% by weight) H3P〇4 (% by weight) Additive a ( Weight %) MEK DR (maximum number of passes) Wedge shape • Bending (% of bad) LAP test Comparative Example E DER 669E 15 0.75 — 125 25 3 21 9T / 3 83 / IPA (Example 6) 15 0.75 --- 175 3 0 0 22 9T / 3 83 / IPA (Embodiment 6) 25 0.75 — 200 41 4 23 9T / 3 83 / IPA (Embodiment 6) 15 1.50 —— 125 33 4 24 7T / 383 / IPA (Example 3 ) 15 1.50 0.1 150 33 2 25 9T / 3 83 / TPA (Example 9) 15 0.75 0.1 150 3 0 2 30 200835708

Table IV. is a soluble acid resin hardener and a H3P〇4 catalyst at 2〇5. Properties of the resin coating cured under the arm for 10 minutes

The results of the aByk-31 antimony surfactant in Table IV show that the uncrosslinked soluble high shell coating of the present invention can be obtained from the present invention by reference to a particular Pieces. Ming, but those who have in the technical field, the second narrative and the invention itself can lead to the need to k * 0 硪 will understand this

^ ^ ^ t The syllabus explained in this article, test and determine the true scope of the invention. Accordingly, the scope of the patent. The attached application (simplified description of the drawing) cover [main symbol description] 31

Claims (1)

200835708 X. Patent application scope: Material, = gel-free aromatic group-containing epoxy vinegar resin composition and right second I3 has terminal epoxy group, with epoxy functionality greater than Bu: !=: at 1 and A soluble high molecular weight epoxy vinegar resin having an epoxy equivalent (eew) of about or more, and a % by weight; the uncrosslinked 7-merity high molecular weight epoxy resin is directly derived from (4) a low molecular weight aromatic side The reaction of a bis-oxygen resin with (b) a dicarboxylic acid. 2_: Root (4) The epoxy S resin of the first aspect of the patent range, wherein the low-quantity aromatic epoxy resin comprises a di-cut diepoxypropyl bond. 3. The epoxy S resin according to item 2 of the scope of the patent application, wherein the second reading comprises 4,4,_isopropylidene double, 4,4,_di-diphenylethyl-t,3 '3 - mono-diphenyldiethylmethane, 3,4, dihydroxydiphenyl-methylpropyl-methyl-salt, 4,4'-di-diyl-diphenyl scale, 4,4, -di-diphenyldiphenyl-based methane, 4,4,-dihydroxybiphenyl '4,4, dihydroxybenzophenone, 4,4,_-pyridyl diphenyl sulfide bond 4,4,_ Di-based diphenyl stone, 2,6-di-pyridyl, M, · di-naphthalene 'catechol' meta-benzoquinone hydrogen snail or tetrabromo bis-A. 4. The epoxy vinegar resin according to item 2 of the patent application scope, wherein the bis-lactic propyl ether comprises a bicyclo propylene propyl ether of hydrogen bismuth, a diethylene oxide propyl squam or a resorcinol Di-epoxypropyl ether. 32 1 · Resin according to the first item of the fourth paragraph of the fourth paragraph, wherein the diterpene acid comprises adipic acid, isophthalic acid, p-dicarboxylic acid or a mixture thereof. A binder composition comprising an epoxy ester resin as claimed in the first item of the patent application. A binder composition comprising an epoxy ester resin and a hardener as described in the patent application No. 200835708. 8_ The binder composition according to claim 7, wherein the hardener comprises an amine-terminated polymer or a polymer, a carboxyl-terminated oligomer or polymer, and a phenol-terminated oligomer Polymer or polymer, phenolic resole polymer or polymer, polyfunctional amine, carboxylic acid or phenol. 9. The binder composition according to item 8 of the patent application, which further comprises a pigment, a filler, a flow modifier, a surfactant, a lubricant or a solvent. 10. A liquid coating material comprising a binder composition as in claim 7 of the patent application. 1 1 · A complex material a' which comprises a binder composition and a substrate as claimed in claim 7 of the patent application. 12 · According to the application of the patent, | s, - 引 围 围 围 11 11 11 11 11 11 11 11 11 围 围 围 围 围 围 围 11 11 11 11 11 11 11 Acyclic: 33