JPS6228192B2 - - Google Patents
Info
- Publication number
- JPS6228192B2 JPS6228192B2 JP52019156A JP1915677A JPS6228192B2 JP S6228192 B2 JPS6228192 B2 JP S6228192B2 JP 52019156 A JP52019156 A JP 52019156A JP 1915677 A JP1915677 A JP 1915677A JP S6228192 B2 JPS6228192 B2 JP S6228192B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- acid
- group
- parts
- acid anhydride
- 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
Links
- 229920001225 polyester resin Polymers 0.000 claims description 55
- 239000004645 polyester resin Substances 0.000 claims description 55
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 125000004018 acid anhydride group Chemical group 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000003973 paint Substances 0.000 description 15
- 238000012691 depolymerization reaction Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- -1 anhydride compound Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 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 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 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
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は、貯蔵安定性、硬化性に優れていると
共に、優れた性能の塗膜を形成する粉体塗料に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a powder coating that has excellent storage stability and curability, and forms a coating film with excellent performance.
カルボキシル基含有ポリエステル樹脂をポリエ
ポキシド、水酸基含有ポリエステル樹脂等の如き
カルボキシル基反応性架橋成分と組合せて成る粉
体塗料は周知である。しかしカルボキシル基含有
ポリエステル樹脂を含むため、硬化性が充分でな
いし、厚塗りすると著るしく発泡が生じる欠点が
ある。しかもカルボキシル基含有ポリエステル樹
脂は経日的に軟化点が上昇する傾向があるので、
粉体塗料の保存期間が長いほど得られる塗膜の平
滑性が低下する欠点がある。 Powder coatings comprising carboxyl group-containing polyester resins in combination with carboxyl group-reactive crosslinking components such as polyepoxides, hydroxyl group-containing polyester resins, etc. are well known. However, since it contains a carboxyl group-containing polyester resin, it does not have sufficient curability and has the disadvantage of causing significant foaming when applied thickly. Moreover, the softening point of carboxyl group-containing polyester resins tends to increase over time.
A drawback is that the longer the powder coating is stored, the lower the smoothness of the resulting coating film becomes.
本発明者等は、鋭意研究の結果、カルボキシル
基含有ポリエステル樹脂中に酸無水基を導入する
ことにより、上記欠点が改良できることを見い出
し、本発明にいたつたのである。 As a result of intensive research, the present inventors have discovered that the above-mentioned drawbacks can be improved by introducing an acid anhydride group into a carboxyl group-containing polyester resin, and have arrived at the present invention.
本発明は、主たる酸原料が芳香族多価カルボン
酸である水酸基含有ポリエステル樹脂（以後、こ
れを中間ポリエステル樹脂と略字する。）にそれ
ぞれ１個のカルボキシル基と酸無水基とを併せ有
する無水化合物を、上記水酸基に対して酸無水基
が過剰となるように加えて解重合せしめて得られ
る、数平均分子量が500〜6000で、しかも樹脂固
形分1000ｇ当りの官能基当量数が0.4〜5.0当量で
あり、かつ該官能基当量数に占める酸無水基当量
が８％以上なるカルボキシル基および酸無水基を
含有するポリエステル樹脂と（以後、最終ポリエ
ステル樹脂と略記する。）と、カルボキシル基反
応性架橋成分とから成る粉体塗料を提供しようと
するものである。 The present invention is directed to an anhydrous compound having one carboxyl group and one acid anhydride group in a hydroxyl group-containing polyester resin (hereinafter abbreviated as intermediate polyester resin) whose main acid raw material is an aromatic polyhydric carboxylic acid. is added and depolymerized so that acid anhydride groups are in excess relative to the above hydroxyl groups, and the number average molecular weight is 500 to 6000, and the number of functional group equivalents per 1000 g of resin solid content is 0.4 to 5.0 equivalents. and a polyester resin containing a carboxyl group and an acid anhydride group (hereinafter abbreviated as the final polyester resin) whose acid anhydride group equivalents account for 8% or more of the number of functional group equivalents (hereinafter abbreviated as the final polyester resin), and a carboxyl group-reactive crosslinking The object of the present invention is to provide a powder coating consisting of the following components.
本発明で使用する中間ポリエステル樹脂は、芳
香族多価カルボン酸を主とする酸原料とアルコー
ル原料との縮合物のことで、分岐及び線状の両方
がある。酸原料としては、貯蔵安定性の点から芳
香族多価カルボン酸が全酸原料の少くとも70％を
占めるのが好ましい、酸原料の例にはテレフタル
酸、イソフタル酸、フタル酸、トリメリツト酸、
ピロメリツト酸、アジピン酸、セバシン酸、コハ
ク酸、マレイン酸、フマル酸、テトラヒドロフタ
ル酸、ヘキサヒドロフタル酸、ベンゾフエノンテ
トラカルボン酸、エンドメチレンテトラヒドロフ
タル酸、テトラクロルフタル酸、それらの無水物
及びそれらを再生する誘導体等がある。またアル
コール原料の例にはエチレングリコール、プロピ
レングリコール、ブタンジオール、ヘキサンジオ
ール、ジエチレングリコール、ジプロピレングリ
コール、ネオペンチルグリコール、トリメチロー
ルエタン、トリメチロールプロパン、グリセリ
ン、ペンタエリスリトール等があり、モノエポキ
シ化合物もアルコール原料として使用できる。 The intermediate polyester resin used in the present invention is a condensate of an acid raw material mainly consisting of an aromatic polycarboxylic acid and an alcohol raw material, and is both branched and linear. As the acid raw material, it is preferable that aromatic polycarboxylic acids account for at least 70% of the total acid raw material from the viewpoint of storage stability. Examples of acid raw materials include terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid,
Pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, benzophenonetetracarboxylic acid, endomethylenetetrahydrophthalic acid, tetrachlorophthalic acid, their anhydrides and There are derivatives etc. that regenerate them. Examples of alcohol raw materials include ethylene glycol, propylene glycol, butanediol, hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, etc. Monoepoxy compounds are also alcoholic. Can be used as raw material.
中間ポリエステル樹脂の数平均分子量について
は、解重合により最終ポリエステル樹脂を形成す
るのに充分な値であれば良く、特に制限はない
が、1000〜10000の範囲が適当である。その構造
には分岐と線状の２通りあるが、好ましくは分岐
構造である。 The number average molecular weight of the intermediate polyester resin is not particularly limited as long as it is sufficient to form the final polyester resin through depolymerization, but a range of 1,000 to 10,000 is suitable. There are two types of structure: branched and linear, but branched structure is preferred.
また、当該中間ポリエステル樹脂の水酸基は前
記無水化合物中の酸無水基の一部を付加せしめる
ために必要なものであり、当該中間ポリエステル
樹脂の水酸基価としては、通常10以上、好ましく
は40〜100なる範囲が適当である。 Further, the hydroxyl group of the intermediate polyester resin is necessary for adding a part of the acid anhydride group in the anhydride compound, and the hydroxyl value of the intermediate polyester resin is usually 10 or more, preferably 40 to 100. A range of
各実施例に示される処からも、前記した最終ポ
リエステル樹脂中に官能基が殆どない場合とか、
実質的にカルボキシル基のみの場合には、本発明
の目的の一つである、この最終ポリエステル樹脂
の経時的な軟化点上昇を防止せしめる効果も十分
得られないし、解重合中においても芳香族多価カ
ルボン酸が沈澱し、塗膜にもブツが発生するなど
好ましからざる事態が発生する。かゝる中間ポリ
エステル樹脂の製造は、前記の酸原料とアルコー
ル原料とを周知方法で反応させることにより可能
であるし、また一旦製造した高分子量のポリエス
テル樹脂を多価アルコールで解重合することによ
つても可能である。またこれらポリエステル樹脂
の水酸基が解重合時に必然的に生じる副反応（エ
ステル反応）を避けるために、事前に当量の無水
化合物とエステル反応させて、未端官能基をカル
ボキシル基に変えるという二段反応を行うことが
できる。 From the places shown in each example, there are cases where there are almost no functional groups in the final polyester resin,
In the case of substantially only carboxyl groups, the effect of preventing the softening point of the final polyester resin from increasing over time, which is one of the purposes of the present invention, cannot be sufficiently achieved, and even during depolymerization, aromatic polyester Undesirable situations occur, such as the precipitate of carboxylic acids and the formation of spots on the coating film. The production of such an intermediate polyester resin is possible by reacting the above-mentioned acid raw material and alcohol raw material by a well-known method, or by depolymerizing the high molecular weight polyester resin once produced with a polyhydric alcohol. It is possible even if it is twisted. In addition, in order to avoid side reactions (ester reactions) that inevitably occur when the hydroxyl groups of these polyester resins are depolymerized, they are subjected to an ester reaction with an equivalent amount of an anhydride compound in advance, resulting in a two-step reaction in which the hydroxyl groups of these polyester resins are converted into carboxyl groups. It can be performed.
中間ポリエステル樹脂を解重合させる無水化合
物は、１個のカルボキシル基と１個の酸無水基と
を併せ持つ化合物である。その典型例は無水トリ
メリツト酸であるが、その他に無水ピロメリツト
酸と一価アルコール（モル比１：１）のモノハー
フエステル、無水トリメリツト酸と二価アルコー
ル（モル比２：１）のエステルに一価アルコール
を反応（モル比１：１）させた酸無水基含有モノ
ハーフエステル等がある。 The anhydride compound that depolymerizes the intermediate polyester resin is a compound having both one carboxyl group and one acid anhydride group. A typical example is trimellitic anhydride, but there are also monohalf esters of pyromellitic anhydride and monohydric alcohol (molar ratio 1:1), and monohalf esters of trimellitic anhydride and dihydric alcohol (molar ratio 2:1). There are acid anhydride group-containing monohalf esters made by reacting alcohols (molar ratio 1:1).
解重合反応は、中間ポリエステル樹脂中のエス
テル結合の水酸基部分とカルボキシル基部分との
うち、前者の水酸基に無水化合物のカルボキシル
基が反応した酸無水基を含有する部分と、後者で
あるカルボキシル基を含有する部分とを生成す
る。この解重合反応を線状の中間ポリエステル樹
脂と無水トリメリツト酸とを使用する典型的な例
について図示すると次の通りである。 The depolymerization reaction is performed between the hydroxyl group and carboxyl group of the ester bond in the intermediate polyester resin, the former hydroxyl group being reacted with the carboxyl group of the anhydride compound, and the latter carboxyl group. The containing part is generated. A typical example of this depolymerization reaction using a linear intermediate polyester resin and trimellitic anhydride is illustrated as follows.
中間ポリエステル樹脂が一端または両端に水酸
基を有するため、解重合反応前に、これら中間ポ
リエステル樹脂の末端官能基は無水化合物の酸無
水基とエステル反応させてカルボキシル基に変換
され、しかるのち解重合反応によつて生ずる酸無
水基を含有する部分(A)は、一端が酸無水基で他端
がカルボキシル基となり、一方、カルボキシル基
を含有する部分(B)は両端ともカルボキシル基とな
る。 Since the intermediate polyester resin has a hydroxyl group at one or both ends, before the depolymerization reaction, the terminal functional groups of the intermediate polyester resin are converted into carboxyl groups through an ester reaction with the acid anhydride group of the anhydride compound, and then the depolymerization reaction takes place. The acid anhydride group-containing moiety (A) produced by this has an acid anhydride group at one end and a carboxyl group at the other end, while the carboxyl group-containing moiety (B) has carboxyl groups at both ends.
解重合の反応に当つては、目的とする最終ポリ
エステル樹脂を生成するに適した中間ポリエステ
ル樹脂及び無水化合物の種類を選択すると共に、
それら二成分の仕込み量は、最終ポリエステル樹
脂としてはカルボキシル基と酸無水基とが含有さ
れる処から、中間ポリエステル樹脂の水酸基に対
して無水化合物の酸無水基が過剰になるようにす
る必要がある。その際仕込んだ無水化合物は必ら
ずしも全量反応せず未反応のまゝ残留することに
なるが、最終ポリエステル樹脂に無水化合物が多
量に混在していると、無水化合物に基因する不都
合が生じるので、残留分は、解重合反応生成物の
10重量％以下になるよう配慮するのが好ましい。 In the depolymerization reaction, select the type of intermediate polyester resin and anhydride compound suitable for producing the desired final polyester resin, and
Since the final polyester resin contains carboxyl groups and acid anhydride groups, it is necessary to adjust the amounts of these two components so that the acid anhydride groups of the anhydride compound are in excess of the hydroxyl groups of the intermediate polyester resin. be. The anhydrous compound charged at this time does not necessarily react in its entirety and remains unreacted, but if a large amount of anhydrous compound is mixed in the final polyester resin, problems caused by the anhydrous compound may occur. The residue is the depolymerization reaction product.
It is preferable to take care to keep the content to 10% by weight or less.
解重合の反応は、140〜280℃の温度条件で行う
のが適当である。温度条件が140℃未満である
と、反応速度が著るしく低いし、一方280℃を越
すと無水化合物が昇華し、反応生成物の着色が著
るしくなるので、好ましくない。中間ポリエステ
ル樹脂と無水化合物との反応の程度は、ゲル透過
型クロマトグラフイにより追跡できるので、最終
ポリエステル樹脂の数平均分子量、１分子当りの
酸無水基の導入量は容易に決定することができ
る。 The depolymerization reaction is suitably carried out at a temperature of 140 to 280°C. If the temperature condition is less than 140°C, the reaction rate will be extremely low, while if it exceeds 280°C, the anhydrous compound will sublime and the reaction product will become significantly colored, which is not preferable. Since the degree of reaction between the intermediate polyester resin and the anhydride compound can be monitored by gel permeation chromatography, the number average molecular weight of the final polyester resin and the amount of acid anhydride groups introduced per molecule can be easily determined. .
最終ポリエステル樹脂は数平均分子量が500〜
6000好ましくは700〜4000であり、カルボキシル
基と酸無水基とを含有している。酸無水基は、樹
脂１分子当り0.1個以上、好ましくは0.3個以上有
しているのが好ましい。最終ポリエステル樹脂１
分子量が含有する平均官能基数（遊離カルボキシ
ル基１個を１単位、酸無水基を１単位として両方
を合計した値）は、通常2.2個以上、好ましくは
2.5個以上が適当である。また最終ポリエステル
樹脂固形分1000ｇ当りの官能基当量数（遊離カル
ボキシル基１個を１当量、酸無水基１個を１当量
として、両方を合計した値）としては、硬化性と
塗面の平滑性の点から、0.4〜5.0当量好ましくは
0.8〜4.0当量が適しており、官能基当量数に占め
る好ましい酸無水基当量は８％以上である。この
最終ポリエステル樹脂の使用割合が多い場合、そ
の軟化点（環球法による）は70〜150℃の範囲に
あることを要する。 The final polyester resin has a number average molecular weight of 500~
6000, preferably 700 to 4000, and contains a carboxyl group and an acid anhydride group. The number of acid anhydride groups per resin molecule is preferably 0.1 or more, preferably 0.3 or more. Final polyester resin 1
The average number of functional groups contained in the molecular weight (one free carboxyl group is one unit, one acid anhydride group is one unit, and the sum of both) is usually 2.2 or more, preferably
2.5 or more is appropriate. In addition, the number of functional group equivalents per 1000 g of final polyester resin solid content (one free carboxyl group is 1 equivalent, one acid anhydride group is 1 equivalent, and the sum of both) is based on curability and coating surface smoothness. From the point of view, preferably 0.4 to 5.0 equivalents
A suitable amount is 0.8 to 4.0 equivalents, and the preferred acid anhydride equivalents in the number of functional group equivalents are 8% or more. When this final polyester resin is used in a large proportion, its softening point (according to the ring and ball method) is required to be in the range of 70 to 150°C.
かゝる最終ポリエステル樹脂と併用するカルボ
キシル基反応性架橋成分とは最終ポリエステル樹
脂中の酸無水基及びカルボキシル基と反応性の官
能基を有しており、それら官能基間の反応により
系全体を架橋硬化させる成分のことである。その
うち最適のものは水酸基を多数含有するポリエス
テル樹脂であるが、その他に例えば水酸基を多数
含有するビニル系重合体、ビスフエノール型グリ
シジルエーテル、多価カルボン酸のポリグリシジ
ルエステル、トリグリシジルイソシアヌレート、
グリシジル基を多数含有するビニル系重合物等が
ある。水酸基を多数含有する架橋成分としては、
水酸基価が70〜300好ましくは100〜250で、酸価
30以下好ましくは20以下のものが適当である。こ
れら架橋成分の使用割合が多い場合、その軟化点
は70〜150℃であることを要する。 The carboxyl group-reactive crosslinking component used in combination with the final polyester resin has a functional group that is reactive with the acid anhydride groups and carboxyl groups in the final polyester resin, and the reaction between these functional groups can cause the entire system to be damaged. This is a component that crosslinks and hardens. Among these, the most suitable is polyester resin containing many hydroxyl groups, but other examples include vinyl polymers containing many hydroxyl groups, bisphenol type glycidyl ether, polyglycidyl ester of polyhydric carboxylic acid, triglycidyl isocyanurate,
There are vinyl polymers containing a large number of glycidyl groups. As a crosslinking component containing a large number of hydroxyl groups,
The hydroxyl value is 70 to 300, preferably 100 to 250, and the acid value is
A value of 30 or less, preferably 20 or less is suitable. When these crosslinking components are used in a large proportion, the softening point must be 70 to 150°C.
最終ポリエステル樹脂とカルボキシル基反応性
架橋成分との使用割合は重量比で95／５〜５／95
の範囲が適当である。 The ratio of the final polyester resin to the carboxyl group-reactive crosslinking component is 95/5 to 5/95 by weight.
A range of is appropriate.
粉体塗料を調製するには、公知のいずれの方法
も採用できるが、通常は最終ポリエステル樹脂、
カルボキシル基反応性架橋成分、顔料、流動調整
剤及び必要により周知の架橋反応促進剤等をドラ
イブレンド後、溶融混練し冷却固化させてから微
粉砕する方法が適当である。かくして得られる粉
体塗料は、硬化性に優れており、基体に塗着後
150℃以上好ましくは170〜220℃に加熱すると充
分硬化して塗膜外観及び機械的性能に優れた硬化
塗膜を生成する。その際厚塗りしても塗面には殆
んど発泡が生じない。またかゝる粉体塗料は、貯
蔵安定性に優れているため、長期間保存後使用し
ても塗膜の平滑性の低下はない。 Any known method can be used to prepare powder coatings, but typically the final polyester resin,
A suitable method is to dry blend a carboxyl group-reactive crosslinking component, a pigment, a fluidity regulator, and if necessary a well-known crosslinking reaction accelerator, and then melt-knead, solidify by cooling, and then finely pulverize. The powder coating thus obtained has excellent curing properties, and after being applied to the substrate,
When heated to 150° C. or higher, preferably 170 to 220° C., it is sufficiently cured to produce a cured coating film with excellent coating appearance and mechanical performance. At that time, even if it is applied thickly, there is almost no foaming on the coated surface. Furthermore, since such powder coatings have excellent storage stability, the smoothness of the coating film does not deteriorate even when used after long-term storage.
以下に本発明を実施例に従つて説明する。文中
の部は重量部を示す。 The present invention will be explained below based on examples. Parts in the text indicate parts by weight.
参考例 １
最終ポリエステルの合成
ネオペンチルグリコール362部、エチレングリ
コール92部、トリメチロールプロパン27部、ジメ
チルテレフタレート919部および酢酸亜鉛0.7部か
らなる混合物を生成するメタノールを連続的に系
外に除去しながら155℃に１時間加熱後徐々に210
℃まで昇温し同温度で２時間加熱した。さらに
210℃に保持したまま70mmHgの減圧にて１時間保
持して、水酸基価100、分子量1270なる中間ポリ
エステル樹脂を得た。次いで、このポリエステル
樹脂の1000部に180℃で342部の無水トリメリツト
酸を添加し、同温度で２時間加熱したのち、無水
トリメリツト酸170部を追加し同温度で６時間解
重合反応を行なつて、１分子平均の官能基数3.51
個（酸無水基0.47個、分子量1020、官能基当量数
3.61当量／1000ｇ樹脂（但し酸無水基0.48当量／
1000ｇ樹脂、カルボキシル基3.13当量／1000ｇ樹
脂）、軟化点105℃の最終ポリエステル樹脂を得
た。尚、ゲル透明型クロマトグラフイーにより測
定した解重合反応における無水トリメリツト酸の
反応率は80％であつた。また、赤外線吸収スペク
トルにより分析を行なつた結果、解重合反応開始
直後と解重合反応終了時における酸無水基による
1788および1865cm-1の吸収強度の変化は全く認め
られず、消費された無水トリメリツト酸は全て解
重合反応によりポリエステル樹脂中に導入された
ことを確認した。最終ポリエステル樹脂を室温
で３ケ月間保存しても軟化点の上昇は認められな
かつた。Reference Example 1 Synthesis of final polyester A mixture consisting of 362 parts of neopentyl glycol, 92 parts of ethylene glycol, 27 parts of trimethylolpropane, 919 parts of dimethyl terephthalate and 0.7 parts of zinc acetate was produced while continuously removing methanol from the system. After heating to 155℃ for 1 hour, gradually increase to 210℃.
The temperature was raised to ℃ and heated at the same temperature for 2 hours. moreover
The temperature was maintained at 210° C. and maintained at a reduced pressure of 70 mmHg for 1 hour to obtain an intermediate polyester resin having a hydroxyl value of 100 and a molecular weight of 1,270. Next, 342 parts of trimellitic anhydride was added to 1000 parts of this polyester resin at 180°C, and after heating at the same temperature for 2 hours, 170 parts of trimellitic anhydride was added and a depolymerization reaction was carried out at the same temperature for 6 hours. The average number of functional groups per molecule is 3.51.
(0.47 acid anhydride groups, molecular weight 1020, number of functional group equivalents)
3.61 equivalents/1000g resin (however, acid anhydride group 0.48 equivalents/
A final polyester resin having a softening point of 105° C. was obtained. The reaction rate of trimellitic anhydride in the depolymerization reaction measured by transparent gel chromatography was 80%. In addition, as a result of analysis using infrared absorption spectroscopy, it was found that acid anhydride groups were present immediately after the start of the depolymerization reaction and at the end of the depolymerization reaction.
No change in absorption intensity at 1788 and 1865 cm -1 was observed, confirming that all of the consumed trimellitic anhydride was introduced into the polyester resin through the depolymerization reaction. No increase in softening point was observed when the final polyester resin was stored at room temperature for 3 months.
参考例 ２
最終ポリエステルの合成
ネオペンチルグリコール264部、エチレングリ
コール114部、ジメチルテレフタレート426部およ
び酢酸亜鉛0.4部からなる混合物を生成するメタ
ノールを連続的に系外に除去しながら155℃に１
時間、210℃に２時間加熱した。ついでトリメチ
ロールプロパン36部、テレフタル酸373部、セバ
シン酸10部およびジブチルスズオキサイド0.5部
を添加して、210℃で４時間240℃で９時間加熱脱
水して酸価５、水酸基価40、軟化点100℃のポリ
エステル樹脂を得た。さらにこのポリエステル樹
脂1000部に無水トリメリツト酸137部を加え、180
℃で２時間加熱した後（酸価75、水酸基価０、軟
化点116℃、分子量3640）、無水トリメリツト酸
100部を添加し200℃で６時間解重合反応を行なつ
て軟化点112℃、官能基当量数1.90当量／1000ｇ
樹脂（酸無水基0.32当量／1000ｇ樹脂、カルボキ
シル基1.58当量／1000ｇ樹脂）分子量1700、１分
子平均の官能基数3.23個（酸無水基0.56個）最終
ポリエステルを得た。尚、ゲル透過型クロマト
グラフイーより測定した無水トリメリツト酸の反
応率は75％であつた。最終ポリエステルを室温
に３ケ月間貯蔵しても軟化点の上昇は全く認めら
れなかつた。Reference Example 2 Synthesis of final polyester A mixture consisting of 264 parts of neopentyl glycol, 114 parts of ethylene glycol, 426 parts of dimethyl terephthalate, and 0.4 parts of zinc acetate was produced at 155°C while continuously removing methanol from the system.
The mixture was heated to 210° C. for 2 hours. Next, 36 parts of trimethylolpropane, 373 parts of terephthalic acid, 10 parts of sebacic acid, and 0.5 parts of dibutyltin oxide were added and dehydrated by heating at 210°C for 4 hours and 240°C for 9 hours to obtain an acid value of 5, a hydroxyl value of 40, and a softening point. A polyester resin at 100°C was obtained. Furthermore, 137 parts of trimellitic anhydride was added to 1000 parts of this polyester resin, and 180 parts of trimellitic anhydride was added.
After heating at ℃ for 2 hours (acid value 75, hydroxyl value 0, softening point 116℃, molecular weight 3640), trimellitic anhydride
Add 100 parts and perform a depolymerization reaction at 200℃ for 6 hours to obtain a softening point of 112℃ and functional group equivalent number of 1.90 equivalents/1000g.
Resin (0.32 equivalents of acid anhydride groups/1000 g resin, 1.58 equivalents of carboxyl groups/1000 g resin) A final polyester having a molecular weight of 1700 and an average number of functional groups per molecule of 3.23 (0.56 acid anhydride groups) was obtained. Incidentally, the reaction rate of trimellitic anhydride measured by gel permeation chromatography was 75%. No increase in softening point was observed when the final polyester was stored at room temperature for 3 months.
実施例 １
最終ポリエステル 23部、エピクロン4050
（大日本インキ化学工業(株)製ビスフエノールＡの
ジグリシジルエーテル型エポキシ樹脂、エポキシ
当量930）75部、流動調整剤0.5部および酸化チタ
ン43部から成る混合物を溶融混練後冷却微粉砕
し、150メツシユ金網を通して白色粉体塗料を得
た。かくして得られた粉体塗料を静電塗装法によ
り軟鋼板に塗布し、180℃で15分間焼付けること
により、膜厚150μでピンホールの発生が全くな
く、機械的強度、外観が極めて優れた硬化塗膜を
得た。また、この塗料を35℃で１ケ月間貯蔵後塗
装焼付して得られた塗膜の外観および機械的強度
は貯蔵前の粉体塗料による塗膜と全く同じであつ
た。Example 1 23 parts final polyester, Epicron 4050
A mixture consisting of 75 parts of bisphenol A diglycidyl ether type epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., epoxy equivalent: 930), 0.5 parts of a fluidity regulator and 43 parts of titanium oxide was melt-kneaded, cooled and finely pulverized, A white powder coating was obtained through a 150 mesh wire mesh. The powder coating thus obtained was applied to a mild steel plate using the electrostatic coating method and baked at 180°C for 15 minutes, resulting in a film with a thickness of 150 μm, no pinholes, and extremely excellent mechanical strength and appearance. A cured coating film was obtained. Furthermore, the appearance and mechanical strength of the paint film obtained by storing this paint at 35° C. for one month and baking it was exactly the same as that of the paint film made with the powder paint before storage.
比較例 １
最終ポリエステルを製造する際に使用した中
間ポリエステル樹脂（室温に１ケ月間貯蔵すると
軟化点は130℃まで上昇した）30部、エピクロン
4050 70部、流動調整剤0.5部および酸化チタン43
部から実施例１と同様にして白色粉体塗料を得
た。この白色粉塗料から得た硬化塗膜は膜厚130
μで著るしく発泡し、機械的強度、外観は実施例
１の塗膜に比較して劣つていた。また、この塗料
を35℃で１ケ月間貯蔵後、塗装し焼付けて得た塗
膜の平滑性は貯蔵前の粉体塗料による塗膜に比べ
て著しく劣つていた。Comparative Example 1 30 parts of intermediate polyester resin (softening point rose to 130°C when stored at room temperature for 1 month) used in producing the final polyester, Epiclon
70 parts of 4050, 0.5 part of flow regulator and titanium oxide 43
A white powder paint was obtained from the sample in the same manner as in Example 1. The cured film obtained from this white powder paint has a film thickness of 130
It foamed significantly at μ, and its mechanical strength and appearance were inferior to the coating film of Example 1. Furthermore, after storing this paint at 35° C. for one month, the smoothness of the paint film obtained by painting and baking was significantly inferior to that of the powder paint film before storage.
実施例 ２
最終ポリエステル 36部、エピクロン4050
64部、流動調整剤0.5部および酸化チタン43部か
ら成る混合物から実施例１と同様にして白色粉体
塗料を得た。この塗料から得た硬化塗膜（180
℃、15分間焼付）は膜厚140μで全く発泡がなく
機械的強度、外観が極めて優れていた。Example 2 Final polyester 36 parts, Epicron 4050
A white powder coating was obtained in the same manner as in Example 1 from a mixture consisting of 64 parts of titanium oxide, 0.5 parts of flow regulator and 43 parts of titanium oxide. Cured film obtained from this paint (180
℃ for 15 minutes) had a film thickness of 140 μm, no foaming at all, and excellent mechanical strength and appearance.
実施例 ３
エチレングリコール179部、ネオペンチルグリ
コール63部、ジメチルテレフタレート280部およ
び酢酸亜鉛0.3部から成る混合物を生成するメタ
ノールを連続的に反応系外に除去しながら155℃
に２時間加熱後徐々に210℃まで昇温し同温度で
２時間加熱した。ついでトリメチロールプロパン
171部、テレフタル酸318部およびジブチルスズオ
キサイド0.5部を添加し220℃で８時間加熱して酸
価3.0、水酸基価190、軟化点99℃のポリエステル
樹脂を得た。このポリエステル樹脂55部、最終ポ
リエステル 45部、流動調整剤0.5部および酸
化チタン43部から成る混合物から実施例１と同様
にして白色粉体塗料を得た。この塗料から実施例
１と同様にして、200℃で20分間焼付けて得た硬
化塗膜は、150μの膜厚で全く発泡せず、機械強
度、平滑性、鮮映性は極めて優れていた。また、
この塗料を35℃で１ケ月間貯蔵後塗装焼付けして
得た塗膜の他観および機械的強度は貯蔵前の粉体
塗料による塗膜と全く同じであつた。Example 3 A mixture of 179 parts of ethylene glycol, 63 parts of neopentyl glycol, 280 parts of dimethyl terephthalate, and 0.3 parts of zinc acetate was produced at 155° C. while continuously removing methanol from the reaction system.
After heating for 2 hours, the temperature was gradually raised to 210°C and heated at the same temperature for 2 hours. Then trimethylolpropane
171 parts of terephthalic acid, 318 parts of terephthalic acid, and 0.5 parts of dibutyltin oxide were added and heated at 220°C for 8 hours to obtain a polyester resin having an acid value of 3.0, a hydroxyl value of 190, and a softening point of 99°C. A white powder paint was obtained in the same manner as in Example 1 from a mixture consisting of 55 parts of this polyester resin, 45 parts of the final polyester, 0.5 parts of flow regulator and 43 parts of titanium oxide. A cured coating film obtained by baking this coating material at 200° C. for 20 minutes in the same manner as in Example 1 had a film thickness of 150 μm, no foaming at all, and extremely excellent mechanical strength, smoothness, and image clarity. Also,
This paint was stored at 35° C. for one month and then baked, and the appearance and mechanical strength of the paint film obtained were exactly the same as those of the powder paint film before storage.
実施例 ４
実施例３において得たポリエステル樹脂40部、
最終ポリエステル60部、流動調整剤0.5部及び
酸化チタンから実施例１と同様にして粉体塗料を
得た。この塗料から実施例３と全く同様にして得
た硬化塗膜は膜厚150μで全く発泡せず、機械強
度、平滑性、鮮映性は極めて優れていた。Example 4 40 parts of the polyester resin obtained in Example 3,
A powder coating material was obtained in the same manner as in Example 1 from 60 parts of the final polyester, 0.5 parts of flow regulator and titanium oxide. A cured coating film obtained from this paint in exactly the same manner as in Example 3 had a film thickness of 150 μm, no foaming at all, and extremely excellent mechanical strength, smoothness, and image clarity.
Claims (1)
水酸基含有ポリエステル樹脂に１個のカルボキシ
ル基と１個の酸無水基とを併せ有する化合物を、
前記の水酸基に対して酸無水基が過剰となるよう
に加えて解重合せしめて得られる、数平均分子量
が500〜6000で、しかも樹脂固形分1000ｇ当りの
官能基当量数（遊離カルボキシル基１個を１当
量、酸無水基１個を１当量として、両者を合計し
た値）が0.4〜5.0当量であり、かつ該官能基当量
数に占める酸無水基当量が８％以上なるカルボキ
シル基および酸無水基を含有するポリエステル樹
脂と、カルボキシル基反応性架橋成分とから成
る、粉体塗料。1. A compound having both one carboxyl group and one acid anhydride group in a hydroxyl group-containing polyester resin whose main acid raw material is an aromatic polyhydric carboxylic acid,
A number average molecular weight of 500 to 6000 is obtained by adding acid anhydride groups in excess to the above hydroxyl groups and depolymerizing them, and the number of functional group equivalents per 1000 g of resin solid content (1 free carboxyl group) carboxyl group and acid anhydride, in which the total value of both is 0.4 to 5.0 equivalent, and the equivalent of acid anhydride group accounts for 8% or more of the number of equivalents of the functional group. A powder coating consisting of a polyester resin containing groups and a carboxyl group-reactive crosslinking component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1915677A JPS53104634A (en) | 1977-02-25 | 1977-02-25 | Powder coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1915677A JPS53104634A (en) | 1977-02-25 | 1977-02-25 | Powder coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53104634A JPS53104634A (en) | 1978-09-12 |
| JPS6228192B2 true JPS6228192B2 (en) | 1987-06-18 |
Family
ID=11991543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1915677A Granted JPS53104634A (en) | 1977-02-25 | 1977-02-25 | Powder coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53104634A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5371112A (en) * | 1992-01-23 | 1994-12-06 | The Sherwin-Williams Company | Aqueous coating compositions from polyethylene terephthalate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525844A (en) * | 1975-07-02 | 1977-01-17 | Mitsubishi Electric Corp | Process for preparing a powder coating |
-
1977
- 1977-02-25 JP JP1915677A patent/JPS53104634A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS525844A (en) * | 1975-07-02 | 1977-01-17 | Mitsubishi Electric Corp | Process for preparing a powder coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53104634A (en) | 1978-09-12 |
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