JPH0372672B2 - - Google Patents
Info
- Publication number
- JPH0372672B2 JPH0372672B2 JP59046990A JP4699084A JPH0372672B2 JP H0372672 B2 JPH0372672 B2 JP H0372672B2 JP 59046990 A JP59046990 A JP 59046990A JP 4699084 A JP4699084 A JP 4699084A JP H0372672 B2 JPH0372672 B2 JP H0372672B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acid
- polyester
- polyester resin
- reference example
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- 229920001225 polyester resin Polymers 0.000 claims description 34
- 239000004645 polyester resin Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 34
- 229920000728 polyester Polymers 0.000 description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 19
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 11
- 150000008064 anhydrides Chemical class 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 125000003158 alcohol group Chemical group 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- -1 isopentyl glycol Chemical compound 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
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The present invention relates to an improved resin composition for powder coatings, and more particularly to a resin composition with a specific acid value obtained by reacting a polyester resin with a specific hydroxyl value with a polyfunctional organic carboxylic acid anhydride. had,
It forms a coating film that is excellent in appearance, mechanical strength, and corrosion resistance, and has a polyester resin with residual hydroxyl groups and a polyepoxy compound as essential components, and is also useful because it has excellent storage stability. The present invention relates to a resin composition. BACKGROUND ART Powder coatings made of carboxyl group-containing polyester resins and polyepoxy compounds have been used for a wide range of purposes because of their excellent mechanical strength, adhesion, and corrosion resistance. At this time, it is particularly important to use a carboxyl group-containing polyester resin obtained by reacting a polyester resin having hydroxyl groups with a polyfunctional organic carboxylic acid anhydride as the base polyester resin to be combined with the polyepoxy compound. It is described in the specification of Japanese Patent Publication No. 55-15506 and the specification of Japanese Patent Publication No. 58-29342 and is well known. However, as long as the techniques described in these known documents are followed, powder coatings are mainly based on polyester resins with relatively high acid values, mainly in the range of 40 to 70. Therefore, the storage stability of powder coatings is unavoidable, and reactions progress during storage, resulting in many coatings using such coatings having poor smoothness. Since a resin with almost no hydroxyl groups is used as the base polyester resin, it tends to have insufficient compatibility with polyepoxy compounds, and especially when increasing the pigment concentration, it is difficult to melt. Another drawback is that poor dispersion occurs during kneading, resulting in poor coating film smoothness or image clarity. However, in view of the various shortcomings in the prior art as described above, the inventors of the present invention conducted extensive research and found that a polyester resin having a hydroxyl value within a specific range, that is, a polyfunctional polyester having a valence of 3 or more, is used as an intermediate polyester. The specific acid value and softening point obtained by reacting a divalent or higher polyfunctional organic carboxylic acid anhydride (hereinafter also referred to as polycarboxylic acid anhydride) containing a polycarboxylic acid anhydride as an essential component. The present invention was completed based on the discovery that all of the above-mentioned drawbacks can be overcome by using a polyester resin having a polyester resin having hydroxyl groups remaining. That is, the present invention has a hydroxyl value of 12.5 to 70KOH.
mg/g (hereinafter, units are omitted) and has an acid value of 2 to 10 (a-1) (hereinafter,
Abbreviated as intermediate polyester. ) with a polycarboxylic anhydride (a-2), a polyester resin (A) having an acid value of 15 or more and less than 30, a hydroxyl value of 2 or more, and a softening point of 80 to 150°C
60 to 97 parts by weight as a base polyester resin component, and 3 to 40 parts by weight as a crosslinking curing agent component of a polyepoxy compound (B) having at least two epoxy groups in one molecule. It has good compatibility with the polyepoxy compound, which is composed of The present invention provides a resin composition for powder coatings that has excellent smoothness and sharpness. Here, the above-mentioned polyester resin (A), which is one essential component of the composition of the present invention, is obtained by reacting a polycarboxylic anhydride (a-2) with an intermediate polyester (a-1) having a hydroxyl group as described later. obtained, each having an acid value of 15 to less than 30, preferably 16 to 28, and a hydroxyl value of 2 or more, preferably 3 to 20, and a softening point of 80 to 150°C,
Preferably within the range of 90 to 130°C, it should be noted that by actively leaving hydroxyl groups,
It refers to a resin designed to be compatible with the polyepoxy compound (B). If the acid value is lower than 15, the resulting coating film will inevitably have insufficient mechanical strength;
If it is more than 30, the storage stability of the powder coating inevitably decreases, and the reaction progresses during storage, resulting in deterioration of the smoothness of the coating film. Undesirable. On the other hand, it is an essential condition that hydroxyl groups remain in the polyester resin (A), and if the hydroxyl value is lower than 2, it will inevitably be incompatible with the polyepoxy compound (B) described later. This is not preferable because it results in poor pigment dispersibility. As mentioned above, the polyester resin (A) is an intermediate polyester having a hydroxyl group (a-
1) and polycarboxylic anhydride (a-2), and there are no particular restrictions on the method of reaction between these two compounds (a-1) and (a-2). However, among them, the representative one is intermediate polyester (a
-1) with a polycarboxylic anhydride (a-2), or an intermediate polyester (a-1).
Examples include a method in which a polycarboxylic anhydride (a-2) is added to 1) and then further subjected to a condensation reaction. Here, the intermediate polyester (a-
1) has a hydroxyl value of 12.5 to 70, preferably 13 to 50, and an acid value of 2 to 10, preferably 3.
-8, and as long as it falls within this range, it may have a branched structure or a linear structure. There is no particular restriction on the method for preparing the intermediate polyester (a-1), and well-known and commonly used methods can be applied as they are, and as the acid component and the alcohol component, well-known and commonly used dibasic acids and/or Alternatively, polybasic acids, dihydric alcohols (glycols), and/or polyhydric alcohols can be used as they are, but typical acid components include terephthalic acid, isophthalic acid, phthalic acid, and methyl terephthalic acid. , trimellitic acid, pyromellitic acid and their anhydrides or adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyl-tetrahydrophthalic acid, hexahydrophthalic acid, methyl-hexahydrophthalic acid and the like. On the other hand, typical alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-butanediol.
Hexanediol, neopentyl glycol, isopentyl glycol, bishydroxyethyl terephthalate, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, trimethylolethane, trimethylol Examples include propane, glycerin, pentaerythritol, and 2,2,4-trimethylpentane-1,3-diol, but monoepoxy compounds can also be used as one of the glycols in the present invention. On the other hand, the polycarboxylic acid anhydride (a-2) to be reacted with the intermediate polyester (a-1)
As a divalent aromatic, aliphatic or alicyclic acid anhydride containing 30 to 100% by weight of a trivalent or higher polybasic organic carboxylic anhydride based on the total polycarboxylic anhydride, it is possible to apply. Among them, the most representative ones are terephthalic acid, isophthalic acid, phthalic acid,
These include acid anhydrides such as trimellitic acid, pyromellitic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, tetrahydrophthalic acid or hexahydrophthalic acid. The polyepoxy compound (B), which is another essential component of the composition of the present invention, refers to a compound having at least two epoxy groups in one molecule, and among these, particularly representative ones are: are diglycidyl ethers of bisphenol A or bisphenol F, glycidyl esters/ethers of oxybenzoic acid; polydiglycyl ethers of polyhydric alcohols such as diglycidyl ethers of ethylene glycol or glycidyl ethers of trimethylolpropane; Diglycidyl esters of dibasic acids such as glycidyl esters; or triglycidyl isocyanurates. Therefore, the resin composition for powder coating of the present invention contains the above-mentioned polyester resin (A) and polyepoxy compound (B) as essential components, and both of these essential components The usage ratio is 60 to 97 parts by weight of component (A): component (B).
40-3 parts by weight, preferably 65-96 parts by weight: 35-4
A ratio of parts by weight is appropriate. In order to further promote the crosslinking and curing reaction, a well-known catalyst can be appropriately added to the composition of the present invention, and it also prevents the formation of craters on the coating surface and further improves the smoothness. For this purpose, an acrylic acid long-chain alkyl ester polymer, a fluorine compound, or the like may be added as a flow control agent (flow agent). A powder coating can be prepared using the thus obtained composition of the present invention by any known method. By applying the resulting powder coating by a well-known method such as electrostatic spraying or fluidized dipping and then baking, a coating film with excellent performance can be obtained. Next, the present invention will be specifically explained using reference examples, examples, and comparative examples, and all parts and percentages are based on weight unless otherwise specified. Reference Example 1 [Preparation example of polyester resin (A)] A mixture consisting of 83 parts of ethylene glycol, 327 parts of neopentyl glycol, 435 parts of dimethyl terephthalate and 0.4 parts of zinc acetate was prepared by removing the methanol produced from the reaction system. While removing, the temperature was gradually raised to 210°C, and the same temperature was then maintained for 2 hours to continue the alcohol exchange reaction. Next, here is 6 of trimethylolpropane.
149 parts of terephthalic acid, 224 parts of isophthalic acid and 0.5 part of di-n-butyltin oxide were added, the temperature was raised to 240°C over 8 hours, and further dehydration condensation was carried out at the same temperature to form hydroxyl groups. An intermediate polyester (a-1) having a value of 14 and an acid value of 7 was obtained. After that, this polyester (a-1)
The temperature was lowered to 200°C, and then the trimellitic anhydride was heated to 29
When the mixture was reacted at the same temperature for 2 hours, the target resin (A) having an acid value of 23, a hydroxyl value of 5, and a softening point of 123°C was obtained. Hereinafter, this will be abbreviated as polyester (A-1). Reference Example 2 (same as above) The amounts of ethylene glycol, neopentyl glycol and dimethyl terephthalate were
The alcohol exchange reaction was carried out in the same manner as in Reference Example 1, except that the amounts were changed to 159 parts, 218 parts, and 452 parts. Then, the use of isophthalic acid was omitted, and the amounts of trimethylolpropane and terephthalic acid were changed to 20 parts and 20 parts, respectively. A dehydration condensation reaction was carried out in the same manner as in Reference Example 1, except that the amount was changed to 384 parts, to obtain an intermediate polyester (a-1) having a hydroxyl value of 30 and an acid value of 3. After that, the amount of trimellitic anhydride used was reduced to 45%.
The intermediate polyester was reacted in the same manner as in Reference Example 1 except that the acid value was 28,
A target resin (A) having a hydroxyl value of 16 and a softening point of 124°C was obtained. Hereinafter, this will be abbreviated as polyester (A-2). Reference Example 3 (same as above) The amounts of ethylene glycol, neopentyl glycol and dimethyl terephthalate were changed to 136 parts, 253 parts and 472 parts, respectively, and 1,
The alcohol exchange reaction was carried out in the same manner as in Reference Example 1, except that 29 parts of 6-hexanediol was also used, and then 33 parts of adipic acid was used instead of 20 parts of trimethylolpropane. A dehydration condensation reaction was carried out in the same manner as in Reference Example 2, except that the amount of terephthalic acid used was changed to 308 parts, to obtain an intermediate polyester (a-1) having a hydroxyl value of 45 and an acid value of 6. Ta. After that, this polyester (a-1)
The temperature was lowered to 200°C, and then 60°C of trimellitic anhydride was added.
240 g of water and kept at the same temperature for 2 hours, then
When the temperature was raised to â and reacted at the same temperature for 3 hours, the acid value was 25, the hydroxyl value was 12, and the softening point was 119â.
The desired resin (A) was obtained. Hereinafter, this will be abbreviated as polyester (A-3). Reference Example 4 [Preparation example of polyester resin for comparison] The same procedure as Reference Example 2 was carried out except that the amount of trimellitic anhydride used was changed to 102 parts, and the acid value was 57, the hydroxyl value was 0, and the softening A control polyester resin (A') having a temperature of 126°C was obtained. Hereinafter, this will be abbreviated as polyester (A'-1). Reference Example 5 (same as above) except that the amounts of ethylene glycol, neopentyl glycol, and dimethyl terephthalate were changed to 141 parts, 236 parts, and 440 parts, respectively.
The alcohol exchange reaction was carried out in the same manner as in Reference Example 1, and then the dehydration condensation was carried out in the same manner as in Reference Example 1, except that the amounts of trimethylolpropane, terephthalic acid, and isophthalic acid used were changed to 5 parts, 172 parts, and 235 parts, respectively. After the reaction, the hydroxyl value is 6,
A control intermediate polyester (a'-1) having an acid value of 20 was obtained. Afterwards, the amount of trimellitic anhydride used was reduced to 7
This is changed to the above polyester (aâ²-
The acid value was 24, the hydroxyl value was 4,
A control polyester resin (A') having a softening point of 118°C was obtained. Hereinafter, this will be abbreviated as polyester (A'-2). Reference Example 6 [Preparation example of polyester resin (A)] Except that the amounts of ethylene glycol, neopentyl glycol, and dimethyl terephthalate were changed to 127 parts, 261 parts, and 442 parts, respectively.
The alcohol exchange reaction was carried out in the same manner as in Reference Example 1, except that the amounts of trimethylolpropane and terephthalic acid used were changed to 19 parts and 378 parts.
A dehydration condensation reaction was carried out in the same manner as in Reference Example 2 to obtain an intermediate polyester (a-1) having a hydroxyl value of 27 and an acid value of 3. After that, the amount of trimellitic anhydride used was reduced to 37%.
parts, and also used 13 parts of phthalic anhydride, and both of these polycarboxylic anhydrides (a-
2) was changed to react with the above polyester (a-1) in the same manner as in Reference Example 1, and the acid value was 28, the hydroxyl value was 10, and the softening point was 125 ° C.
A desired polyester resin (A) was obtained. below,
This is abbreviated as polyester (A-4). Reference Example 7 [Preparation example of polyester resin (A)] 455.5 parts of dimethyl terephthalate (DMT),
The procedure was carried out in the same manner as in Reference Example 1, except that a mixture consisting of 145.7 parts of ethylene glycol (EG), 244.4 parts of neopentyl glycol (NG), and 0.4 parts of zinc acetate was used, and then terephthalic acid ( 385.4 parts of TPA) and 0.5 parts of di-n-butyltin dioxide were added and subjected to dehydration condensation to obtain an intermediate polyester (a-1) having a hydroxyl value of 12.5 and an acid value of 9. Next, this intermediate polyester (a-1)
The reaction was carried out in the same manner as in Reference Example 1, except that 27 parts of trimellitic anhydride was added to 1000 parts, to obtain a target polyester resin having an acid value of 24 and a hydroxyl value of 2. Hereinafter, this will be abbreviated as polyester resin (A-5). Reference Example 8 (same as above) A target polyester having an acid value of 28 and a hydroxyl value of 2 was produced in the same manner as Reference Example 7, except that the amount of trimellitic anhydride (TMA) used was changed to 36 parts. Resin was obtained. Hereinafter, this will be abbreviated as polyester resin (A-6). Reference Example 9 [Example of preparation of control polyester resin (A')] 455.2 parts of DMT, 145.6 parts of EG, 244.3 parts of NPG
A control intermediate polyester having a hydroxyl value of 12 and an acid value of 9 was obtained in the same manner as in Reference Example 7 except that TPA was changed to 385.9 parts. Next, the acid value was determined in the same manner as in Reference Example 7, except that the amount of TMA used was changed to 23.9 parts.
22 and a hydroxyl value of 5, a control polyester resin was obtained. Hereinafter, this will be abbreviated as polyester resin (A'-3). Reference example 10 (same as above) 455.2 parts of DMT, 145.3 parts of EG, 243.7 parts of NPG
A control intermediate polyester having a hydroxyl value of 10 and an acid value of 9 was obtained in the same manner as in Reference Example 7 except that TPA was changed to 387.9 parts. Next, a control polyester resin having an acid value of 28 and a hydroxyl value of 2 was obtained in the same manner as in Reference Example 7 except that the amount of TMA used was changed to 36 parts. This is abbreviated as polyester resin (A'-3). Examples 6 and 7 and Comparative Examples 3 and 4 Each component was mixed in the composition ratio shown in Table 1, and then made into a paint in the same manner as in Example 2, and then the coating film performance was compared. I considered it. The results are summarized in the same table. Examples 1 to 5 and Comparative Examples 1 and 2 Each component was mixed in the composition ratio as shown in Table 1, and then each mixture was melt-kneaded using "Conneader PR-46" manufactured by Buss, Switzerland. After pulverization, the amount that passed through 150 meshes was applied to a 0.8 mm thick zinc phosphate treated steel plate separately by electrostatic spraying to a film thickness of 50 to 60 Όm, and then baked at 200° C. for 20 minutes. The coating film performance test results for each paint are summarized in the same table.
ãè¡šããtableã
Claims (1)
ãã€é žäŸ¡ãïŒã10KOHmgïŒïœãªãããªãšã¹ãã«
æš¹èïŒïœâïŒïŒã«å€å®èœæ§ææ©ã«ã«ãã³é žç¡æ°Žç©
ïŒïœâïŒïŒãåå¿ãããŠåŸããããé žäŸ¡ã15KOH
mgïŒïœä»¥äž30KOHmgïŒïœæªæºã§ãæ°Žé žåºäŸ¡ã
2KOHmgïŒïœä»¥äžã§ããã€è»åç¹ã80ã150âãª
ãããªãšã¹ãã«æš¹èã®60ã97éééšãšã ïŒïŒ¢ïŒïŒååäžã«å°ãªããšãïŒåã®ãšããã·åº
ãæããããªãšããã·ååç©ã®ïŒã40éééš ãšãå¿ é ã®æåãšããŠå«ãã§æããç²äœå¡æçšæš¹
èçµæç©ã[Scope of Claims] 1 (A) A hydroxyl value of 12.5 to 70 KOHmg/g,
and an acid value of 15 KOH obtained by reacting a polyester resin (a-1) with an acid value of 2 to 10 KOH mg/g with a polyfunctional organic carboxylic acid anhydride (a-2).
mg/g or more and less than 30KOH mg/g, and the hydroxyl value is
60 to 97 parts by weight of a polyester resin containing 2KOHmg/g or more and having a softening point of 80 to 150°C; (B) 3 to 40 parts by weight of a polyepoxy compound having at least two epoxy groups in one molecule; A resin composition for powder coating, comprising as an essential component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4699084A JPS60192772A (en) | 1984-03-14 | 1984-03-14 | Resin composition for powder coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4699084A JPS60192772A (en) | 1984-03-14 | 1984-03-14 | Resin composition for powder coating |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60192772A JPS60192772A (en) | 1985-10-01 |
JPH0372672B2 true JPH0372672B2 (en) | 1991-11-19 |
Family
ID=12762633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4699084A Granted JPS60192772A (en) | 1984-03-14 | 1984-03-14 | Resin composition for powder coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60192772A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62260871A (en) * | 1986-05-07 | 1987-11-13 | Dainippon Ink & Chem Inc | Resin composition for powder coating |
JPH01141961A (en) * | 1987-11-30 | 1989-06-02 | Nippon Light Metal Co Ltd | Coating composition for preventing filamentous corrosion of aluminum material |
JP2539706B2 (en) * | 1991-02-22 | 1996-10-02 | 倧æ¥æ¬å¡ææ ªåŒäŒç€Ÿ | Powder coating composition |
KR19990061666A (en) * | 1997-12-31 | 1999-07-26 | ê¹ì¶©ìž | Heat Resistant Powder Coating Composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53132034A (en) * | 1977-04-25 | 1978-11-17 | Dainippon Ink & Chem Inc | Resin composition for coating powder |
JPS5667373A (en) * | 1979-11-02 | 1981-06-06 | Toyobo Co Ltd | Resin composition for powdered paint |
-
1984
- 1984-03-14 JP JP4699084A patent/JPS60192772A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53132034A (en) * | 1977-04-25 | 1978-11-17 | Dainippon Ink & Chem Inc | Resin composition for coating powder |
JPS5667373A (en) * | 1979-11-02 | 1981-06-06 | Toyobo Co Ltd | Resin composition for powdered paint |
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JPS60192772A (en) | 1985-10-01 |
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