TW425420B - Outdoor durable coating compositions and acid functional polyester resins and polyglycidyl esters thereof usable therefor - Google Patents

Abstract

A tertiary carboxyl functional polyester resin obtainable by reaction of: (a) at least one aliphatic compound A comprising two aliphatic hydroxyl groups which may each independently be a primary or secondary hydroxyl group and a tertiary carboxyl group, (b) optionally one or more hydroxyl compounds B, each compound comprising two aliphatic hydroxyl groups which may each independently be a primary or secondary hydroxyl group, (c) at least one cycloaliphatic carboxylic acid compound C comprising two secondary aliphatic carboxyl groups or the anhydride thereof, (d) optionally one or more dicarboxylic acid compounds D comprising two aliphatic carboxyl groups or the anhydride thereof, and (e) optionally either one or more compounds E comprising one primary or secondary hydroxyl group and optionally a tertiary carboxyl group, or one or more monocarboxylic acid compounds (G) comprising a primary or secondary carboxyl group together with equivalent molecular amounts of one or more compounds (F) selected from the groups for A and B, the molar ratio of compounds (A+B) : (C+D) : E : F : G being (X-1) : X : K : L : M, wherein X ranges from 2 to 14, K ranges from 0 to 2, L ranges from 0 to 2 and M ranges from 0 to the value of L. These polyester resins may be used together with a suitable curing agent for the production of powder coatings, or may be converted into the corresponding glycidylesters, which in combination with a suitable curing agent can be used for the production of powder coatings.

Description

Patent Application No. 87102566 of the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China— ". Chinese Revised Sheet (March 88) B7 r | V. Description of the Invention (1) L —... .4 25 :: 本The invention relates to outdoor durable coating compositions, which are derived from a third functional polyester and / or a polyglycidyl ester resin derived from the third carboxy functional polyester, and describe the third carboxy functional polyester The resin itself and especially the linear resin, and the polyglycidyl ester resin obtained by glycidizing the third carboxy-functional polyester resin. More specifically, the present invention describes a powder coating composition 'this contains the third functional polyester resin and / or the polyglycidyl resin and describes the hardened product obtained using the coating composition and shows improvement Outdoor nature. A widely used system for manufacturing outdoor durable powder coatings is based on a polyester / diglycidyl isotricyanate (T GIC) blend. The coating film made from such a mixture shows quite good outdoor durability, but it needs to be further improved from the environmental point of view. In addition, the use of TGIC is questionable for health and safety reasons. TGIC is quite toxic (oral administration of 0.45 g / kg of L D50 in mice) and this compound was identified as a substance that induces mutations according to the Ames mutation test. Other widely used systems, especially those for automotive topcoats, include acrylic resins crosslinked with melamine resin and / or (blocked or unblocked) isocyanate. However, the hardening reaction of this type of system is bad for the environment because (usually) methanol is released. And 'this system does not provide the required level of durability for acid-catalyzed hydrolysis', especially for the hydrolysis of " Acid Rain 11 which contains sulfuric acid in rainwater. In addition, the durability of this system to UV light is generally acceptable, but obviously there is still room for improvement. It has been known for a long time that powders based on glycidyl solids obtained by the reaction of 2,2-bis (4-hydroxyphenyl) propane (bisfluorene A) with epichlorohydrin-4-paper size Applicable to China National Standards (CNS) A4 specification (210X 297mm) I ~-(Please read the precautions on the back before filling this page) -I ^ '定 弟 871〇2566 Chinese manual amendment page (March 88) A7 B7 V. Description of the invention (2 425420

Printed coating compositions of the Central Standards Bureau of the Ministry of Economic Affairs, Jeonggong Consumer Cooperative, "The hardened products prepared based on these compositions are resistant to hydrolysis. However, their resistance to ultraviolet rays is very low, so they are not suitable for use where high quality is required The application of outdoor durability such as building parts or car finishes " Reference material in this regard is on EP_0T20997A, especially Tuxia, which is found based on epiKOTE (2,2_bis_ (4_hydroxyphenyl) propane Bis glycidyl ether) and many commercial polyester / acrylic resin powder coatings show only moderate weather resistance. Other known coating compositions are based on hydrogenated hydrocarbons, such as the glycidyl ethers of hydrogenated bisphenol A. Since there is no aromatic group, the U V resistance of the hydrogenated compound is better than that of the non-hydrogenated compound. However, since it has an aliphatic ether group, its outdoor durability is still relatively low, and its acid resistance is also very low. The third carboxylic acid functional polyester resin is described in European Patent Application No. OHWMA, U.S. Patent No. 3,749,758, British Patent No. i, 048,893, and Japanese Patent Application No. JP-A-58,189,261A. However, the examples actually prepared are based on resins containing aromatic dicarboxylic acids. Therefore, as in the example of the resin based on double brew A discussed above, the hardened products prepared from these water-based resins will show low UV resistance, and therefore are not suitable for high-quality outdoor durable applications. Known from the European Patent Application No. Brown EP-0 6 3 4 4 3 4 A and EP-0 7 2 0 9 9 7 A ~ When some linear third aliphatic carboxylic acid functional polyesters are used as coating compositions, In the hardened state, outdoor durability (UV stability) and hydrolysis resistance are required. Due to the increasing requirements of coating compositions for modern industrial applications, especially for economic and / or environmental considerations of powder coating compositions, the Chinese National Standard (CNS) Α4 for 5-paper standards applies ( 210X 297 mm) --- HI --- I- n I -------- 1 n τ · " * τ {Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by the employee consumer cooperative ^ · 425420 A7 ____B7 V. Description of the invention (3) The coating is still needed and the compound still needs to be further improved—improved through the use of substitutes, especially more convenient starting materials, to harden Improvements in properties, especially lower temperature hardening 'and elimination of environmentally unwanted solvents, and improvements in some properties of hardened products and / or by-products', especially improved flexibility, weather resistance and acid resistance. From the above description, it can be seen that there is still a need for resin system compositions (crosslinking agents and / or epoxy compounds), which is particularly suitable for powder coating compositions, which are comparable to current polyester / TGIC systems Non-toxic and shows excellent outdoor resistance in a hardened state. These systems also show quite low hardening temperatures and good hardened product properties. It is therefore an object of the present invention to provide an acid functional polyester resin, preferably a linear resin, wherein the acid functional group contains only a third aliphatic carboxylic acid functional group, which can be glycidized to form a polyglycidyl ester resin. The third carboxylic acid-functional polyester resin and the polyglycidyl ester resin are particularly suitable for outdoor resistance to powdery coating compositions, which have good weather resistance and acid resistance to environmentally friendly and hardened resin products. The backbone of the resin according to the present invention does not contain any ester functional groups that would hydrolyze under fairly mild conditions, and the polyester resin does not contain any UV-sensitive functional groups. The terminal group (i.e., in the center) of the resin according to the present invention is preferably a carboxyl group, especially a second group, but also a hydroxyl group, especially a second group, or optionally an esterified hydroxyl group. Therefore, the present invention relates to a third carboxy-functional polyester resin obtained by the following reaction: a) at least one aliphatic compound a which contains two aliphatic hydroxyl groups each independently being the first or second warp group; And the third carboxyl group, ______ _ ^ 6- This paper scale towel watch cell (2 like 297 male ^^ -— ----? '---^^ 1 ........ I 士 久 I --II-^^ 1-. __ T »——.mu II _ __ I n-U3-5 \ · (Please read the precautions on the back before filling this page) A7 425420 5. Description of the invention (4) b ) One or more hydroxyl compounds b as appropriate, each compound containing two aliphatic hydroxyl groups, each of which is independently a first or a second hydroxyl group, c) at least one cycloaliphatic carboxylic acid compound C, which contains two Dialiphatic carboxyl groups or their anhydrides, d) as appropriate-one or more dicarboxylic acid compounds d containing two aliphatic groups or their anhydrides, and e) as appropriate, one or more compounds E, containing A first or first base and optionally a third side_group 'or one or more mono-acid compounds (G), which contain the first or Molar ratio of dicarboxyl and isomole / one or more compounds (F) selected from the group consisting of octa and B, the molar ratio of compound (A + B): (C + D): E: F: G is (χ-υ: X: K: L: M, where X ranges from 2 to 14, K ranges from 0 to 2, L ranges from 0 to 2 and M ranges from 0 to L 値. Actually selected from A or B and The preferred compounds of F are the same, but in principle the representatives defined to two or more different groups of A and B can actually be used as compounds A, B, and F. On the other hand, the present invention describes the preparation of the foregoing specific The method of polyester resin. Depending on the equivalent of the starting material used, it is best to perform the method until all, or substantially all, of the non-third carboxyl group present initially in the reaction mixture is completely reacted, or until all, or Virtually all hydroxyl groups present in the reaction mixture are completely reacted. It is known that in addition to pure (or almost pure) compounds A, B, C, D, E, F, and G, two or more compounds can be used A, B, C, D, £, F, and G. Compounds a, B, C, D, E, F, and G are straight-chain or branched (cyclic) hydrocarbon compounds And it is preferable that the winter paper size applies the Chinese National Standard (CNS) Λ4 坭 辂 (2 丨 0: < 297 Gong) I ---.------ ^ ------, 玎- ----- Λ-· (Please read the precautions on the back before filling out this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 425420 A7 B7 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 何 ^ 基 m contains only and / Qianji. The big makeup word used above means at least 92%, preferably at least ㈣ at least ㈣, and most preferably at least 99% of the initial non-third-party or superbase has been reacted. When the acid 値 of the third polyfunctional polyacetate thus generated is equal to the theoretical 値 calculated from the amount of the third carboxyl group and the amount of the reaction carboxyl group and the hydroxyl group initially present in the reaction mixture, they actually have no non-third secret. . As used herein, the term "actually" means that the error from the theoretical value is at most +/- 8%, preferably 5%, and more preferably 3% '. This is obtained by the standard alkali titration method. The artist will understand that the molecular weight distribution and number average molecular weight of the resin depends on the reactants used in the method of the present invention and their proportions. When the third aliphatic group is present in compound A, it is used in the esterification reaction. In fact, E does not react. These third aliphatic carboxyl groups and epigases will produce a glycidation reaction under standard alkaline conditions to obtain a polyglycidyl acetic acid resin. It contains low hydrolyzable southernin, It is usually less than 0.5% of the total weight of the composition. And 'there is almost no backbone of the resin to be hydrolyzed during the glycidation reaction', so no low molecular weight products are produced. Since there are no relatively low molecular weight products, the polyester of the present invention Resins are particularly suitable for preparing powder coatings. It is understood that during the esterification reaction, the first hydroxyl group is more active than the second hydroxyl group and they are also more active than the third hydroxyl group. Sex has the same order. The activity of acid is higher than the related (di) acid. And the substitution of the 'hydroxy or truncated beta (beta) position usually affects the activity and usually results in lower activity 。Based on the order of the activity 'the above tree-8- This paper size applies the Chinese National Standard (CNS) Λ4 gauge (2! OX 297) while taking advantage of ----------- installation ----- -Order -----.—— 泉-响 (Please read the notes on the back before filling this page) 4 2 5 4 2 0 A7 ___Q7 V. Description of the invention (6) ~~ ~ The molecular weight distribution of the fat is still It is possible to predict the most likely chemical structure. In a preferred embodiment of the present invention, the order of addition can be selected (first one equivalent of the acid anhydride C is added to two equivalents of the dihydroxy compound A 'and then The remaining initial compounds include a as the second groove of the component ρ · and the reaction is complete) so that the smallest molecule formed always contains two eight molecules and three C molecules, that is, its molecular weight is at least 700. This means that After glycidation, 'even the smallest aliquot has a fairly high molecular weight, so the product is expected The toxicity will be very low. The polyester intermediate used in the invention is preferably a linear product because it will form the southernmost Tg temperature. Therefore, the initial compound of the polyester is preferably a difunctional group and can participate in the ester of the resin center. Therefore, the amount of the polyfunctional compound, especially the di- and tetra-energetic compounds, is preferably better than the total amount of the initial compound, less than 25 mol%, more preferably less than 15 mol%, and most preferably less than 5 mol%. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs' ·-> 1!-! < ^^ 1-, I ....... III ί n. 03. -V * ». (Please Read the notes on the back before filling in this page. The method for preparing the polyester resin of the present invention can be done according to the traditional esterification method, and the azeotropic condensation reaction is preferred. In particular, the condensation reaction can be carried out by charging the initial compound into the reactor, and reacting it to 22 ° C 'and continuing the reaction until the non-third carboxyl group originally present in the reaction mixture disappears. The reaction is usually completed in 2 to 12 hours, often in 3 to δ hours. If the compounds e or f and G are intended to be end groups of the polymer chain, they are preferably added before the reaction is terminated, otherwise these compounds will be added to the chain. If it is a monofunctional compound E, or a pre-condensed monofunctional conjugate of j: and G, these reactants can also be added at the beginning of the reaction or during the reaction. = If compound F is the same as compound A or B, then You can also respond to ________ _ 9- This paper is compliant with Chinese National Standards (CNS) Λ4 Regulation & (2〗 0χ 297 公 和) ~-425420 A7 ____B7 V. Description of Invention (7) ~~ At the beginning Or add them to the reaction. Usually, the removal of azeotrope of water is continued until the reaction product of acid 値 equal to the above theoretical 上述 is obtained. , Zinc octoate and lithium ricinoleate 'and preferably no catalyst is used. However, if necessary, an esterification catalyst can be used. The polyester resin of the present invention is suitably derived from a compound A selected from the group consisting of a compound containing a third aliphatic amine group and two first warp groups. Suitable compound a is a fluorenyl-substituted dimethylolacetic acid compound, the alkyl group is a linear or branched c h, and the gauge group is, in particular, a Ci_4 fluorenyl group. The better compound a is printed by methyl propionate. 0 Printed by I Industrial Consumer Cooperative of Zhongrong Sample Standard Bureau of the Ministry of Economic Affairs-Hr — —I i 4 1 ^^^ —1 I--(谙 Read the precautions on the back first (Fill in this page again.) The polyester resin of the present invention is suitably derived from Compound B selected from compounds containing two aliphatic or cyclopentadiene groups. Compound b suitable for the present invention may optionally include branched aliphatic or cycloaliphatic compounds ^ Especially compound B is a linear chain substituted with one or more C! _4 fluorenyl groups, ω-alkanediol compounds, A cyclohexyl compound having two hydroxyl groups on the cyclohexyl ring and optionally substituted by one or more C 1 -4, such as 1,4-cyclohexanediol, or a perhydrodihydric compound, such as a hydrogenated bis Phenol A or F compound. Preferred compound B is an omega-alkanediol compound containing up to 8 carbon atoms and optionally substituted by one or more methyl groups or cyclohexanediol optionally substituted by one or more methyl groups. The polyester resin of the present invention is suitably derived from compound C containing a compound containing two or three, preferably two second carboxylic acid groups, or an anhydride thereof. For example, a suitable compound C is hexahydrophthalic acid (HPA) , Methylhexahydrog, too acidic, Jiuyangcao ____- 10-_ This paper rule is suitable; q Chinese National Standard (CNS) Λ4 Regulations (2 丨 0: < 297 public trip) ~ _ Ministry of Economic Affairs Central Printed by the Consumer Cooperatives of the Standards Bureau 425420 A7 ^ ---------- V. Description of the invention (8) ^ i-bridged methyltetrahydrophthalic acid, methyl bridged methyltetrahydrophthalic acid, 1 '4-cyclohexanedicarboxylic acid and 1, 3-cyclohexanedicarboxylic acid or an anhydride thereof, or a combination thereof. The preferred compound c is a cyclooctane dicarboxylic acid, especially cyclohexyl diazaic acid, which may be substituted with one or more methyl groups as necessary. Book M, especially its anhydride, is better. The polyester resin of the present invention is suitably derived from a compound D 'selected from the group consisting of aliphatic dicarboxylic acids or anhydrides thereof, and in particular, optionally substituted by 1 or more c 1 -alkyl dicarboxylic acids. Preferred D is a ω-alkanedicarboxylic acid containing 4 to 14 carbon atoms in the alkane chain, especially 6 to 10 carbon atoms. The most suitable chemical compounds are octanoic acid, nonanoic acid, sebacic acid, and 1 1 12 oxadipic acid. Compounds D having an even number of carbon atoms are preferred because they generally lead to higher melting points. The compound E used in the present invention is suitably an aliphatic or cycloaliphatic alcohol, preferably containing one to ten carbon atoms, and optionally substituted with a third carboxyl group. Suitable compounds E of the soil are propanol, isopropanol, n__, s_, or i_butanol, aromatic%, cyclohexanol, cyclohexanol, and hydroxytrimethylacetic acid. Compound E is a hydrocarbon compound 'which does not contain any other functional groups or substituents except one hydroxyl group and optionally a carboxyl group. The preferred compound E is hydroxytrimethylacetic acid. Optionally, within the conjugate F + G used in the present invention, the compound a may be appropriately selected from the same compounds as defined by A and B. The preferred compound F is a cyclohexanediol compound, in particular], 4-cyclohexanediol, or dimethylolpropionic acid. 3 The compound G used in the method of the present invention suitably contains only a few -11- This paper size applies to the Chinese National Standard (CNS) Λ4 gauge cypress factory (210χ 297 Gongchu 7 J --.--------- seed clothing ------ II ------ .. 4 '( (阅读 Read the notes on the back before filling out this page)

Patent Application No. 87102566 4 25 4 2 0 Chinese Manual Correction Page (March 88) ^ V. Description of the Invention (9) Acid (cyclic) hydrocarbon group. Compound 0 is especially an aliphatic or cycloaliphatic acid, and even a second acid. The preferred compound G is a cycloaliphatic acid, and more preferably a second cycloaliphatic acid. The preferred compound G is a cycloalkylcarboxylic acid, especially a cycloalkylcarboxylic acid, more preferably a cyclohexylcarboxylic acid. As mentioned above, 'compounds A, B, c, D, E, F, and G are hydrocarbon groups containing one or more carbyl groups and / or several groups. Compounds may or may not be substituted. Substitutions must not damage the outdoor durability of the hardened product. Preferred compounds are those which are not substituted. It has been found that the molar ratio within the formula of the third carboxy-functional polyester according to the present invention is a suitable X value between 3 and 12, preferably between 5 and 10, and more preferably between Between 6 and 9. The K value can reach 2 and the L value can reach 2 and the preferred K and L · values are 2 °. A suitable A / (A + B) ratio is at least 0, preferably at least 0.75, more preferably at least 0.9, And the best is! . The C / (C + D) ratio is at least 0.6 ', preferably at least 0.75', more preferably at least 9 ', and most preferably 1. According to a preferred embodiment of the polyester resin, the Mo number of B is less than the Mo number of C. The present invention also describes a method for preparing the aforementioned third carboxy-functional polyester resin through the following reaction: Printed by the Consumer Standards Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs a) One kind of fatty compound A ′ contains two Each is independently an aliphatic hydroxyl group and a third carboxyl group of the first or second hydroxyl group, b) one or more hydroxyl compounds b as appropriate, each compound contains two aliphatic light groups, each of which is independently the first or the second Two light bases, c) at least one cycloaliphatic acid-acquiring compound c, which contains two second-aliphatic radicals or their acid residues, -12- this paper is in accordance with the Chinese National Standard (CNS) A4 specification {210X 297 public %) Printed by the Consumers 'Cooperative in the Ministry of Economic Affairs 425 4 2 0 A7 B7 ~ " "-.' ~ —— V. Description of the invention (10) d) Select one or more dicarboxylic acid compounds as appropriate D, which contains two aliphatic carboxyl groups or their anhydrides, and e) optionally one or more compounds e, which contain a first or second hydroxyl group and optionally a third carboxyl group, or one or more monocarboxylic Acid compound (G) It contains a first or second compound and an equimolar amount of one or more compounds (f), 'compounds (A + β): (c + D): (C + D): E: F: G The ear ratio is (X-1): X: K: L: Μ, where the range of X is 2 to 14, the range of κ is 0 to 2, the range of L is 0 to 2 and the range of M is 0. To 値. The preferred reaction temperature of this method is 120 to 220 ° C ', and more preferably 180 to 200 ° C, until all non-third carboxyl groups initially present in the reaction mixture are reacted. The third carboxy-functional polyester resin according to the present invention can be converted into a polyglycidyl ester resin and this forms another part of the present invention. This conversion can be carried out according to methods known in the art, i.e., reaction with an excess surface haloalkane in the presence of a suitable base and optionally a catalyst. The most commonly used is surface vapor deposition. & W Patent Application No. 04473 60 A discloses a composition which can be used mainly for outdoor resistant coatings and molds. However, due to the terminal beta of the terminal fluorenyl group of the precursor before carboxylic acid conversion, strong conditions must be avoided during the glycidation of these tricarboxylic acid conversion products to avoid the formation of glycidyl & vinegar hydrolysis and / Or Shuyue 0-one or more alcohol-based hydrolysis. The result is that the glycidol produced will contain a considerable amount of hydrolyzable gas and / or will contain low molecular weight hydrolysates and this will cause a problem of toxicity. In Example 2 measured by Ερ_Α_〇44, a large amount of hydrolyzable gas is reflected and this is 2:] hexahydrophthalic anhydride and --------- 1-13-this paper rule is quite rich n. Nu-— I n-t ^^-] ί nn ϋ TI! ------ I U3-aV, _ I, {Please read the notes on the back before filling K-page) 425420 Patent Application No. 87102566 Γ-Chinese Manual Correction Page (March SS) From the fifth, invention description (11), the results of glycidation of dimethylolpropionic acid. The chlorine content of the obtained product was 1.5%. This large amount of residual gas is not needed in the coating composition. In addition, due to the fact that the glycidyl esters reported in EP-A-0447360 are liquid, they are not usable as a powder coating composition. It has been found that both the third carboxy-functional polyester resin and the polyglycidyl ester resin of the present invention are suitable for use in a powdery coating composition, and in the hardened state, they show improved outdoor durability, especially improved weather resistance and acid resistance. And because of the polymer properties of the polyglycidyl ester resins of the present invention, their toxicity is lower than that of TGIC, so they can be used to favorably replace TGIC in powder coatings. 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 out this page) The third carboxy-functional polyester resin or polyglycidyl resin obtained by glycidizing the third carboxy-functional polyester resin ° The amount of the crosslinking compound used in the powdery coating composition of the present invention can usually be Provide approximately equal amounts of the reactive group of the branched compound and the epoxy group present in the tertiary group or the polyglycidyl glycidyl resin present in the polyester. The temperature at which the hardening is performed may be between 100 and 240 °, preferably between 120 and 200 ° C. The hardening temperature is usually 20-40 ° C lower than the composition of the prior art, while still obtaining the same degree of crosslinking. Use a catalyst if necessary. A suitable hardening time is 5 to 60 minutes, especially 10 to 30 minutes. Good results are usually obtained by curing at 140- 丨 60 ° C for 15 minutes. Crosslinked resins suitable for use in combination with the third carboxy-functional polyester resin of the present invention, such as outdoor durable epoxy resins, such as the polyglycidyl ester resin according to the present invention, as disclosed in European Patent Application No. 05 1 8,408A Α, α -14- This paper method scale is applicable to China National Standards (CNS) Α4 specifications (210 × 297 mm) A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Associate Bureau of the Ministry of Economic Affairs 5. Description of invention (12 ~~ points Polyglycidyl diglyceride and polyglycidyl polybasic acid with two alkyl substituents on each carbon atom as disclosed in European Patent Application No. 0366,205A. Suitable for the present invention Crosslinked resins used in combination with polyglycidyl ester resins, such as the (relevant) acidic functional polyester resins of the present invention: solid polybasic acids such as sebacic acid, adipic acid, 1,1,2-dodecanedicarboxylic acid ; Anhydrides such as polyazepate and triphenylhexacarboxylic anhydride: acid-functional polyesters such as the reaction product of 1 mole of trimethylolpropane and 3 mole of hexahydrophthalic anhydride, 丨, 6 _ Diacid and one molar excess 1,] 2_ The reaction product of dioxane dicarboxylic acid, 4-mole decanedioic acid,) .49 mole of adipic acid, 0.47 mole of 1,1,1 · -tri- (hydroxymethyl) _propane and 0. 27 moles of isoprene tetraol reaction product, 4 moles of 1,10-decanedioic acid, 12 moles of adipic acid, 45 moles of trimethylolpropane, 0.29 moles of The reaction product of isopentaerythritol and 021 moles of methyl propionic acid and the reaction product of 1 mole of hexamethylol fluorenyl melamine mol of trimethyl acetic acid: cyanuric acid: and solid Experiential sclerosing agents such as cyanoguanidine and BF 3 _ complex. The preferred hardener is the reaction product of the acidic polyacetic acid of the present invention with 1 mole of trimethylolpropane and 3 mole of hexahydrophthalic anhydride. This February's uncle-like coating composition may further include a catalyst and, as the case may be, other horses; Taigazhai 丨 『Park Weishi

Jd, substances known in this art to be suitable for use in powder coating compositions. Suitable catalysts such as the fourth ammonium and phosphonium salts: metal salts / compounds such as octanoic acid ": basic compounds such as micon: and third amines such as " -diazepines Ηj Γ .----- ----- ¾ ------ ΐτ ------ 1 τ * (Please read the notes on the back before filling in this page) This paper size is applicable to China® Home Standard (C. \ S) Λ4 ^ * -15 (210X297 public trend) Central Standard of the Ministry of Economic Affairs 印 Printed for the Industrial and Consumer Cooperatives -4 254 2 0 Α7 Β7 V. Description of the invention (13) The amount of catalyst used is usually the powder coating composition The range of 0.1% to 2% of the total amount. The following examples are used to illustrate the present invention, but its range is not limited to these specific specific examples. Example 1 Hexahydrophthalic anhydride (9 moles), two Hydroxymethylpropionic acid (8 moles) and hydroxytrimethylacetic acid (2 moles) were added to a round-bottom glass reactor equipped with a mechanical stirrer, temperature controller, nitrogen inlet, and venting facility. The mixture was stirred under nitrogen. And heated to 150 ° C ° spare 95 mbar of emptying. The temperature of the reaction mixture was increased to 200 ° C within 1 hour and maintained at 200 ° C until reaching Up to the acidic acid discussed = Pour out the acid functional polyester and let it cool to room temperature. Acidic acid: 3.94 meq / g: Molecular weight: 2535: Melting point 8 0-11 (TC. Example 2. Hexahydrophthalic anhydride (7 moles), dimethylolpropionic acid (8 moles), and dodecanedioic acid (2 moles) were added to a round-bottomed glass reaction equipped with a mechanical stirrer, temperature controller, nitrogen inlet, and venting facility Inside the vessel. Stir the mixture under nitrogen and heat to 50 ° C. Use a 950 mbar vacuum. Increase the temperature of the reaction mixture to 200 ° C and maintain it at 200 ° C until the theoretical acid temperature is reached. 3 Decant the acidic functional group and let it cool to room temperature. 3 acid hydrazone: 4 〇8 meq / g: molecular weight: 245 1: melting point 60-7 5T: Example 3 The method described in Example 1 uses hexahydrophthalein. Acid anhydride (5 moles), methylpropionic acid (4 moles), and trimethylacetic acid (2 moles) to prepare acidic functional groups. Product: acid hydrazone: 4 · 1 3: molecular weight 1453 : Marriage point 7 〇_ 8 5 ° C. ________ This paper size is applicable to the Chinese National Standard (CNS) Λ4 ^ grid (210X 297 cm) '--- --- L ------ pack ---- --Order ------ ^-. (Please read the precautions on the back before filling in this page) 425420 Printed by A7 B7 of the Consumers' Cooperatives of the Ministry of Economic Affairs of the Ministry of Economic Affairs. 5. Description of the invention (14) Such as EP-0634434A (S ) The method described in Example 2 uses hydrogenated dihydroxyphenylpropane (6 moles), hexahydrophthalic anhydride (9 moles), dimethylolpropionic acid (2 moles) and hydroxytrimethyl Acetic acid (2 moles) is an acidic functional polyacetate to prepare the related glycidyl esters. Precursor: acid 値 1.20: dosing amount 3340: melting point i5_125 ° C: product: EGC 1120 mmol / kg: melting point 85-90 ° C. Example 5 The method described in Example 2 of EP-0634434A uses dihydrobenzyl propane (3 moles) derived from hydrogenation, hexahydrophthalic anhydride (9 moles), and dihydroxymethylpropionic acid (5 moles). And hydroxytrimethylacetic acid (2 moles) acid functional polyester to prepare related glycidyl esters. Precursor: acid sulfonium 2.38; molecular weight 2937; point 99-120 ° C: product: EGC 1.79; melting point < 50 ° C. Example 6 The method described in Example 2 of EP-0634434A uses hydrogenated diphenylpropane (3 moles), hexahydrophthalic anhydride (6 moles), and dimethylolpropionic acid (2 moles). And Xiangji trimethylacetic acid (2 moles) acid functional polyester to prepare related glycidyl esters. Precursor: acid osmium 1.82; molecular weight 2 198; bright point 105-115'C: product: EGC 1.40: melting point < 50 ° C. Example 7 The method described in Example 3 of EP-0720997A uses the earlier preparation of hydrogenated dihydroxyphenylpropane (6 moles), hexahydrophthalic anhydride (9 moles), and dimethylolpropionic acid (4 moles) Ear) acidic functional polyester to prepare related glycidyl esters precursors: acid osmium 1.19: molecular weight 3372: product: EGC 1170 -17- This paper size applies to Chinese National Standard (CNS) Λ4 present grid (2IOX 297 public Chu) (Please read the notes on the back before filling in this page)

42542 Ο Α7 Β7 _ __ '' .....— ’_ ~~ ~ I I ι ι. ____

V. Description of the invention IM mmol / kg; melting point 80-9CTC. Example 8 The method described in Example 1 uses hydrogenated dihydroxyphenylpropane (4 moles), hexahydrophthalic anhydride (9 moles), dimethylolpropionic acid (4 moles), and p-tetrabutyl Cyclohexanol (2 moles) was used as a starting material to make acid functional polyester. The nature of the product was 1.32 mmol / kg acid; molecular weight 3036: melting point 105-200 ° C. The acid-functional polyester was converted to glycidyl ester by dissolving 1 carboxy equivalent of polyester in 8 mol of epichlorohydrin and isopropanol (e.g. the same volume as ECH). The solution was added to a glass reactor equipped with a temperature controller, a stirrer, and a reflux condenser. The temperature was then slowly increased to 70 ° C, and a 1.05 mole NaOH aqueous solution was slowly added over 60 minutes. After the reaction i 0 minutes, the contents of the reaction were precipitated and the aqueous phase was separated from the organic phase, and then washed several times with water. Product properties: EGC 1230 mmol / kg; melting point 75-85 ° C. Example 9 Printed by the Central Standards Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives--, '1-JH-! * Shiliang I — n----^ ~ ^. --Se-* (Please read the precautions on the back before (Fill in this page) CIO Koch acid vinyl ester (trade name Veova-10) (22 parts by weight), 1 'methyl cis butadiene, dilute and cool (6.5 parts by weight), styrene ethyl cotton' (43.0 parts Weight), methyl methacrylate (11.5 parts by weight), glycidyl methylpropionate (1 7.0 parts by weight), and di-quad-butyl peroxide (2 parts by weight) are reacted to prepare one Epoxy functional polymer. Add the vinyl ester and dimethyl maleate of Koch acid to a glass-breaking reactor equipped with a mechanical stirrer, temperature controller, nitrogen inlet, monomer inlet tube, and reflux condenser directly into the reactor. . The reactor was heated to 1 55-170. (:. Add the remaining monomers and starters to the reactor at a certain rate within 5 hours, and then ___.____- 18 -________ This paper standard is common in China and National Standards (CNS) Λ4 specifications (210X297 Gong) 425420 Λ7 B7 Five 'invention description (16 hours under 2 hours of reaction. Then the polymer is decanted and cooled. Properties of the product ·· EGC _ 雠 〇Ukg ·· Tg 312K: Mn (Gp (:) 7 〇 * 〇8, Mw (GPC) 30.2 * 108 ° Example 1 0 The same method as described in Example 4 of EP-0720997A was used to prepare the coating. The coating was printed and applied by the Central Consumer Bureau of the Ministry of Economic Affairs. Composition—Acid Polyester Example 1 Example 1 Example 1 Example 2 Example 2 Example 3 Example 3 Epoxy Reactant Example 4 Example 7 Example 8 Example 9 Example 4 Example 8 Example 5 Example 6 Comparative Example Polyacetate / TGIC C Asphalt / IC, MF Hardening temperature [° c] 200 200 200 200 200 200 160 160 180 160 160 Konig hardness of coating film properties "[s] 220 200 210 200 200 200 200 190 190 210 170 Ductility M Unqualified Qualified Unqualified Pass Pass Pass Pass Q [inch brick] < 20 < 20 < 20 < 20 < 20 < 20 P20 P20 P40 < 20 Acid resistance d > 5 4-5 4-5 3-4 3-4 3-4 4 4 3 1-2 weather resistance qf * 100 h] i > 35 > 25 > 35 25 > 30 > 30 30 35 5 25 a) Do 1 on Erichsen model 299/300 >) Do c on £ 1 ^ 115611 model 3 12) Do d on Erichsen model 304) Test method: Drop the 0.6N H2S04 droplets onto the coating film without covering -19- This paper size is applicable to China National Standard (CNS) Λ4 gauge cotton (210X 297 cm) (Please read the precautions on the back first (Fill in this page again.)-Pack. D,-* 425420 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Masonry Consumer Cooperatives. 5. Description of the invention (17) · Place in 5 (TC oven for 90 minutes. Use u 5 Visually evaluate its performance = the coating film is completely dissolved, 5 = the coating film is not attacked.) E) the time of exposure to the weather meter until the gloss is reduced to 50%. Test method: SAE J1960-1989 = Comparative example of TGIC is a hardened reaction product based on TGIC with equivalent amounts of commercial acid functional polypropylene resins (URALAC 42000, DSM, based on terephthalic acid and glycerol). — The comparative example of C # acid vinegar is based on glycidyl methacrylate (eg, / UCB) and decanoic acid (Synthacryl, Hoechst, acid 300 mg KOH, M2000, 'melting point 80-90 C) and Cross-linked by the same amount of melamine (mf). MEK resistance is measured by rubbing the sample with MEK until the coating film is damaged and the number of times the iron plate can be seen. The hardness is measured according to the pendulum clock test (Konig hardness) of ISO 1522_1973 ° The weather resistance is measured according to the Society of Automotive Engineers (SAe J1960-1989) ° The test method is designed to accelerate the outside of the car due to sunlight, heat and moisture ( Humidity, condensation, or rain). The Atlas C 165 Xenon Arc Weather Meter was used for testing until the gloss was reduced by 50%. Acid resistance was measured by dropping a drop of 0.6N H2SCU onto the coating film and leaving it at 50 ° C for 90 minutes. The results are described on a scale of 1 to 5: dissolve, 2-soften, 3-turn white, 4-slightly, 5, not damaged. -20- The size of this paper is applicable to China National Standards < CNS) Λ4 Specification (210X297mm f) ----- H 1Γ ί ---- I 'I__ • ♦ (Please read the precautions on the back before filling in this page)

'1T

Claims (1)

4 25 4 2 0 Patent application No. 87102566 χ8 BS Landlord applies for special brake Lugang ^, τ table leap year n g Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 11 VI. Apply for a patent + 1- A third carboxy-functional polyester resin obtained by the following reaction ... a) at least one aliphatic compound a, which contains two Each independently an aliphatic hydroxyl group and a third carboxyl group of the first or second hydroxyl group, b) one or more base compounds b as appropriate, each compound contains two aliphatic hydroxyl groups, each of which is independently the first or second Dikiaryl, 'c) at least one cycloaliphatic carboxylic acid compound c, which contains two second aliphatic condensates or their acid fields, d) optionally one or more dicarboxylic acid compounds d, which contain two Aliphatic radicals or their acid fibers, and e) optionally one or more compounds containing a first or second hydroxyl group and optionally a third carboxyl group, or one or more monocarboxylic acid compounds (G ) 'Comprising one or more compounds (F) selected from A and B, the first or second carboxyl group and isomol τ, compound (A + B): (C + D): E: F: G Ear ratio is (X · 1): X: K: L: Μ, where X ranges from 2 14, the range of 0 to 2 K 'L range to the range of 2 billion and Μ is square to the L value. 2. The third carboxy-functional polyester according to item 1 of the application, wherein the compounds A or B and F are the same. 3. For example, the tertiary functional polyester resin of item 1 in the scope of patent application, wherein compound A is dimethylolpropionic acid. 4. For example, the third carboxy-functional polyester resin of items i to 3 of the patent application park, wherein compound B is a straight chain α containing up to 8 carbon atoms' and optionally substituted by one or more methyl groups. , Ω-alkanediol compounds or may be used in accordance with the 11 national standards (CNS) A4 (210X297 mm) a tur-^^^ 1 ^^^ 1 in ί β HI: _ II ^^^ 1-1 ^ -β (Please read the notes on the back before filling out this page} 425420 Μ Β6 α D8 Printed and patented by the Industrial and Commercial Cooperatives of the Central Bureau of Standards of the Ministry of Economy—one or more methyl groups Substituted Cyclohexanediol "5. If the third carboxylate is applied for in the scope of the patent application! Energy-based polyester resin 'wherein compound C is hexahydrophthalic acid. 6. If the third carboxylate in the scope of the patent application is applied for! A functional polyester resin, wherein compound D is an alkanoic acid containing 4 to 14 carbon atoms in the alkane chain. 7. The third carboxy-functional polyester resin 'where the compound E is a hydroxyl group, such as in the first patent application Trimethylacetic acid. 8. For example, the third carboxy-functional polyester resin 'where the compound F is dimethylol. Propionic acid and compound G is a C5-Cs cycloalkylcarboxylic acid. 9. For example, the third carboxy-functional polyester resin 'in the scope of patent application item 1 where X is 6 to 9. 10. In the scope of patent application item 1 The third carboxy-functional polyester resin 'wherein the A / (A + B) ratio is at least 0.6' and wherein the c / (C + D) ratio is at least 0.6 0 11. The third carboxy-gamma-based polyester resin, wherein the ratio of A / (A + B) is at least 0.9 'and wherein the ratio of c / (C + D) is at least 0.9. 12. A polyglycidyl ester resin' It is obtained by reacting the tertiary functional polyester resin with epitope alcohol such as item 1 in the scope of the patent application in the presence of an appropriate base ^ 13. A powdery coating composition comprising Polyglycidyl ester resin and cross-linking agent for item 2.-In. ≪. Nn i--i -1-< n ^^^ 1 In I—-1— --- ei (please first Please read the notes on the back of the reading and fill in this page again.) The paper size is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) 4 2542 G ii D8. 6. Scope of patent application. Powder coating 15. The powder coating composition according to item 13 or 14 of the scope of patent application, which is used to prepare a weathering and acid resistant hardening resin matrix. 16. Such as A powdery coating composition according to claim 15 in which a hardened resin matrix is used to coat a shaped article. (Please read the notes on the back before filling out this page) The printed paper size of the employees ’cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs shall be printed in China (CNS > A4 size (210X297 mm)). 87.2.23 Case No. R7107566 Category (the above blocks are filled by this bureau) Xiuyubu t A4 C4 (revised in March 1988) 11 Patent Specification Name New Lithium Chinese Outdoor Durable Coating Composition and Acid Functional Polyester Resin and Polyglycidyl Ester Suitable for the Composition English OUTDOOR DURABLE COATING COMPOSITIONS AND ACID FUNCTIONAL POLYESTER RESINS AND POLYGLYCIDYL ESTERS THEREOF USABLE THEREFOR Name 1. Jayne Frilix 2. Roland Petus, Clemente Gülen 3_Gregory John Higgins 4. Pituus Glados Koman nationality was invented in the Netherlands, the two 'creative residences and residences were in Amsterdam, the Netherlands No. 3 Bedhuis Road, Shenzhen City (Office) The Hague City, The Netherlands, It's Difficult | I-i * ilt Zfr Ρ, Γί! Ri if] Representative Name Lingyin® Family Logo: Annis Yatfan Zhu Difen_ -1-^ (CNS)- ----- The size of this paper is applicable to the China National Standards for Standards (cns) A4c, the Ministry of Economic Affairs, Central Government Standards Bureau, Employee Consumer Cooperatives Cooperative Press No. 87102566 patent application --- ". Chinese Manual Correction Page (March 88 ) B7 r | V. Description of the invention (1) L —... .4 25 :: The present invention relates to outdoor durable coating compositions, which are derived from the third functional polyester and / or from the third carboxylic functional Polyglycidyl ester resin based on polyester, and describe the third carboxyl functional polyester resin itself and especially linear resin, and polyglycidyl ester resin obtained by glycidizing the third carboxyl functional polyester resin. More specifically, the present invention describes a powder coating composition 'this contains the third functional polyester resin and / or the polyglycidyl resin and describes the hardened product obtained using the coating composition and shows improvement Outdoor properties. The breadth of outdoor durable powder coatings The system used is based on a polyester / diglycidyl isocyanurate (T GIC) blend. The coatings made from this blend show quite good outdoor durability, but from an environmental standpoint Further improvements are needed. In addition, the use of TGIC is questionable for health and safety reasons. TGIC is quite toxic (oral administration of 0.45 g / kg of L D50 in mice) and this compound was identified as a substance that induces mutations according to the Ames mutation test. Other widely used systems, especially those for automotive topcoats, include acrylic resins crosslinked with melamine resin and / or (blocked or unblocked) isocyanate. However, the hardening reaction of this type of system is bad for the environment because (usually) methanol is released. And 'this system does not provide the required level of durability for acid-catalyzed hydrolysis', especially for the hydrolysis of " Acid Rain 11 which contains sulfuric acid in rainwater. In addition, the durability of this system to UV light is generally acceptable, but obviously there is still room for improvement. It has been known for a long time that powders based on glycidyl solids obtained by the reaction of 2,2-bis (4-hydroxyphenyl) propane (bisfluorene A) with epichlorohydrin-4-paper size Applicable to China National Standards (CNS) A4 specification (210X 297mm) I ~-(Please read the precautions on the back before filling this page) -I ^ '定 弟 871〇2566 Chinese manual amendment page (March 88) A7 B7 V. Description of the invention (2 425420 Printed coating compositions of the Central Standards Bureau of the Ministry of Economic Affairs, Jeonggong Consumer Cooperative, "The hardened products prepared based on these compositions are resistant to hydrolysis. However, their resistance to ultraviolet rays is very low, so they are not suitable for use where high quality is required. The application of outdoor durability such as building parts or car finishes " Reference material in this regard is on EP_0T20997A, especially Tuxia, which is found based on epiKOTE (2,2_bis_ (4_hydroxyphenyl) propane Bis glycidyl ether) and many commercial polyester / acrylic resin powder coatings show only moderate weather resistance. Other known coating compositions are based on hydrogenated hydrocarbons, such as the glycidyl ethers of hydrogenated bisphenol A. Since there is no aromatic group, the U V resistance of the hydrogenated compound is better than that of the non-hydrogenated compound. However, since it has an aliphatic ether group, its outdoor durability is still relatively low, and its acid resistance is also very low. The third carboxylic acid functional polyester resin is described in European Patent Application No. OHWMA, U.S. Patent No. 3,749,758, British Patent No. i, 048,893, and Japanese Patent Application No. JP-A-58,189,261A. However, the examples actually prepared are based on resins containing aromatic dicarboxylic acids. Therefore, as in the example of the resin based on double brew A discussed above, the hardened products prepared from these water-based resins will show low UV resistance, and therefore are not suitable for high-quality outdoor durable applications. Known from the European Patent Application No. Brown EP-0 6 3 4 4 3 4 A and EP-0 7 2 0 9 9 7 A ~ When some linear third aliphatic carboxylic acid functional polyesters are used as coating compositions, In the hardened state, outdoor durability (UV stability) and hydrolysis resistance are required. Due to the increasing requirements of coating compositions for modern industrial applications, especially for economic and / or environmental considerations of powder coating compositions, the Chinese National Standard (CNS) Α4 for 5-paper standards applies ( 210X 297 mm) --- HI --- I- n I -------- 1 n τ · " * τ {Please read the precautions on the back before filling this page) Patent Application No. 87102566 4 25 4 2 0 Chinese Manual Correction Page (March 88) ^ V. Description of the Invention (9) Acid (cyclic) hydrocarbon group. Compound 0 is especially an aliphatic or cycloaliphatic acid, and even a second acid. The preferred compound G is a cycloaliphatic acid, and more preferably a second cycloaliphatic acid. The preferred compound G is a cycloalkylcarboxylic acid, especially a cycloalkylcarboxylic acid, more preferably a cyclohexylcarboxylic acid. As mentioned above, 'compounds A, B, c, D, E, F, and G are hydrocarbon groups containing one or more carbyl groups and / or several groups. Compounds may or may not be substituted. Substitutions must not damage the outdoor durability of the hardened product. Preferred compounds are those which are not substituted. It has been found that the molar ratio within the formula of the third carboxy-functional polyester according to the present invention is a suitable X value between 3 and 12, preferably between 5 and 10, and more preferably between Between 6 and 9. The K value can reach 2 and the L value can reach 2 and the preferred K and L · values are 2 °. A suitable A / (A + B) ratio is at least 0, preferably at least 0.75, more preferably at least 0.9, And the best is! . The C / (C + D) ratio is at least 0.6 ', preferably at least 0.75', more preferably at least 9 ', and most preferably 1. According to a preferred embodiment of the polyester resin, the Mo number of B is less than the Mo number of C. The present invention also describes a method for preparing the aforementioned third carboxy-functional polyester resin through the following reaction: Printed by the Consumer Standards Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs a) One kind of fatty compound A ′ contains two Each is independently an aliphatic hydroxyl group and a third carboxyl group of the first or second hydroxyl group, b) one or more hydroxyl compounds b as appropriate, each compound contains two aliphatic light groups, each of which is independently the first or the second Two light bases, c) at least one cycloaliphatic acid-acquiring compound c, which contains two second-aliphatic radicals or their acid residues, -12- this paper is in accordance with the Chinese National Standard (CNS) A4 specification {210X 297 public (Centi) 425420 Patent Application No. 87102566 Γ-Chinese Specification Correction Sheet (March SS) From the fifth, invention description (11), the result of glycidation of dimethylolpropionic acid. The chlorine content of the obtained product was 1.5%. This large amount of residual gas is not needed in the coating composition. In addition, due to the fact that the glycidyl esters reported in EP-A-0447360 are liquid, they are not usable as a powder coating composition. It has been found that both the third carboxy-functional polyester resin and the polyglycidyl ester resin of the present invention are suitable for use in a powdery coating composition, and in the hardened state, they show improved outdoor durability, especially improved weather resistance and acid resistance. And because of the polymer properties of the polyglycidyl ester resins of the present invention, their toxicity is lower than that of TGIC, so they can be used to favorably replace TGIC in powder coatings. 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 out this page) The third carboxy-functional polyester resin or polyglycidyl resin obtained by glycidizing the third carboxy-functional polyester resin ° The amount of the crosslinking compound used in the powdery coating composition of the present invention can usually be Provide approximately equal amounts of the reactive group of the branched compound and the epoxy group present in the tertiary group or the polyglycidyl glycidyl resin present in the polyester. The temperature at which the hardening is performed may be between 100 and 240 °, preferably between 120 and 200 ° C. The hardening temperature is usually 20-40 ° C lower than the composition of the prior art, while still obtaining the same degree of crosslinking. Use a catalyst if necessary. A suitable hardening time is 5 to 60 minutes, especially 10 to 30 minutes. Good results are usually obtained by curing at 140- 丨 60 ° C for 15 minutes. Crosslinked resins suitable for use in combination with the third carboxy-functional polyester resin of the present invention, such as outdoor durable epoxy resins, such as the polyglycidyl ester resin according to the present invention, as disclosed in European Patent Application No. 05 1 8,408A Of α, α -14- The size of the paper method is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) No. 87102566 Patent Application Chinese Specification Correction Sheet (March 88) 425420 A B5 Μ .t: t IV. Abstract of Chinese Invention (Name of the invention: outdoor long-time coating composition and acidic functional polyacetate resin) Polyglycidyl vinegar suitable for the composition The present invention relates to a kind obtained by the following reaction: Tertiary functional polyester resin: a) at least one aliphatic compound A, which contains two aliphatic hydroxyl groups and a third carboxyl group which are each independently a first or a second hydroxyl group, and b) one or more kinds selected as appropriate Via a compound B, each compound contains two aliphatic hydroxyl groups, each of which is independently a first or a second hydroxyl group, c) at least one cycloaliphatic carboxylic acid compound C, which contains two second aliphatic acids Or its anhydride, d) optionally one or more dibasic acid compounds D, which contain two aliphatic limb groups or their acid fibers, and e) optionally one or more compounds E, which contain a first or The second hydroxy group and a third carboxyl group or one or more monocarboxylic acid groups are selected as the case may be. / G OUT / OR OUTDOOR DURABLE COATING COMPOSITIONS AND- Abstract of the Invention (Invention (Name: ACID FUNCTIONAL POLYESTER RESrNS AND) POLYGLYCIDYL ESTERS THEREOF USABLE THEREFOR A tertiary carboxyl 'functional polyes l: er resin obtc \. \ N ^ bie by rencti.cm oC: a) at least one a 丄 ipfialiic cornpou n cl Λ -coiTip ^ rising Lwo alipha tic .1 groups which may'each .independen tl y be s primary or secondary hydroxyl group and a tertiary carboxyl group, _. Printed by the Consumers ’Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economy r IN —»-'If. *-I---- -—I (Please read the notes on the back before filling in the palms on this page) Thread b) optioniilly one or. Mo re 1 ί y cj j: o y.) / .1. Compounds B, 'p ^ icli 1 compound comprisi ng two aliphatic hydroxyl groups which nic! y each j. ndependsn L.ly be a p.ir lina ry. or secondary hydroy. y .1. gj: σ up, c) at: least one cy cO. ο π J. ip 1 ί at λ c (cr .r: boxy .1. Ic ri cid compound C coinp ri si. Jig dagger w〇seconds ry a 1 ip! Il: j. C ca r boxy l U roups or the anh yd ri de t: hie i; eo f,, ci) option nil y one or rn〇T: edi car!. · > 〇 >; yj. ic cid compooncis D comprising tw〇alipha tic carboxyl groups or tlie an It ride -2- The standard of this paper is applicable to Chinese National Standard (CNS) A4 specification (2.0 × 297 mm) 4 25 4 2 0 Patent application No. 87102566 X8 BS Landlord application special brake Lugang ^, τ table Leap year ng Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 11 VI. Apply for a patent + 1- A third carboxy-functional polyester resin obtained by the following reaction ... a) at least one aliphatic compound a, which contains two Each independently an aliphatic hydroxyl group and a third carboxyl group of the first or second hydroxyl group, b) one or more base compounds b as appropriate, each compound contains two aliphatic hydroxyl groups, each of which is independently the first or second Dikiaryl, 'c) at least one cycloaliphatic carboxylic acid compound c, which contains two second aliphatic condensates or their acid fields, d) optionally one or more dicarboxylic acid compounds d, which contain two Aliphatic radicals or their acid fibers, and e) optionally one or more compounds containing a first or second hydroxyl group and optionally a third carboxyl group, or one or more monocarboxylic acid compounds (G ) 'Comprising one or more compounds (F) selected from A and B, the first or second carboxyl group and isomol τ, compound (A + B): (C + D): E: F: G Ear ratio is (X · 1): X: K: L: Μ, where X ranges from 2 14, the range of 0 to 2 K 'L range to the range of 2 billion and Μ is square to the L value. 2. The third carboxy-functional polyester according to item 1 of the application, wherein the compounds A or B and F are the same. 3. For example, the tertiary functional polyester resin of item 1 in the scope of patent application, wherein compound A is dimethylolpropionic acid. 4. For example, the third carboxy-functional polyester resin of items i to 3 of the patent application park, wherein compound B is a straight chain α containing up to 8 carbon atoms' and optionally substituted by one or more methyl groups. , Ω-alkanediol compounds or may be used in accordance with the 11 national standards (CNS) A4 (210X297 mm) a tur-^^^ 1 ^^^ 1 in ί β HI: _ II ^^^ 1-1 ^ -β (Please read the notes on the back before filling this page}