TW561164B - Acid functional and epoxy functional polyester resins - Google Patents

Abstract

Carboxyl functional polyester resins obtainable by reaction of (a) at least a compound of the formula I, wherein x >= 1 wherein R1 and R2 each may represent an alkyl group having from 1 to 4 carbon atoms or wherein R1 and R2 may form together the remainder of cyclic cycloalkylgroup (A1), optionally mixed with minor amounts of a corresponding compound of formula I wherein x=0, or anhydride thereof (A2), (b) at least one diol compound B, comprising two aliphatic hydroxyl groups, which may each independently be a primary or a secondary hydroxyl group; (c) optionally one dihydroxymonocarboxylic acid compound C, comprising a tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups which may each independently be primary or secondary hydroxyl, and (d) optionally a trihydroxyalkane (D1) or tetrahydroxyalkane (D2); the molar ratio of compounds (A1+A2):B:C:D1:D2 being X+Y+2Z+3Q+P:X:Y:Z:Q, wherein X ranges from 1 to 8, Y ranges from 0 to 8, Z ranges from 0 to 4 and Q ranges from 0 to 3 and wherein P ranges from 1 to 5, preferably from 1 to 3 and is most preferably equal to 1, at a temperature of from 100 to 240, until essentially all the hydroxyl groups as initially present in the reaction mixture have been reacted; linear or branched polyglycidyl esters derived there-from and powder coating compositions comprising one or both type of these ester types.

Description

56ll64 A7 · B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs i. Description of the invention (1) The present invention relates to a polyester resin having a carboxyl functional group, a method for preparing the resin, and a glycidol of the polyester resin having a compound base. The obtained polyglycidyl ester resin, a coating composition, in particular a powder coating composition or a liquid coating composition composed of the carboxyl-containing polyester resin or the polyglycidyl ester resin, and the use of the mentioned coating A hardened product obtained from the composition. Powder coating compositions composed of the solid reaction product 2,2-bis- (4-stemylphenyl) propane and epichlorine have long been known. The composition obtained by this method can resist hydrolysis, but its UV resistance is not good, so it cannot be applied to places where the outdoor environment is highly tolerant, such as building materials or car paints. The diglycidyl ester resin published in European Patent Application No. 44736〇A (EP · A-447,360) exhibits good quality when applied to outdoor highly tolerant coatings and molding compositions. Because the carboxyl group present at the end of the ester chain in the precursor of the tricarboxylic acid pre-addition causes the precursor to have the characteristics of an acid anhydride half-ester group, it is necessary to avoid strong testing when glycerination of a thin version such as the driver & water. It is carried out under ambient conditions to avoid hydrolysis of the glycidyl esters formed and / or hydrolysis of one or more ester groups on the resin backbone. Therefore, the triglycidyl esters prepared will contain a considerable amount of hydrolyzable gas and / or will contain low molecular weight, which will cause: the problem of hydrolysates, as described in the following documents, water bases with excellent alkaline stability Sex Paint " Xlllth im. Conf. 187, Athens, Greece, P 175. From Example 2 of EP-A-447,360, a high content of hydrolyzable chlorine was observed, and this was related to the prepolymer of anhydrous hexahydroanthraphthalic acid with epoxidized 2.1. This product contains 15% chlorine. Such high levels of residual gas are undesired in general coating compositions. And, according to the paper size Gu Gu Country_County (CNS) Α4 specifications) (Please read the precautions on the back before filling this page)

561164 A7 B7 V. Description of the Invention (2) EP-A-447,360 reports that triglycidyl ester is a liquid and cannot be applied to powder coating compositions. For example, in international application WO 96/11238, it is indicated that those skilled in the art are engaged in this special hardenable coating. Because the epoxy resin contains an alicyclic structure, the cured film can only exhibit the disadvantage of brittleness. Brittleness also makes it unsuitable for coating applications, as brittleness often results in reduced adhesion. From European Patent Application No. 06 3 443 4 A2, it can be known that a linear tertiary aliphatic carboxyl functional polyester resin can be prepared by the following reaction: (a) at least one composed of a monofunctional primary or secondary hydroxyl group Compound Af and / or at least one compound A "consisting of a monofunctional primary or secondary and hydroxyl group and a tertiary aliphatic carboxyl group; (b) at least one compound consisting of two aromatic or secondary aliphatic carboxyl groups or Aromatic or cycloaliphatic dicarboxylic acid compound B composed of anhydrous anhydride; printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) (c) at least one type consists of two fats Diol compounds c consisting of hydroxyl groups, both of which may be primary or secondary hydroxyl groups; and (d) at least one dihydroxy monocarboxylic acid composed of tertiary aliphatic carboxyl groups and two aliphatic hydroxyl groups Compound D, in which the hydroxyl group may be a primary or secondary light group; the molar ratio of compound A ′: A '': B: C: D is M: N: X + Υ + 1: χ: γ where M + N = 2, X goes from 2 to 8 and Y goes from 2-N to 8, controlling temperature Within the range of 100 ° C to 240 ° C until the reaction of all non-tertiary carboxyl groups in the reactants is complete. _______ ~ 5 ~ _ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 561164 A7 __________ 5. Description of the Invention (3) And this patent also published that the polyglycidyl ester resin is composed of the polyester resin containing linear tertiary aliphatic carboxyl functional groups and Excess epichlorohydrin is formed by reacting with appropriate catalyst under appropriate test environment. It is preferred that the polyester resin is reacted with epichlorohydrin, whether it is a polyester resin or an epoxidized polymer obtained by the reaction. The ester resin can be reacted with a cross-linking agent to be applied to a powder coating composition. From European Patent Application No. 0720 997 A2, these polyester resins containing a linear tertiary carboxyl functional group and an epoxy group-containing polymer are known. These polyester resins are formed by the reaction of: a) at least one aromatic and / or cycloaliphatic acid compound A consisting of two aromatic and / or secondary aliphatic carboxyl groups or their anhydrous anhydrides ; b) At least one hydroxy compound b composed of two aliphatic hydroxyl groups, both of which may be primary or secondary hydroxyl groups; c) at least one hydroxy-substituted carboxyl group composed of an aliphatic carboxyl group and at least two aliphatic hydroxy groups Acid compound C, where the hydroxyl groups may be primary or secondary hydroxyl groups, and d) a carboxylic compound composed of a monocarboxyl group may be present; the molar ratio of compound A: B: C: D is

(X + Y-1): X: Y: Z where X is from 2 to 8, Y is from 2 to 8, and Z is from 0 to 2. These polyester resins can be used with appropriate hardeners to make powder coatings. Product, or react it to the relative glycidyl ester resin, and then use it with appropriate hardener to become a powder coating product. Although the linear tertiary aliphatic carboxyl functional polyester resin or polyglycidyl ester resin requires high outdoor tolerance (ultraviolet light stability) and hardened material resistance ______- 6 -___ This paper standard applies to Chinese national standards ( CNS) A4 specification (210X297mm) --- r-I-^ ---- φII (Please read the notes on the back before filling out this page}-Order f 561164 A7 B7 V. Description of the invention (4) Hydrolyzability Some improvements have been made to make it suitable for commercial powder coatings, but it is still necessary to further improve the above properties. On the other hand, it is derived from carboxylated polyester resin and epoxidized. Novel coating adhesives for the highly tolerant powder coatings market obtained by resin hardening have been proposed at the following seminars: Waterborne, Higher Solids and Powder Coating Symposium, February 5-7, 1997, New Orleans LA, USA, T Agawa and ED Dumain, p. 342-353, uNew Two-component Powder Coating Binders: Polyester acrylate hybrid as TGIC Cure Alternative o Nevertheless, as described on page 3 5 3, for the flatness of the coating film and lower hardening temperature And UV light tolerance need to be further improved to facilitate the competitiveness of automotive finishes and exterior window frame finishes. Therefore, an object of the present invention is to obtain a polyester resin with an acid functional group, and it can be easily glycidized. In order to form a polyglycidyl ester resin, the carboxylic acid functional polyester resin and the polyglycidyl ester resin must exhibit better properties in order to be used in outdoor tolerant powder coating compositions, and exhibit better environmental protection. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (read the precautions on the back and then fill out this page) Based on a large amount of research work and experiments, the target polyester resin with carboxylic acid functional groups has been developed Therefore, the polyester resin having a carboxylic acid functional group provided by the present invention is formed by the following reaction: a) At least one compound of the following formula I-7-This paper is in accordance with Chinese National Standard (CNS) A4 specifications ( 210X 297 mm) 561164 A7 B7 — ----- V. Description of the invention (5)

〇 0 II Η Η II HO-C-C- (CH2) x-C-COH Ding

II R1 R2 where d where R i and R2 may each represent an alkyl group containing 1 to 4 carbon atoms, or where R # R2 may be linked to ~ CH_ (CH2) X-CH ~ cycloalkyl, preferably 1, 4 -Cyclohexanedicarboxylic acid (A1) is combined and may be mixed with a small amount of molecular formula Ηπο) or its anhydride compound (A2); b) at least one diol compound B, which includes two aliphatic hydroxyl groups, of which hydroxyl groups It may be a primary or secondary hydroxyl group; c) a dihydroxy monocarboxylic acid compound c, which includes a tertiary aliphatic carboxyl group and two aliphatic hydroxyl groups, and each of the hydroxyl groups may be a primary or secondary hydroxyl group; and ( d) one of the trihydroxyalkanes (D1) or tetrahydroxyalkanes (d2); printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) A1 + A2) ·· B ·· C ·· D1: D2 can be expressed as X + Y + 2Z + 3Q + P: X: γ: z: q, where 乂 由! From 8, γ is from 0 to 8, Z is from 0 to 4, Q is from 0 to 3, and P is from 1 to 5, preferably from 1 to 3, and most preferably equal to 1. The temperature is controlled between 100 ° and 240 ° C. If compound C is present, the temperature is preferably controlled between 180 ° and 210 ° C until the hydroxyl groups in all the initial compounds are completely reacted. A few words of the use amount of A2 means that it should account for 0 to 10% of the total moles of a 1 and a2. The preferred carboxylic acid-functional polyester resin should be controlled at γ > 〇 (when ---- -------------- 8-______ This paper size applies Chinese National Standard (CNS) Α4 specification (210 × 297 mm) " " 561164 A7 V. Description of the invention (6) Z + Q = 0), or Z + Q> 0 (when γ = 0). Polyester resins with aliphatic carboxyl groups have the advantage that the side groups on the main chain are all tertiary carboxyl groups except that the secondary carboxyl group is generated from 1,4-cyclohexane dicarboxylic acid at the chain end. By changing the compounds D 1 and D 2, the shape of the main chain can be controlled to be linear (without the addition of Compound D) or branched (with the addition of Compounds 0 1 and / or d 2). The advantage of using the above technique is that the molecular weight distribution of the invention and the number average molecular weight of the resin can be controlled by special reactants and their ratios. When the tertiary aliphatic carboxyl group that may appear in the compound C does not participate in the given esterification reaction, the non-terminal secondary aliphatic carboxyl group and the terminal secondary fat can be made with epigas in a standard alkaline environment. The carboxyl group of the group is glycidized to form a polyglycidyl ester resin having a low hydrolyzable content. The weight ratio of hydrolysable halide content to the total composition is usually less than 1%, and preferably less than 0.7%. The present invention exhibits other advantages exhibited by glycidation, and the coating composition, especially by the The advantages of the carboxyl polyester resin and / or the powder coating composition or liquid coating composed of the polyglycidyl ester resin and its hardened product are the same as the advantages of the carboxyl polyester resin mentioned above. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) The preparation of fatty carboxyl polyester resins is generally performed by traditional esterification, preferably by azeotropic condensation. Note that the secondary carboxyl group at the end is provided by 1,4-5 hexanedicarboxylic acid. In this condensation reaction, compounds A, B, C may exist, 01 or 02 may be placed in the reactor at the same time, and then the temperature is increased from room temperature to 180 to 240 degrees. If compound 6 is present, the temperature is preferably 1 8 Between 0 degrees and 2 10 degrees, maintain for 3 to 8 hours, making anti -____ _____ ~ 9 ~ ___ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public 1-56ll64 central standard of the Ministry of Economic Affairs) Printed by the Consumer Cooperative of the Bureau A7 B7 Fifth, the invention description (7) should be started and removed by continuous azeotropy. Usually azeotropic removal of water continues until at least 90% of the hydroxyl reaction is completed, preferably 95% The benzyl reaction is completed. Accelerators used in the esterification technique, such as dibutyltin oxide, p-toluenesulfonic acid, tin octoate, zinc octoate, and castor oil esters, can be used in the esterification reaction, but in general There is no need to add an accelerator. To make sure that the first-order groups of the end are derived from the diacid of the formula I (x >> l), especially 1,4 · cyclohexanedicarboxylic acid, and not 1,2-structure from χ == 〇, especially 丨, 2 _cyclohexanedi A part of the monoacid derived from the acid, such as 1,4-cyclohexanedioic acid, is preferably added to the reaction at the end of the reaction. The compound B suitable for the method of the present invention has two aliphatic hydroxyl groups. The "compounds" include branched aliphatic, cycloaliphatic, or araliphatic compounds, and the # to radicals thereof may be primary or secondary light radicals. For example, propylene glycol, neopentyl glycol, hydrogenated dihydroxyphenylpropane (HDPP ), Hydrogenated 4,4, -dihydroxybiphenyl, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy -2,2-Dimethylpropyl ester and 2-butyl-2-ethyl-1,3-propanediol or mixtures thereof. Among them, HDPP is particularly suitable. A typical example of compound C suitable for the method of the present invention is two Methylolpropionic acid. A general and preferred example of compound D 1 used in the preparation of the branched carboxyl polyester resin of the present invention is trimethylhydroxypropane, and a preferred example of compound D 2 is isoprene tetraol. As mentioned above It is stated that the fatty carboxyl polyacetate resin of the present invention prepared by this method can be used in an appropriate alkaline environment. , Addition of excess gas -____ table --10 _ ______ This paper scales applicable Chinese National Standard (CNS) Α4 size (210X297 public Chu) (Please read the Notes on the back page and then fill in}

、 1T f 1 × ^ ---- 1__________________ 6 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5 A7 '-......... — ， Invention description (8) ~ Reaction of alkanes with possible accelerators A polyglycidyl ester resin is formed. Ordinary epichlorohydrin can be used for this reaction. The polyglycidyl ester resin of the present invention combines the advantages of low toxicity and excellent coating properties <. More special is that it has excellent weather resistance, acid resistance, excellent coating fluidity, smooth and compact appearance, and also takes into account the characteristics of hardness and toughness. The polyglycidyl ester resin derived from the polyester resin having a carboxyl group (wherein y is from i to 4, while X is from 1 to 6, z is from 0 to 2 and Q is from 0 to 2) The result is the most excellent coating composition suitable for outdoor tolerance. The best polyglycidyl ester resin can be obtained according to X = 3, γ = 丨 5, z = 〇, Q = 0. The powder coating composition developed from the present invention can be added with a crosslinkable resin to the linear, branched or star-shaped aliphatic carboxy polyester resin of the present invention mentioned above, or can be crosslinked. The resin is a polyglycidyl ester resin obtained by glycidizing the linear, branched aliphatic carboxyl-containing polyester resin. The powder coating composition developed from the present invention has an additive amount of a crosslinkable resin. Generally speaking, it provides the number of reactive groups of the crosslinkable resin and a linear or branched aliphatic aliphatic carboxyl polyester resin. The number of hydroxyl groups is the same or the epoxy group of the polyglycidyl ester resin is the same. Crosslinkable resins suitable for the aliphatic carboxyl polyester resins of the present invention include high-endurance epoxy resins for outdoor use, for example, polyglycidyl ester resins according to the present invention, published by European Patent Application Publication No. 5 Polyglycidyl ester of α, α, -di-branched dicarboxylated glyceride published in 18,408 This paper applies Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) (Please read the precautions on the back before Fill out this page]

561164 A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (9) Resin, and a polycarboxylic acid published by European Patent Application Publication No. 366,205, which is connected to two calcined substituents by an alpha carbon atom Of polyglycidyl ester. Crosslinkable resins suitable for combination with the polyglycidyl ester resin of the present invention are corresponding acid-functional polyester resins such as the present invention, solid polybasic acids (such as sebacic acid, 1,12-dodecanedicarboxylic acid), Anhydrides such as polyazelaic polyanhydrides, acid-functional polyesters such as the reaction product of 1 mole trimethylolpropane and 3 mole hexahydrophthalic anhydride, 1,6-hexanediol and excess 1 , 12-Dodecanedioic acid reaction product, 4 mol 1,10-decyl diacid, 149 mol hexanediol, 0.47 mol 1,1, 3, trimethylol propane and 〇27 A product of the co-reaction of Moore's isopentaerythritol, 4 moles of 1,10-decyl diacid, 12 moles of hexanediol, 0.45 moles of trimethylolpropane, 029 moles of isoprene tetraol, and 0.21 The product of the reaction of Mol dimethylolpropionic acid, the product of the reaction of 1 Mol hexamethoxymethyl melamine and 3 Mol hydroxytrimethylacetic acid and amine hardener. Most of the preferred combinations are aliphatic carboxy-functional polyester resins and polyglycidyl ester resins obtained by glycidol. The powder coating composition derived from the present invention may further contain accelerators and other additives, just like other processes suitable for use in powder coating compositions. Suitable accelerators are, for example, quaternary amines and phosphine salts; metal salts / compounds such as octanyl tin (Π); test compounds such as midazolam; and tertiary amines such as diazobicyclic undecylcarbamate . The amount of accelerator added is generally from 0.1 · 2% to 2% by weight of the total powder coating composition. This paper is suitable for size_ (CNS) A4 «FT21〇X 297 ^ t) (Please read the note on the back first (Fill in this page again)

1T f. M1164 \ Five A7 _______ Description of the invention (10) The hardening time and hardening temperature applicable to the powder coating derived from the present invention are the same as those used in traditional powder coating systems. The following examples will illustrate the details of manufacturing the invention, but the invention is not limited to this. Example 1 According to the present invention, polyester resins 1 to 6 having aliphatic carboxyl groups were prepared. Compounds A 1 to D 2 were added to a round-bottom glass reactor equipped with a condenser, a temperature controller, a nitrogen system, a stirrer, and a venting system according to the mole ratios shown in Table 1. The mixture was heated to 50 in 30 minutes. Increase the temperature to 210 ° C over the next two hours and maintain it at 210 ° C until at least 94% of the initial sea-based reaction is complete. In this way, a polyester resin having an acid functional group can be obtained, and the temperature of the reactor can be lowered to room temperature and the resin can be taken out. (Please read the notes on the back before filling this page) Φ.

'1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 1 1) 2) ^ 1 base of poly @ Purpose resin 1 2 3 4 5 6 7 8 1, 4-CHCA (A1) 9 9 9 7 21 6 5.5 6.5 HHPA (A2)----DMPA (C) 2.5 2 1.2-1.5 1.5 HDPP (B) 5.5 6 6.8 4 8 1 3 4 TMP (Dl)--1 3 1 _ PENTA (D2)---1 -Earn 1,4-DMCH (B)-----2--1) The numbers in the table represent Example 1 to prepare a polyester resin with a linear tertiary carboxyl group jf. Ear count. 2) The compounds represented by the English and Chinese abbreviations in the table are as follows: —-__- 13 -_ Applicable to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 561164 A7 _ B7 __ V. Invention Explanation (U) 1,4-CHCA: 1,4-cyclohexanedicarboxylic acid ΗΗPA: hexahydrophthalic anhydride DMPA: dimethylol alcohol propionic acid HDPP: hydrogenated diphenylhydroxypropane TMP: trimethylol Propane PENTA: 1,4-DMCH: 1,4-DMCH: 1,4-dimethylolcyclohexane Example 2 According to the present invention, a polyester resin 9 having an aliphatic carboxyl group was prepared. Compounds HHPA, HDPP, and TMP were added to a round-bottomed glass reactor with a condenser, temperature controller, nitrogen system, stirrer, and evacuation system at a molar ratio of 1: 8: 2. The mixture is heated to 190 ° C and maintained at this temperature until the acid value is below 0.1 eq / g. Next, based on 1,4-cyclohexanedicarboxylic acid (CHCA) + HHPA, HDPP, TMP, 1,4-dimethyl alcohol cyclohexane molar ratio 1 3: 8: 1: 2, and 1,4-cyclo Hexenedioic acid allowed the mixture to continue to react until 94% of the initial hydroxyl reaction was complete. In this way, a polyester resin having an acid functional group can be obtained, the temperature of the reactor can be reduced to room temperature, and the resin can be taken out. Example 3 The corresponding polyglycidyl acetate resins A'B, C, D, E and F were prepared. From the sample numbers 1, 2, 3, 4, 7, and 8 in Table 1, each of the linear tertiary and partial secondary aliphatic carboxy polyester resins with 1 carboxy equivalent was dissolved in j 6 mole of epichlorohydrin (ECH), 15.5 moles of isopropyl alcohol (IPA), and 15.5 moles of hemi-water. This solution was placed in a glass reactor with a thermostat, a stirrer and a reflux condenser. Next, raise the temperature to 70 ° C, and then at 20 minutes. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Α7 --------- mi I (Please read the precautions on the back before filling out this page)-, 1Ί il.

， Reine slowly added a water solution with a weight ratio of 50 and a solution of 0.16 mol sodium hydroxide. In this process, the reaction temperature will increase from 7 (rc to 8 (rc.). At this time, the mixture is continuously stirred until all the acid groups are completely reacted (about 50 minutes and 4 miles). Then, the mixture is cooled to 551. At this temperature, In 60 minutes, slowly add 50% water / cereal solution composed of 0.92 moles of sodium hydroxide. Then, after 5 minutes of reaction, add 5 moles of water Stir for 5 minutes. At this point the reaction is complete and the brine can be isolated by the organic phase. Excess epichlorohydrin, isopropanol and residual water can be removed by evacuation. The obtained epoxy resin has the following properties : Table 2 The obtained unrefined resins A, B, c, D, E and F can be dissolved in methyl isobutyl ketone (MIBK, MIBK / resin = 5/1 volume ratio), at 70 to 75. C 以Wash with water 4 times (water / resin g / ι volume ratio). MIBK is then removed by flashing with dagger, and the remaining polyglycidyl ester resin can be taken out of the reactor to cool it. Resin ABCDEF epoxy equivalent (milliliter) Moore / kg) 1360 1214 996 1355 1400 1250 Total gas content (mg / kg) 5640 5338 5029 6212 7500 6500 Viscosity (Poise, 200. 〇9 11 16 14 9 16 Slope glass transition temperature (.35 39 47 38 32 39 (secondary scan, number of inflection points)) 1 degree, 1 foot, 1 sheet, 1 copy Standards! Family secrets I read 561164 A7

7 B V. Description of the invention (IS) Table 3 Composition * P1 P2 P3 P4 P5 Polyglycidyl acetate resin (1) A 600--Polyglycidyl ester resin (1) B-750---Polyglycidyl ester resin ( 1) C--750--Polyglycidyl resin (1) D---738-Polyglycidyl resin (1) E---1000 Carboxyl resin (2) 6 397 450 369 500 724 Antimony dioxide 299 360 336 371 517 Modaflow (3) 19.4 23.4 21.9 24.8 33.6 Benzoin 8.0 9.6 9.0 9.9 14.8 Catalyst 3.0 3.6 3.4 3.7 5.2 Powder properties Extrusion V Ί 王 / Storage stability @ 30 ° C Moderate good good moderate moderate good coating外观 Appearance J Umbrella, Fragrance V \ I / Gloss (5) 85 89 85 86 87 Rebound impact (6) > 60 > 20 > 10 > 40 > 40 Accelerated weatherability (7) > 1800 > 1800 > 1800 1500 > 1800 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) * All quantities are based on grams (1) Prepared according to Example 3 (2 ) Prepared according to Example 1 (3) Modaflow III is an acrylic glidant produced by Monsanto Company (CNS) A4 size (210X 297 mm) i-ice 1164 V. Description of the invention (M) (4) Coating: Q-plate of AL-36, hardened at 20 (TC / 15 minutes, coating thickness 40-60 Micron (5) Measured with Gardner micro-TRI-gloss device at an incident angle of 6 0 ^ (6) According to Ericksen type 3 04 ISO-TR-6272 / 1 979-D IN _ 5 5 6 6 9 in inches / pounds Measured in units (7) Hours required to reduce total weight by 50% with Atlas Weather-Ometer according to SAE J1960 !: ΨII (Please read the precautions on the back before filling this page), 11 t Central of the Ministry of Economy Printed by the Standards Bureau Consumer Cooperatives 17 This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

561164 ABCD 087103223 Patent Application Chinese Patent Application Replacement (May 1992) Patent Application Scope 1. A linear or £ chain polycondensation guide | Resin, which is in the presence of a base and a catalyst or In the absence, it is obtained by reacting a carboxy-functional polyester resin with an excess of epichlorobenzene. The carboxy-functional polyester resin is obtained by the following reaction, (a) at least one compound of formula I: 0 〇 Η η II ho-cc- (ch2) xc-coh I Ri where X2 1 where R i and R2 may each represent an alkyl group containing i to 4 carbon atoms, or where 1 ^ and 汉 2 may be combined with ~ 〇1 ^ (( : 112)) (-0 ^ ~ cycloalkyl (eight 1 combination; (b) at least one diol compound b, which includes two aliphatic hydroxyl groups, which may be independently independently first- or second-order vial groups (C) use or not use a dihydroxy monocarboxylic acid compound c, which includes a second-order aliphatic group and two aliphatic groups, which may be independently first- or second-order hydroxyl groups; and (d) the use or absence of a trihydroxyalkane (D1) or a tetrahydroxyalkane (〇2); : B: C: D 1: D2 can be expressed as X + Y + 2Z + 3Q + P: X: γ: z: q, of which, the paper size is suitable for S @ 家 standard (CNS) A4 specification (21GX 29? (Public Director) ------ 561164 A8 B8 C8 D8 VI. Patent application range Y from 1 to 4 'z from Q to 2, Q from 0 to 2, and P from 1 to 3; control the temperature to 1 0 0 to 2 0 0 ° C, until all the hydroxyl groups originally present in the reaction mixture are completely reacted. 2 · Polyglycidyl ester resin according to item 1 of the patent application scope, wherein component B is propylene glycol, neopentyl Alcohol, hydrogenated dihydroxyphenylpropane, hydrogenated *, 4 '· dihydroxybiphenyl, 1,4-cyclohexanedimethanol, i, 4-dihydroxycyclohexane, 3-hydroxy-2,2-di Methylpropyl-3-hydroxy-2,2-dimethylpropyl ester and 2-butyl-2-ethyl · 1,3-propanediol or a mixture thereof, component c is dimethylolpropionic acid, Component D 1 is trishydroxymethylpropane, and component d 2 is isopentaerythritol. 3. Polyglycidyl g resin according to item 1 of the scope of patent application, wherein component A1 is 1, 4 · cyclohexyl Diacid, component b is hydrogenated dihydroxyphenylpropane (HDPP), component C Is dimethylolpropionic acid, component D1 is trimethylolpropane, and component D2 is isoprene tetraol. 4. Polyglycidyl ester resin according to item 1 of the scope of patent application, where p is 1 〇 ·· A powder coating composition comprising a polyglycidyl ester resin and a crosslinking agent according to item 1 of the scope of patent application. 6. The powder coating composition according to item 5 of the scope of the patent application, wherein a carboxy-functional polyester intermediate system for preparing the polyglycidyl ester resin is used as the crosslinking agent. -2- This paper size applies to China National Standard (CNS) A4 (21 × 297 public directors)