TW531553B - Powder coating for cast iron pipe - Google Patents

Abstract

To obtain the subject coating material remarkably excellent in curability, capable of proceeding low temperature curing and good storage stability as well as other coating physical properties. This powder coating material contains (A) a solid bisphenol type epoxy resin having an alpha-glycol content of 0.03-0.07 meq/g and a hydrolyzable chlorine content of <= 200 ppm and (B) a curing agent as essential components.

Description

Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs of the People's Republic of China 5. Description of the Invention (1) ~~-[Technical Field of the Invention] The present invention relates to powder coatings suitable for use on the inner and outer surfaces of painted cast iron pipes, and more particularly A powder coating for cast iron pipes that is excellent in tightness, water resistance, chemical resistance, and mechanical properties, and also has rapid hardening and storage stability. In order to prevent the external corrosion phenomenon embedded in the soil and the internal corrosion phenomenon of the fluid, the cast iron pipes used for various fluid transportation such as sewage pipes, industrial water officials, and gas pipes are painted. In recent years, in order to obtain excellent corrosion resistance, tightness, water resistance, chemical resistance, and mechanical properties, the number of examples of coating with epoxy powder coatings has increased. The powder coating must be preheated before painting, and the powder coating is flattened and hardened by the heat. The energy cost of preheating the coated object will affect the manufacturing cost of the manufactured object. Therefore, it is necessary to use a hardening system that reduces the preheating temperature above 200 ° C to 150 ~ 180 ° C. In order to sufficiently perform powder hardening and coating film formation at the above-mentioned low temperature, it is necessary to improve the hardening property of the powder coating material. The method is, for example, a technique in which a solid bisphenol A (biSphenol-type epoxy resin is added with a part of a novolac epoxy resin. [Problems to be Solved by the Invention] However, the above-mentioned problem is solved in bisphenol A. A part of the powder coating of phenolic epoxy resin is added to the type epoxy resin, although it can improve the hardenability. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). Please fill out this page if you want to remove the matter) I 1 · I · Called 553 Printed bags A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) --- but it will cause the storage stability of the paint Problems such as poor performance and poor coating film. Furthermore, the above powder coatings for cast iron pipes using solid bisphenol A epoxy resin have poor storage stability and are prone to gelation during long-term storage. Therefore, hot coating It is difficult to form a film at the same time, and paint spots are generated due to reduced fluidity, which leads to the problem of corrosion resistance when painted cast iron pipes. In addition, powder coatings are stored in a powder state, so they are very gelled. It is difficult to find out that it is not known whether it has been mixed into the gel or not until it is actually painted. In order to solve the above-mentioned problems, the present invention provides a powder coating for cast iron pipes, which has significantly hardenability. Excellent, can be hardened at low temperature, and at the same time, storage stability and coating film properties are good. [Solution to the problem] In order to solve the above problems, the present inventors made efforts to study and found that epoxy resin used in powder coating for cast iron pipes, By making ^ specific bisphenol-type epoxy resins, it is possible to avoid storage stability and decrease the physical properties of the coating film and significantly improve the hardenability, and finally to complete the present invention. That is, in order to solve the above problems, the present invention relates to a kind of Powder coatings for cast iron pipes, the essential ingredients include: solid bisphenol epoxy resin (A) 'The amount of α-ethylene glycol is 0.03 ~ 0.07meq / g, and it is hydrolysable The gas is 200 ppm or less; and the hardener (B). The solid bisphenol epoxy resin (A) used in the present invention has an amount of ethylene glycol of 0.03 to 0.07 meq / g, and is hydrolyzable. The gas is less than 200ppm. (Please read the precautions on the back before filling this page) Order · 531553 A7 _ B7____ V. Description of the invention (3) ~~ 'That is, the water-decomposable gas volume is 200ppm or less, which can effectively improve hardening And paint storage stability. On the other hand, even if the amount of hydrolyzable gas is 200 ppm or less, and the amount of α ethylene glycol is less than 0.03 meq / g, or more than 0.07 meq / g, storage Stability is significantly reduced. Here it is important to point out that generally, the lower the amount of α glycol, the better the hardening. However, although the amount of α glycol in solid bisphenol epoxy resin (A) Between 0.03 and 0.07 meq / g, it still exhibits excellent hardenability. Here, α ethylene glycol means a di 3-dihydroxypropyl structure having a ring-opening structure due to the hydrolysis of an epoxy group at the molecular end of the solid bisphenol epoxy resin (A). In the present invention, especially from the viewpoint of the balance between the hardenability and storage stability of the powder coating, the amount of ethylene glycol in the solid bisphenol epoxy resin (8) is 0.03 to 0.07 meq / g, and water is added. The decomposable gas is preferably 100 ppm or less. The above-described Gubin bisphenol epoxy resin (A) is not particularly limited to those at normal temperature, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, and tetrabromobisphenol A ring. Oxygen resin, as well as epoxy resin printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs. Among the above, from the standpoint that the significant effects of the present invention can be achieved, a bisphenol A type epoxy resin is preferred. • Furthermore, the above solid bisphenol epoxy resin is obtained by reacting epihalohyddn with bisphenols, and is manufactured by a so-called one-stage method. Furthermore, the reaction of "Hydrocycline" and double-hop reaction, after the manufacture of double-hop epoxy resin, the material oxygen tree is advanced-step and double_reaction 2 6 A7-1 · &quot; ~-· * ----- ---B7 ____ V. Description of the invention (4)-It can also be produced by the one-stage method. One-stage method can be listed, for example: 〇 The mixture of epichlorohydrin and glycidide is reacted with the double-expanded compound to reach the target molecular weight. '; Η②, epichlorohydrin is reacted with alkali metal hydroxide in advance, and it is treated as a mixture of% tritium propane and glycidol, and secondly, the above mixture is reacted with double hops to reach the target molecular weight. Methods; and ③ a method of reacting epoxy propane with bisphenols to reach a target molecular weight 'to obtain a ϋ-shaped ㈣-type epoxy resin, and then reacting with a metal chloride to test the terminal α to PEGylate. Examples include: ④ Epoxy propane is reacted with an alkali metal hydroxide in advance as a mixture of epichlorohydrin and glycidol. Second, the above mixture is reacted with bisphenols to obtain an intermediate liquid epoxy resin. Second, , Lee A method for quantifying the above-mentioned intermediate liquid epoxy resin by bisphenols; ⑤ reacting epoxy propane with bisphenols to obtain an intermediate liquid epoxy resin, and further, the above intermediate liquid epoxy resin and shrinking Glycerin and difluorene reactions for high molecular weight method; printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs; ⑥ reacting epoxy propane with bisphenols to obtain intermediate liquid epoxy resin; After the epoxy resin reacts with an alkali metal hydrogen compound to PEGy the terminal epoxy group α and then use a method of quantifying the bisphenol polymer; and ⑦ reacting propane epoxy propane with bisphenol to obtain an intermediate liquid ring Oxygen resin, and the above-mentioned intermediate liquid epoxy resin is heightened by 7 bisphenols. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm). 5. Description of the invention u The method of phenolic jade clothing oxygen secret lipid 're-diolated with alkali gold M' epoxy group. Viewpoint U side: go: medium 'from the special purpose of easy adjustment of epoxy equivalent., &gt; Denier, &lt; The two-stage method is preferable, and in particular, the method of ④ is preferable from the viewpoint of easily adjusting the amount of α ethylene glycol. The method of ④ is described in more detail below: That is, the method of ④ Pre-react with the test metal nitrogen oxide aqueous solution to obtain a mixture of epoxy propane and glycidol (step 1). The above mixture is reacted with the double-panes in the presence of the test metal hydroxide to obtain an intermediate liquid ring. Oxygen resin (step 2). Secondly, the above-mentioned intermediate liquid% oxygen resin is reacted with bisphenols to achieve high molecular weight (step 3). Economy, Shao Central Bureau of Standards, Consumer Consumption Cooperative, Printing Step 1, Although the reaction conditions of the epoxy gas propylene oxide compound and the metal hydroxide aqueous solution are not particularly limited, for example, an epoxy chlorohydrin compound and a 1 to 20% alkali metal hydroxide aqueous solution can be exemplified in Fortunately, the method of contacting at 85 ~ 95 ° C can easily produce a mixture of glycidol and epichlorohydrin by the reaction as described above. In this mixture, the 'existing ratio of glycidol to epichlorohydrin is not particularly limited, but from the viewpoint of easily adjusting the content of ethylene glycol in the epoxy resin produced, the weight ratio is preferably the former / The latter is in the range of (2 ~ 10) / (98 ~ 90). Next, step 2 includes, for example, reacting the epoxy propane and glycidyl mixture obtained above with bisphenols in the presence of an alkali metal hydroxide. The specific method here is not particularly limited. However, from the production of this paper, the Chinese National Standard (CNS) A4 specification (210'〆297 mm) is applicable. 531553 Via the Consumer Standards Cooperative of the Central Standards Bureau of Didi Printing Department A7 B7 5. In view of the point of view of the invention (I), after the reaction in step 1 is terminated, a double-pane type is added to the reaction vessel to dissolve it, and then, a method for detecting a metal hydroxide is added. The mixture of epoxy gas propylene glycol and glycidol, and the reaction ratio of bisphenols are not particularly limited. However, from the viewpoint of easily adjusting the amount of α ethylene glycol and reducing the oxygen equivalent, the molar ratio is the former / the latter. = 5 ~ 20 is better. At this time, the specific reaction of glycidyl etherification is as follows: Step 1 of 1: In epoxy propane containing bisphenols and glycidol, it is continuously added under normal pressure or reduced pressure at 70 ～ 11〇 艽. An aqueous solution of an alkali metal rat oxygenate, and after reacting for 3 to 5 hours, an organic solvent and water are added, and the generated sodium gas is separated and removed. Step 2 of 2: Add 5 ~ 50% alkali metal hydroxide aqueous solution to the organic layer at 70 ~ 100. (: The reaction time is υ hours. After the reaction is terminated, water is added to remove the byproduct metal test salt. Furthermore, distillation is used to recover epichlorohydrin to produce an intermediate liquid epoxy resin. At this time, by adjusting step 2 The amount of the alkali metal hydroxide aqueous solution used in 2 can adjust the amount of water-decomposable gas in the intermediate liquid epoxy resin, so the amount of water-decomposable gas in the solid bisphenol-type epoxy resin (A) finally obtained can be adjusted. In order to make the water-decomposable gas amount in the solid bisphenol epoxy resin (A) be 200 ppm or less, it is preferable that the water-decomposable gas amount in the intermediate liquid epoxy resin is 300 ppm. Make the amount of alkali metal hydroxide aqueous solution used in step 2 to 2 correspond to the Chinese paper standard (CNS) A4 specification (210X297 mm) relative to the paper size of the paper (please read the idea on the back and fill in this page)

, 1T is called 553 A7 B7 V. Description of the invention (7)-^, the chlorine atom in the crude epoxy resin obtained in 1 is the ratio of the equivalent. In addition, in order to make the amount of water-decomposable chlorine in the solid bisphenol epoxy resin (A) be 100 ppm or less, it is preferable to set the amount of water-decomposable chlorine in the intermediate liquid epoxy resin to 160 ppm. Preferably, the amount of the alkali metal hydroxide aqueous solution used in step 2-2 is an equivalent ratio of ~ to the gas atoms in the crude epoxy resin obtained in step 2-1. · The bisphenols that can be used here are not particularly limited, and examples thereof include phenol A bisphthalate F, bispan S, and tetrabenzyl a. From the viewpoint of achieving the significant effects of the present invention, bisphenol A is particularly preferred. In addition, in order to make the content of α ethylene glycol in the solid bisphenol epoxy resin (A) in the range of 0.03 to 0.07 meq / g, it is preferable to make the α ethyl glycol in the intermediate liquid epoxy resin obtained in step 2 The diol content was from 0.04 to 0_lmeq / g. In addition, the properties of the intermediate liquid epoxy resin to be produced are not particularly limited, but the epoxy equivalent is in the range of 160 to 23 g / eq, particularly in the range of 170 to 210 g / eq, and the viscosity is 1,000 to 100,000 cps, especially in the range of 3000 to 400 cps. In addition, it is preferable to perform the high molecular weight reaction treatment in step 3, which is relatively easy. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Secondly, step 3 is to make the intermediate liquid epoxy resin further react with bisphenols to obtain an epoxy resin having a higher molecular weight and a higher amount of α glycol. The reaction method is not particularly limited, however, for example, an intermediate liquid epoxy resin and bisphenols may be charged into a reaction vessel, a reaction catalyst may be added, and heating may be performed while stirring in an environment filled with an inert gas. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 male Chu) 531553 A7

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (8 and the method of reaction while stirring.: Treatment: The use of double_ is not particularly limited, double hope F, double hope, four deserts, double, etc. ： ： From the viewpoint of the significant effect of the invention ^ ^ I can reach this point, especially bisphenol A. The catalyst used in step 3 is limited by sodium hydroxide and hydroxide. For example, ^ A ^ calcium 4 alkali metal hydroxide; sodium carbonate i ±-butane 4 amines; phosphines such as triphenylphosphine 丨 and anyone who can be used for the reaction of epoxy groups and phenolic hydroxyl groups. 仃The reaction temperature of this reaction is preferably 100 to 25 (rc.) That is, the reaction is faster at a temperature above 100C, and in addition to making the reaction shorter, it is not easy to cause epoxy groups. The side reaction is easy to adjust the epoxy equivalent car parent. Furthermore, the ethylene glycol content of the solid bisphenol epoxy resin (A) obtained as described above is from 0.03 to 0.07 meq / g, and, The hydrolyzable chlorine is 200 Ppm or less, so storage stability can be greatly improved. The epoxy equivalent and melt viscosity of the oxygen resin are not particularly limited depending on the input ratio of the intermediate liquid epoxy resin to the bisphenols and the resin structure. However, from the standpoint of blocking resistance and easy manufacture of powder coatings It appears that its epoxy equivalent is 500 ~ 1500g / eq, especially 740 ~ 1300g / eq; and the dilution dryness (40% by weight of the resin into a knife is a solution of ethylene glycol monobutyl scale, in The Gardner viscosity at 25 ° C is in the range of C ~ Z9, especially X ~ Z7. Furthermore, the obtained solid bisphenol epoxy resin (the content of ethylene glycol in / ^ is 0.03 ~ 0.07meq / g, and the water-decomposable gas is π Please read it first-Note · Notes _ Fill in this page to order-# This paper size applies to China National Standard (CNS) A4 specification (210'〆297 mm) 531553 Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards, Ministry of Standards, A7, B7 V. Description of the invention (9) Below 20 ppm, however, it will further improve the hardenability and storage of powder coatings.

From the viewpoint of Tibetan stability balance, the amount of α ethylene glycol is preferably in the range of 0.003 to 0.07 meq / g, and the hydrolyzable chlorine is preferably 100 ppm or less. In particular, the epoxy resin obtained by the latter two-stage method is easy to adjust to the desired epoxy equivalent. In addition, bisphenols used in the above-mentioned one-stage method and two-stage method include, for example, bisphenol A. , Bisphenol F, tetrabromobisphenol A, tetrabromobisphenol f, etc. From the viewpoint that the significant effects of the present invention can be achieved, bisphenol A is preferred. The solid bisphenol-type epoxy resin (A The epoxy equivalent of) is not particularly stable. However, from the viewpoint of blocking resistance and easy coating of the powder, its equivalent weight is preferably 500 to 1500 g / eq. Particularly, the viewpoint of significant effect = In particular, it is preferably 740 to 1300 g / kg. 1 Next, the hardener (B) used in the present invention is not particularly limited. However, examples thereof include system compounds, substances, dicyanohydrazide, and derivatives thereof, Imidazole and its derivatives. Of course, from the viewpoint of better chemical properties, imidazoline compounds are better. In addition to greatly improved storage stability, it can be significantly improved when reburned. From the viewpoint of organic acids such as polycarboxylic hydrazide, etc. The hydrazide is preferred. Such as two. = Lynn compounds are not particularly limited, Example 2] (1) 12

This paper size applies to Chinese national standards (CNS (Please read the precautions on the back before filling out this page)

W1553 Five A7 B7, description of the invention (10) (wherein R1 represents an alkyl group having 7 carbon atoms and a phenyl group, and R2 represents hydrogen or an alkyl group having 1 to 3 carbon atoms). Among the above-mentioned imidazoline compounds, especially R1 is a phenyl group, and R2 is a phenylimide group. For the prevention of perforation and resistance, the hardener (B), for example, uses The milsalene-based compound can be used in combination with dicyandiamide-based compounds, polyacid hydrazide and two organisms, saliva and its derivatives, and other oxazoline-based compounds in the range of the general formula ⑴. That is, in the present invention, when the day-to-day soil oxygen resin (C) is added to the above (A) and ⑻, its fluidity can be improved by 4, and the effects are more significant. ^ Crystalline epoxy resins, those who can obtain coatings with strong melting, high fluidity and uniformity, such as the specific examples listed below. (1) Triglycidyl isocyanate (Nissan Chemical Co., Ltd.) trade name "TEPIC G" (2) 4,4'_bis (2,3_glycidoxy) _3,3 |, 5,5,- Tetramethyl Union (Petrochemical Snow Land Epoxy (Shares)) Trade Name "EPICOTE YX-4000 Industry (share bis (2,3-epoxypropoxy) _Cai (Da Yueben Inki Chemical Co., Ltd." EPICLONHP -4032J (4) bis (I, 2-glycidyloxy_naphthyl) _methane (5) 2,2-bis [3,5-dibromo moiety, 2_glycidyloxy) _benzene Base]-Propane Benzene Paper Size Applicable to Chinese National Standard cm) A4f Grid (13 531553 A7 B7 V. Description of Invention (n) (Da Nihon Inka Industrial Chemicals (Stock)) Trade name "EPICLON152-CR" Crystal used The blending ratio of the epoxy resin (C) is not particularly limited, but it is preferably in the range of (A) / (C) = 80/20 to 99/1 on a weight basis. That is, the crystalline epoxy resin ( C) When the blending ratio is (A) / (C) = 99/1 or more, the melt viscosity will decrease, and the fluidity and the prevention of perforation will be improved. Furthermore, (A) / (C) = 80/20 In the following cases, the uniformity of the melt-kneaded product using an extruder becomes excellent during lacquering. Moreover, the clumping property can be improved. From the viewpoint of achieving a significant effect, (A) / (C) = 95/5 to 85/15 is particularly preferable. Furthermore, the amount of the hardener (B) used It is not particularly limited, but the equivalent basis of the hardener (B) is [solid bisphenol epoxy resin (A), or (A) and crystalline epoxy resin (C) combined] / hardener ( B) = 1.0 / 0.10 ~ 1.0 / 0.50. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). That is, the amount of hardener (B) used is [ (A), or (A) + (C)] / (B) = 1.0 / 0.10 or more, the hardenability becomes faster, and the melt viscosity becomes lower, and the fluidity, the prevention of perforation, and the corrosion resistance are improved. Another On the other hand, when it is 1.0 / 0.5 or less, the molecular weight of the hardened material increases and the physical properties of the coating film can be improved. From the viewpoint of the above-mentioned performance balance, it is preferably 1.0 / 0.20 to 1.0 / 0.4. The powder coating for cast iron pipes of the present invention If necessary, extender pigments and / or coloring materials such as titanium dioxide, talc, calcium carbonate, barium carbonate, silicon dioxide, aluminum oxide, carbon black, phthalocyanine green, Phthalocyanine blue, etc. 14 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 531553 A 7 B7 V. Description of the invention (12) When coating with the above materials, it can be done by ordinary methods. That is, , Coarsely pulverize the solid bisphenol epoxy resin (A), hardener (B), crystalline epoxy resin (C), extender pigment / coloring material, and other additives as needed, and then mix, then The above preparation is fully pulverized by a HENSCHEL mixer, melted and kneaded by an extruder after mixing, and then pulverized after being cooled and classified. [Examples] Examples of the present invention are described in detail below, but the present invention is not limited thereto. Synthesis Example 1 [Step 1] 370 g of epoxy propane (4 mol) and lllg of 3% sodium hydroxide were put into a long-necked flask equipped with a stirrer, a thermometer, and a decanter including a cooler, and stirred at 90 ° C. 2 Hours. After stirring was stopped, epichlorohydrin was sampled, and the glycidol content was measured to be about 4.5%. Yin Fan, a Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the legal notices on the back before filling out this page) [Step 2 of 1] After separating and removing the water layer, add 228g (lmol) of bisphenol A, dissolve, and then Under reduced pressure, 158 g (1.9 mol) of 48% sodium hydroxide was dropped at 70 ° C while stirring. In the meantime, the long-necked flask continued to be heated, and epoxy propane remained in the long-necked flask. Furthermore, after stirring for 30 minutes, epichlorohydrin was distilled and recovered at 150 ° C, and then 440 g of toluene and 170 g of water were added to dissolve and agitate the generated sodium gas. After stopping, the sodium gas was removed by liquid separation. Water layer. 15 This paper size applies to China National Standard (CNS) A4 (210X297 mm) A7 B7

V. Description of the Invention (l3) [Step 2 of 2] Secondly, after adding a 5% sodium hydroxide water-soluble solution at tl ° c to teach 1 +, after the teaching is stopped, use the liquid epoxy resin:丨 丨 丨 4—— (Please read the precautions on the back before filling out this page) "Then, add 170g of water for washing, and then discard the water layer. After dehydration and transition steps, f will be recovered by distillation to obtain" a ^ … The properties of the intermediate liquid epoxy resin are as shown in Table 丨 [Step 3] Take 7G.4 parts by weight of the intermediate liquid epoxy resin synthesized by the above method, and 39.6 parts by weight of bisphenol a into a four-necked flask, add 100 ppm of sodium hydroxide 'was heated under nitrogen flow at 14 ° C for 8 hours. The epoxy equivalent of the obtained resin was 91 °-, the viscosity was determined to be Gardner viscosity in a solution of S-T (non-volatile content of 40% diethylene glycol monobutyl ether), and the melting point was 1,000 ° c. Synthesis Example 2 Step 1 is the reaction of epoxy propane with 3% sodium hydroxide for 3 hours. Step 2-2 is the same as that used in Synthesis Example 1 except that 1G () g of 5% sodium hydroxide aqueous solution is used. Step operation to obtain intermediates of liquid epoxy resin printed by employees' cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. The properties of the above intermediate liquid epoxy resins are shown in Table_1. Next, in step 3, the above-mentioned liquid bisphenol A-type epoxy resin and bisphenol a in the proportions shown in Table 1 were charged, and the same reaction as in Synthesis Example 丨 was performed to obtain Resin 2. The properties of the composition are shown in Table 1. Synthetic Example 3 16 531553 A7 B7 Printed Invention Description of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (14) Step 2-2 except that 100 g of 5% sodium hydroxide aqueous solution was used. An intermediate liquid epoxy resin was obtained. The properties of the intermediate liquid epoxy resin are shown in Table 1. Next, in step 3, the above-mentioned liquid bisphenol A-type epoxy resin and bisphenol in the proportions shown in Table 1 were charged, and the same reaction as in Synthesis Example 1 was performed to obtain a resin 3. The properties of the composition are shown in Table 1. Synthesis Example 4 Except that 85 g of a 5% sodium hydroxide aqueous solution was used in Step 2-2, the same procedure was used as in Synthesis Example 1 to obtain an intermediate liquid epoxy resin. The properties of the above intermediate liquid epoxy resin are shown in Table 丨. As shown. Next, in Step 3, the above-mentioned liquid bisphenol A type epoxy resin and bisphenol A 'in the proportions shown in Table 1 were charged and the same reaction as in Synthesis Example i was performed to obtain a resin 4. The properties of the composition are shown in Table 1. Synthesis Example 5 Step 3 A commercially available liquid bi-a-type epoxy resin ("EPICLON 8 side", manufactured by Dainippon Inka Chemical Industry Co., Ltd., ee = i 8 sentences, and double hope A showing a ratio, and The same reaction was performed as in Synthesis Example i to obtain Resin 5. The properties of the composition are shown in Table 1. Synthesis Example In addition to the reaction of propylene oxide with sodium hydroxide at 30/0 for 35 hours, Example 1 uses the same steps to get the middle (please read the precautions on the back before filling this page) L ·

1T φι. 17 This paper is suitable for Guancai County (CNS) MW ^ T2 \ 0 X 291 ^ 531553 A7 B7 V. Description of the invention (b) — Liquid epoxy resin, the properties of the above intermediate liquid epoxy resin As shown in the table "showing 0 its-human 'step 3, the liquid bis A-type epoxy resin and bisphenol a in the proportions shown in Table 1 were put in, and the reaction with the phase of Synthesis Example i was performed to obtain a resin 6. Composition The properties are shown in Table 1. [Table 1] Table-1 Liquid properties of the phenol and the synthesis examples EE (g / eq) α ethylene glycol hydrolyzable chlorine 187 0.07 104 2 189 0.05 145 190 0.07 145 190 0.04 390 184 0.02 100 6 C Please read the notes on the back before filling in this page. J-Order the liquid BPA 60.3 39.7 70.6 29.4 70.7 29.3 70.7 29.3 69.9 30.1 The nature of the composition of printed composites by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs EE ( g / eq) Softening point viscosity 910 100 ST 0.05 75 905 99 ST 0.035 105 907 100 ST 0.05 100 910 99 ST 0.05 280 900 98 ST 0.015 70 α Glycol (meq / g) Hydrolysable gas

61 ΐ / 18 This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm).

T ο 8 531553

五 _I_ Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs I A7 B7 Description of Invention (16). Examples 1 to 6 and Comparative Examples 1 to 4 After coarsely pulverizing the ingredients described in Tables 2 to 4-4, use Table 2 ~ The ratios listed in Table 4 were blended, and then fully pulverized and mixed using a HENSCHEL mixer. After that, the extruder was heated and melted and kneaded, extruded, cooled, and pulverized, and then classified to obtain a powder coating of 80 to 120 µm. Using the obtained powder coatings, the gelation time, storage stability, appearance of hardened coating film, financial impact test, Erichsen test, salt water spray test, and water resistance of each example and comparative example were performed according to each standard. Evaluation and other tests. In addition, a test of the appearance and water resistance of the hardened coating film was performed by spraying the obtained powder coating material on the surface of a test piece heated to 180 to 210 t: this test piece was left with oxidized scale on the surface only after brushing treatment 丨A high-strength cast iron sheet with a size of 50 mm × 70 mm × 7 mm was spray-coated on the test piece and allowed to cool to form a 250-350 μm thick coating film for evaluation. Moreover, the financial impact test and the salt spray test are performed using 150 mm X 70 mm

Steel plates with X2.0 legs, and the Eriksson test uses steel plates with 90 legs x 90mm X 1.2, which also formed coating films of 25 to 35 μm, respectively, for evaluation. (Gelling time) Measured on a baking plate at 170 ° C. (Storage stability) [Gelling time after holding at 40 ° C for 1 week / Gelling time shortly after adjustment] X 100 ---- Ί — — — ^ ------ Order II ---- Φ, *-(Please read the "fir ^ vi- 意 事 'item before filling out this page") This paper size is applicable to the Chinese National Standard (CNS) Α4 specification (21〇 &gt; &lt; 297 public director) 531553 A7 _______B7 Explanation of the invention (17) — (Appearance of hardened coating film) The smoothness of the surface of the coating film was visually evaluated. (Impact resistance test) JIS K 5400_1990-8, 3, and 2 (DuPont-type impact test) were used for testing. (Eriksson Test) Evaluation was performed by method A of JIS Z 2247. (Brine Spray Test) The gap between the coating film surface and the substrate is deep, and then used at 3 μc. NaCl aqueous solution was sprayed continuously for 3,000 hours, the state of the coating film was observed, and a knife was put into the wound to observe the degree of creep peeling. (Water resistance) After immersing the coating material in water for one year, the state of the coating film was measured. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 2 This paper size applies to the Chinese National Standard (0 milk) 8 4 specifications (210 father 297 mm) U53 A7 B7 ____------ Description of the invention (1 piano) [Table 2] Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economy-2 Example 1 ___——--- Example 2 —. —--- Example 3 ---------- &quot; Example 4 Resin 1 100 95 Resin 2 100 Resin 3 100 Resin 4 EPICOTEYX-4000 5 Cinnamon B-phenylimidazoline 4.8 (0.3) 4.8 (0.3) 4.8 (0.3) 5.8 (0.3) Physical pigment Ti〇2 10 10 10 10 SiO , 30 30 30 30 Additive MODAFLOW 0.5 0.5 0.5 0.5 Gelation time 85 86 83 87 Storage stability 87 85 82 82 Appearance (smoothness) of hardened coating film Good Good Good Good ^^ (cm) · 40 40 40 40 Erickson test 4 4 4 4 Saltwater spray weaving abnormal abnormal abnormal creep size_ &lt; 1 mm &lt; 1 mm &lt; 1 mm &lt; 1 mm water resistance (1 year) No abnormality 1 No abnormality No abnormality If there is no abnormality, please read the back first-ii: Matters needing attention before 21 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 531553 A7 B7 V. Description of the invention (19) [Table 3] Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by Shellfish Consumer Cooperatives Table-3 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Resin 2 95 resin 3 95 resin 4 100 resin 5 100 EPICOTE N-690 EPICOTE YX-4000 5 5 phenylimidazolium 5.8 (0.1) 5.8 (0.3) 4.8 (0.3) 5.8 (0.3) Physical pigment Ti02 10 10 10 10 Si02 30 30 30 30 Additive MODAFLOW 0.5 0.5 0.5 0.5 Gelation time 82 83 85 79 Storage stability 80 81 68 73 Appearance (smoothness) of hardened coating film Good Good Good Good 40 40 40 40 Erickson test 3 3 4 4 Salt water Spray test. Abnormal abnormal abnormal screw becomes larger λ! ,, &lt; 1 mm &lt; 1 mm &lt; 1 ram &lt; 1 ram, and only water (1 year) No abnormality No abnormality No abnormality No abnormality 22 Paper size Applicable to China National Standard (CNS) A4 specification (210X 297 mm). ^-ΙΦ, 玎 Φ, (please read the back page, 5: ½ intentions, and then fill out this page) 531553 A7 B7 V. Description of the invention ( 20) [Table 4]

Resin 6 90 90

10 EPIGLON 4050 EPICLON N-690 EPICOTE YX-4000 phenylimidazoline physical pigment Ti02 10 _Ti〇2 30 ----— Additive MODAFLOW Gelation time 83 Storage stability 70 Hard coating Film appearance smoothness) Good impact resistance test (cm) 30 Erickson test 5 Salt water spray test state without abnormal creep mm and water solubility (1 year) No abnormality ^ 5 80 63 Good 20 2 No abnormality 3 mm Ai often [Inventive effect] According to the present invention, it is possible to provide a powder for cast iron pipes, which is particularly excellent in hardenability and can be hardened at low temperature. At the same time, it has good stability, its mothproof, tightness, water resistance and chemical resistance Physical properties such as coating film and mechanical properties are also good. Coating 23

Claims (1)

ΒΒ ΒΒ 六 化 1 Date: 91 · 7 · 5 Scope of patent application β I Moon search α, · P 十 h A kind of powder for cast iron pipe ^ points include: solid double-phase epoxy resin (A), which makes The epoxy equivalent of bisphenols in the form of liquid bisphenol-type oxygenate is 740 ~ 1300g / m. It is a solid bisphenol-type oxygen resin with an α ethylene glycol content of 0 03 ~ 0. 07 meq / g, and the water-repellent rat is 200 ppm or less; and the hardener (B) 'equivalent reference ratio is solid bisphenol epoxy resin (A) / hardener (B) = 1 · 〇 / 〇1〇〜1〇 / 〇 · 50。 The ratio. 2. The powder coating for cast iron pipes as described in item 1 of the scope of the patent application, in which the 5 basal hardener (B) is an imidazoline compound. 3. The powder coating for cast iron pipes according to item 2 of the scope of the patent application, wherein the imidazoline compound is represented by the following general formula (1). (Please read the notes on the back before filling out this page) Installed with Ri NVR, general formula (1) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 'R1 represents the carbon number of alkyl and phenyl, and the ruler 2 represents hydrogen or an alkyl group having 1 to 3 carbon atoms) 4. The powder coating for cast iron pipes according to item 2 of the scope of the patent application, wherein the imidazoline compound is phenylimidazoline. 5. The powder coating for cast iron pipes according to item 1, 2, 3 or 4 of the scope of patent application, which further includes a crystalline epoxy resin (C). 6. Powder coating for cast iron pipes as described in item 5 of the scope of patent application f ^ — §8 6. Application for patent application ^ ^ ^ ----- = 'its t the solid bisphenol epoxy resin (A) and the weight ratio of the crystalline epoxy resin I reference ratio is, (A) / (C) = 80/20 ~ 99/1. Material jj · Powder coating for cast iron pipes as described in item 5 of the scope of the patent application = 1 ^ The equivalent reference ratio of the hardener (B) is [solid bisphenol-type oxygen resin (A) and crystalline ring Oxygen resin (C) total] / hardener (BΗ · ο / 〇 · 10 ~ 10 / 〇50。 ratio. 8. The powder coating for cast iron pipes as described in item 5 of the patent claim, wherein the solid form Bisphenol epoxy resin (A) and crystalline epoxy resin have a weight ratio of 1 based on the ratio of (A) / (B) = 80/20 to 99/1, and the equivalent weight of the hardener (B) is used. The ratio is [total of the solid double-expanded epoxy resin (A) and the crystalline epoxy resin (c)] / hardener (B) = 1.0 / 0 · 10 ~ 1 · 〇 / 〇 · 50. ^- ------- ^-j (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)