JPS6317105B2 - - Google Patents
Info
- Publication number
- JPS6317105B2 JPS6317105B2 JP55001677A JP167780A JPS6317105B2 JP S6317105 B2 JPS6317105 B2 JP S6317105B2 JP 55001677 A JP55001677 A JP 55001677A JP 167780 A JP167780 A JP 167780A JP S6317105 B2 JPS6317105 B2 JP S6317105B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- temperature
- epoxy resin
- acid
- epoxy
- 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 39
- 239000004645 polyester resin Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 24
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012691 depolymerization reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 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
- 229920000642 polymer 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
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 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
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は粉体塗料用ポリエステル樹脂組成物を
安定した品質を有するようにかつ経済的有利に製
造するための方法に関するものである。
近年、粉体塗料は省資源、無公害型の塗料とし
て建材、家電、農業機械あるいは自動車関連など
の諸産業の分野で着実に需要の伸びを示している
ものである。
この場合、粉体塗料用の素材としてはエポキシ
樹脂、アクリル樹脂とともにポリエステル樹脂も
多量に用いられている。その中でも主として末端
基がカルボキシル基である飽和ポリエステル樹脂
とエポキシ樹脂とからなるポリエステル樹脂組成
物は、硬化反応にあたり揮発成分が殆んどないた
め膜厚20〜200ミクロン程度の広い範囲にわたり
「わき」(沸き)のない平滑で美麗な塗膜の形成が
可能であり、かつ物理的あるいは化学的に優れた
塗膜を形成することのできる粉体塗料用の素材と
して最も好ましいものの1つである。
しかしながら、前記の主として末端基がカルボ
キシル基からなるポリエステル樹脂とエポキシ樹
脂とからなるポリエステル樹脂組成物は、ある温
度以上になるとそれ自体反応して硬化してしまう
ため、ポリエステル樹脂とエポキシ樹脂とを、低
温または/および短時間で均一に混合することが
平滑で美麗な塗膜の形成を可能にするためには不
可欠なことである。また、粉体塗料は連続して多
量に使用される場合が多く、かつ回収された塗料
を再使用するため長期にわたり安定した素材の提
供が極めて重要になる。
本発明者らはかかる粉体塗料用ポリエステル樹
脂組成物を安定してかつ経済的有利に製造するべ
く鋭意研究の結果、次のような方法を開発するこ
とによつてその目的を達成することができた。
すなわち、本発明は、軟化点60〜120℃、酸価
20〜80でかつ末端基の少なくとも60%がカルボキ
シル基である飽和ポリエステル樹脂と、分子内に
2個以上のグリシジル基を有するエポキシ樹脂と
からなる粉体塗料用ポリエステル樹脂組成物を製
造する方法において、エポキシ樹脂として室温で
液状のエポキシ樹脂を用い、かつ140℃〜200℃の
温度に保持された溶融状態にある飽和ポリエステ
ル樹脂と、溶融温度以上に保持された溶融状態に
あるエポキシ樹脂とを同時に定量的に、1軸また
は2軸以上のスクリユーを備えた混練機へ供給し
て120〜150℃の温度で連続的に混合払出しするこ
とを特徴とする粉体塗料用ポリエステル樹脂組成
物の製造方法である。
本発明の方法を実施する場合使用するポリエス
テル樹脂は、テレフタル酸、イソフタル酸、フタ
ル酸、ナフタレンジカルボン酸、1・4−シクロ
ヘキサンジカルボン酸、アジピン酸、アゼライン
酸、セバシン酸、ドデカンジカルボン酸などの芳
香族、脂環族、脂肪族ジカルボン酸あるいはこれ
らの低級ジアルキルエステル、トリメリツト酸、
トリメジン酸、ピロメリツト酸などの多価カルボ
ン酸あるいはこれらの無水物、低級アルキルエス
テルを酸成分とし使用し、またエチレングリコー
ル、1・2−プロパンジオール、1・3−プロパ
ンジオール、1・3−ブタンジオール、1・4−
ブタンジオール、1・5−ペンタンジオール、
1・6−ヘキサンジオール、ジエチレングリコー
ル、ネオペンチルグリコール、1・4−シクロヘ
キサンジメタノールなどのジアルコール、トリメ
チロールエタン、トリメチロールプロパン、ペン
タエリスリトールなどの多価アルコールをアルコ
ール成分として使用する。そして必要があれば触
媒の存在下、150〜250℃の温度でエステル化反応
またはエステル交換反応を行い、得られる低重合
体に三酸化アンチモン、酸化ゲルマニウム、テト
ラブチルチタネートのごとき重縮合触媒を加えて
200〜300℃の温度で0.5mmHg以下の減圧下重縮合
反応して高重合度のポリエステルを得る。更にこ
れを目的とするポリエステル樹脂の酸価と平均重
合度に応じて必要量の、前述ジカルボン酸また
は/および多価カルボン酸を用いて、200〜280℃
で解重合反応してポリエステル樹脂を得るが、こ
れが品質の安定という点で最も好ましいものの1
つである。これは単にエステル化反応のみで得ら
れたもの、あるいはエステル化反応に加えて重縮
合反応して得られるポリエステル樹脂であつても
差しつかえない。しかしながら、いずれの方法に
よつて製造されたポリエステル樹脂であつても粉
体塗料用の素材として用いる場合、その軟化点は
60〜120℃、好ましくは80〜100℃に調整すること
が必要である。すなわち、軟化点60℃以下の樹脂
は樹脂そのもので使用する場合、あるいは粉体塗
料として調製した場合に貯蔵安定性に問題が生
じ、他方軟化点120℃以上の樹脂は顔料等を配合
して粉体塗料として調製する際の作業性が著しく
不良となり、かつ塗装、焼き付けによつて平滑で
美麗な塗膜の形成が困難となる。また、ポリエス
テル樹脂の酸価は20〜80の範囲に調整することが
塗料化の作業性、塗料の貯蔵安定性さらには塗膜
性能をバランスさせる上で非常に重要である。す
なわち、通常酸価20未満のポリエステル樹脂は平
均重合度が高くなり溶融粘度が高いため塗料化の
作業性が悪くなり、かつ塗膜、焼き付けによつて
平滑で美麗な塗膜の形成が困難となる。他方酸価
が80をこえるポリエステル樹脂は平均重合度が低
くなりこれも塗料の貯蔵安定性が悪くなる。ま
た、かかるポリエステル樹脂の末端基は60%以
上、好ましくは80%以上がカルボキシル基であ
り、塗膜を焼付ける際の硬化反応にあたり、エポ
キシ樹脂の含有するグリシジル基との反応が支配
的となつて、揮発成分が殆んど無視しうる程度に
少ないことが望ましい。
本発明の方法を実施するにあたり、用い得るエ
ポキシ樹脂としては、たとえば、エピ・ビス型の
エポキシ樹脂など室温で液状であるエポキシ樹脂
があげられる。
ポリエステル樹脂とエポキシ樹脂を溶融混合す
るにあたり、溶融状態にあるポリエステル樹脂と
エポキシ樹脂とを定量的に混合機へ供給し連続的
に混合、払出しすることによつて均一な混合が達
成され、かつ品質も極めて安定したポリエステル
樹脂組成物の調製が可能となる。この場合従来、
通常の溶融状態で製造されたポリエステル樹脂を
冷却・粉体し、エポキシ樹脂と予備混合して再溶
融混合する工程と比較してポリエステル樹脂組成
物調製時の温度管理が非常に容易となり、品質を
安定せしめ得るばかりでなく、エネルギー消費量
も大巾に低減し得るのである。混練機へ供給する
ポリエステル樹脂の温度は140〜200℃の範囲で選
ぶ。すなわち、200℃をこえる高い温度の場合は
相対的に短い時間で混合、払出しを行つてもエポ
キシ樹脂と部分的に反応するためわずかな条件の
変動も品質むらの要因となる。他方、140℃未満
の低い温度では溶融粘度が高くなつて混練機の消
費動力が大きくなり、かつエポキシ樹脂との粘度
差が大きすぎる場合、混練状態が不良になるとい
う欠点を生ずる。混合機へのポリエステル樹脂と
エポキシ樹脂の供給はギアポンプのごとき定量ポ
ンプを用いて連続的に行う。
混練機は1軸または2軸以上のスクリユーを備
えたもので、混合と同時に搬送機能を有するもの
を用いる。混練機のバレルおよび必要な場合には
スクリユーに熱媒を循環し、加熱または冷却のい
ずれも可能な混練機で120〜150℃の範囲で混練機
の消費動力が最も小さく、かつ払出されるポリエ
ステル樹脂組成物の温度が最も小さくなる熱媒温
度に設定して用いる。
次に実施例と参考例を示して本発明方法を具体
的に説明する。
実施例 1
テレフタル酸747Kg、エチレングリコール279
Kg、ネオペンチルグリコール468Kgを採り、150〜
250℃でエステル化反応を行つて160Kgの水を除い
て低重合体を調製する。次に触媒として三酸化ア
ンチモン262gを加えて280℃、0.2mmHgの減圧下
重縮合反応を行つて高重合度ポリエステルを調製
した後、トリメリツト酸47Kgを加えて250℃で解
重合反応を行つて軟化点95℃、酸価35、水酸基価
3のポリエステル樹脂を調製した。
続いて、エポキシ当量190g/当量の室温(25
℃)で液状のエピ・ビス型エポキシ樹脂を下記表
1に示す条件で二軸ニーダー(池貝鉄工社製RC
−100型)へ、ポリエステル樹脂とともにギアポ
ンプを用いて定量的に供給し、連続的に混合、払
出しを行つた。このようにして表2に示すポリエ
ステル樹脂組成物を調製した。
The present invention relates to a method for producing a polyester resin composition for powder coatings with stable quality and economically. In recent years, powder coatings have been steadily increasing in demand as resource-saving and non-polluting coatings in various industries such as building materials, home appliances, agricultural machinery, and automobiles. In this case, as materials for powder coatings, polyester resins are also used in large quantities in addition to epoxy resins and acrylic resins. Among them, polyester resin compositions consisting of saturated polyester resins whose terminal groups are mainly carboxyl groups and epoxy resins have almost no volatile components during the curing reaction, so they can be used over a wide range of film thicknesses of about 20 to 200 microns. It is one of the most preferred materials for powder coatings, as it is capable of forming a smooth and beautiful coating film without (boiling), and is also capable of forming a physically or chemically excellent coating film. However, the above-mentioned polyester resin composition consisting of a polyester resin whose terminal group is mainly a carboxyl group and an epoxy resin reacts and hardens itself when the temperature exceeds a certain temperature. Uniform mixing at a low temperature and/or in a short time is essential in order to form a smooth and beautiful coating film. Furthermore, powder coatings are often used continuously in large quantities, and since the recovered coating materials are reused, it is extremely important to provide materials that are stable over a long period of time. The present inventors have conducted intensive research to produce such a polyester resin composition for powder coatings in a stable and economically advantageous manner, and have found that the objective can be achieved by developing the following method. did it. That is, the present invention has a softening point of 60 to 120°C and an acid value of
20 to 80 and in which at least 60% of the terminal groups are carboxyl groups, and an epoxy resin having two or more glycidyl groups in the molecule. , an epoxy resin that is liquid at room temperature is used as the epoxy resin, and a saturated polyester resin in a molten state maintained at a temperature of 140°C to 200°C and an epoxy resin in a molten state held above the melting temperature are simultaneously used. A method for producing a polyester resin composition for powder coatings, which comprises quantitatively supplying the composition to a kneader equipped with one or more screws and continuously mixing and discharging at a temperature of 120 to 150°C. It is. The polyester resin used when carrying out the method of the present invention has aromatic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. group, alicyclic, aliphatic dicarboxylic acids or their lower dialkyl esters, trimellitic acid,
Polyhydric carboxylic acids such as trimezic acid and pyromellitic acid, their anhydrides, and lower alkyl esters are used as acid components, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butane are used as acid components. Diol, 1,4-
Butanediol, 1,5-pentanediol,
Dialcohols such as 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,4-cyclohexanedimethanol, and polyhydric alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol are used as alcohol components. Then, if necessary, esterification or transesterification is carried out in the presence of a catalyst at a temperature of 150 to 250°C, and a polycondensation catalyst such as antimony trioxide, germanium oxide, or tetrabutyl titanate is added to the resulting low polymer. hand
A polyester with a high degree of polymerization is obtained by performing a polycondensation reaction at a temperature of 200 to 300°C under reduced pressure of 0.5 mmHg or less. Furthermore, using the above-mentioned dicarboxylic acid or/and polycarboxylic acid in the necessary amount depending on the acid value and average degree of polymerization of the polyester resin for this purpose, the temperature is 200 to 280°C.
A depolymerization reaction is carried out to obtain a polyester resin, which is one of the most preferable methods in terms of stable quality.
It is one. This may be a polyester resin obtained simply by an esterification reaction, or a polyester resin obtained by a polycondensation reaction in addition to an esterification reaction. However, when using polyester resin produced by any method as a material for powder coatings, its softening point is
It is necessary to adjust the temperature to 60-120°C, preferably 80-100°C. In other words, resins with a softening point of 60°C or lower may have storage stability problems when used as such or when prepared as a powder coating, while resins with a softening point of 120°C or higher may be mixed with pigments etc. and used as a powder. The workability when preparing a body paint becomes extremely poor, and it becomes difficult to form a smooth and beautiful paint film by painting or baking. Further, it is very important to adjust the acid value of the polyester resin to a range of 20 to 80 in order to balance the workability of forming a paint, the storage stability of the paint, and the performance of the coating film. In other words, polyester resins with an acid value of less than 20 usually have a high average degree of polymerization and a high melt viscosity, making it difficult to work with paints, and making it difficult to form a smooth and beautiful paint film during coating and baking. Become. On the other hand, polyester resins with an acid value exceeding 80 have a low average degree of polymerization, and this also results in poor storage stability of the paint. In addition, 60% or more, preferably 80% or more of the terminal groups of such polyester resin are carboxyl groups, and the reaction with the glycidyl group contained in the epoxy resin becomes dominant in the curing reaction when baking the coating film. Therefore, it is desirable that the volatile components be so small as to be almost negligible. In carrying out the method of the present invention, epoxy resins that can be used include, for example, epoxy resins that are liquid at room temperature, such as epi-bis type epoxy resins. When melt-mixing polyester resin and epoxy resin, uniform mixing is achieved by quantitatively feeding the molten polyester resin and epoxy resin to a mixer, mixing them continuously, and discharging them. It also becomes possible to prepare extremely stable polyester resin compositions. In this case, conventionally,
Compared to the usual process of cooling and powdering polyester resin produced in a molten state, premixing it with epoxy resin, and then remelting and mixing it, temperature control during the preparation of polyester resin compositions is much easier and quality can be improved. Not only can this be stabilized, but energy consumption can also be significantly reduced. The temperature of the polyester resin supplied to the kneader is selected within the range of 140 to 200°C. In other words, in the case of high temperatures exceeding 200°C, even if mixing and dispensing are performed in a relatively short time, the mixture will partially react with the epoxy resin, so even slight variations in conditions will cause uneven quality. On the other hand, at a low temperature of less than 140°C, the melt viscosity becomes high and the power consumption of the kneading machine increases, and if the difference in viscosity from the epoxy resin is too large, the kneading state becomes poor. Polyester resin and epoxy resin are continuously supplied to the mixer using a metering pump such as a gear pump. The kneader is equipped with one or more screws and has mixing and conveying functions at the same time. A kneader that circulates a heat medium through the barrel of the kneader and, if necessary, the screw, and is capable of heating or cooling, is the polyester that consumes the least amount of power in the kneader in the range of 120 to 150°C and can be dispensed. The heating medium temperature is set and used so that the temperature of the resin composition becomes the lowest. Next, the method of the present invention will be specifically explained with reference to Examples and Reference Examples. Example 1 Terephthalic acid 747Kg, ethylene glycol 279
Kg, neopentyl glycol 468Kg was taken, 150~
A low polymer is prepared by carrying out an esterification reaction at 250°C and removing 160 kg of water. Next, 262g of antimony trioxide was added as a catalyst and a polycondensation reaction was carried out at 280°C under reduced pressure of 0.2mmHg to prepare a highly polymerized polyester, and then 47kg of trimellitic acid was added and a depolymerization reaction was carried out at 250°C to soften it. A polyester resin having a temperature of 95°C, an acid value of 35, and a hydroxyl value of 3 was prepared. Subsequently, an epoxy equivalent of 190 g/equivalent at room temperature (25
℃) in a twin-screw kneader (Ikegai Iron Works RC) under the conditions shown in Table 1 below.
-100 type) using a gear pump together with polyester resin, and continuously mixed and dispensed. In this way, polyester resin compositions shown in Table 2 were prepared.
【表】【table】
【表】【table】
【表】
参考例 1
下記表3に示す条件で実施例1と同様にポリエ
ステル樹脂組成物を調製し、表4に示す結果を得
た。[Table] Reference Example 1 A polyester resin composition was prepared in the same manner as in Example 1 under the conditions shown in Table 3 below, and the results shown in Table 4 were obtained.
【表】【table】
【表】【table】
【表】
参考例 2
ポリエステル樹脂をペレツト状(室温)で実施
例1のNo.1と同様にロータリーバルブを用いて供
給し、混合・払出しを行つたがニーダーの受入孔
で半溶融物が蓄積して連続運転が非常に困難であ
つた。
参考例 3
実施例1のNo.1〜9および参考例1のNo.1、34
の各ポリエステル樹脂組成物100重量部あたり酸
化チタン30重量部、触媒としてステアリン酸カル
シウム1重量部、塗面調製剤としてモンサント社
製モダフロー(商品名)1重量部をブス社製PR
−46型コニーダーを用いて混練して粉体後BT
#37鋼板に塗装し、190℃で30分間焼付して塗膜
性能を評価し表5に示す結果を得た。[Table] Reference Example 2 Polyester resin was supplied in pellet form (at room temperature) using a rotary valve in the same manner as No. 1 of Example 1, and mixed and dispensed, but semi-molten material accumulated in the receiving hole of the kneader. Therefore, continuous operation was extremely difficult. Reference Example 3 Nos. 1 to 9 of Example 1 and Nos. 1 and 34 of Reference Example 1
Per 100 parts by weight of each polyester resin composition, 30 parts by weight of titanium oxide, 1 part by weight of calcium stearate as a catalyst, 1 part by weight of Modaflow (trade name) manufactured by Monsanto Co. as a coating surface conditioner, and PR manufactured by Busu Co., Ltd.
- After kneading into powder using a 46 type co-kneader, BT
It was painted on a #37 steel plate and baked at 190°C for 30 minutes to evaluate the coating film performance, and the results shown in Table 5 were obtained.
【表】【table】
【表】
但し、塗膜性能の評価は以下の方法で行つた。
60゜鏡面反射率:JIS Z8741に準ずる。
エリクセンテスト:JIS Z2247に準ずる。
耐衝撃性テスト:デユポン式インパクトテスター
を用いて1/2″−1Kgで測定。
耐沸水性テスト:JIS K6902に準じて処理した
後、エリクセンテストを行う。
耐塩水性テスト:試験片表面に切り傷をつけ40℃
で5%塩化ナトリウム水溶液噴霧雰囲気中に
250時間静置後粘着テープを用いて塗膜を剥離
し、剥離巾を測定。
実施例と参考例とを比較すれば明らかなよう
に、本発明の方法を実施することが従来法に比較
して格別に優れた作用、効果を示している。これ
は主として末端基がカルボキシル基であるポリエ
ステル樹脂とエポキシ樹脂とを実質的に殆んど反
応させることなく均一な混合が達成され、品質の
安定した粉体塗料用ポリエステル樹脂を製造する
ことが可能であることを示している。[Table] However, the coating film performance was evaluated using the following method. 60° specular reflectance: According to JIS Z8741. Erichsen test: According to JIS Z2247. Impact resistance test: Measured at 1/2″-1Kg using a Dupont impact tester. Boiling water resistance test: Perform Erichsen test after processing according to JIS K6902. Salt water resistance test: Cut a cut on the surface of the test piece. Soaked at 40℃
in a 5% sodium chloride aqueous solution spray atmosphere.
After standing for 250 hours, remove the coating using adhesive tape and measure the peeling width. As is clear from a comparison between Examples and Reference Examples, implementing the method of the present invention exhibits exceptionally superior actions and effects compared to conventional methods. This achieves uniform mixing of the polyester resin whose terminal group is mainly a carboxyl group and the epoxy resin with virtually no reaction, making it possible to produce polyester resin for powder coatings with stable quality. It shows that.
Claims (1)
の少なくとも60%がカルボキシル基である飽和ポ
リエステル樹脂と、分子内に2個以上のグリシジ
ル基を有するエポキシ樹脂とからなる粉体塗料用
ポリエステル樹脂組成物を製造する方法におい
て、エポキシ樹脂として室温で液状であるエポキ
シ樹脂を用い、かつ140℃〜200℃の温度に保持さ
れた溶融状態にある飽和ポリエステル樹脂と、溶
融温度以上に保持された溶融状態にあるエポキシ
樹脂とを同時に定量的に、1軸または2軸以上の
スクリユーを備えた混練機へ供給して120〜150℃
の温度で連続的に混合払出しすることを特徴とす
る粉体塗料用ポリエステル樹脂組成物の製造法。1 Powder coating made of a saturated polyester resin with a softening point of 60 to 120°C, an acid value of 20 to 80, and at least 60% of the terminal groups are carboxyl groups, and an epoxy resin having two or more glycidyl groups in the molecule. In the method for producing a polyester resin composition for use, an epoxy resin that is liquid at room temperature is used as the epoxy resin, a saturated polyester resin that is in a molten state maintained at a temperature of 140 ° C to 200 ° C, and a saturated polyester resin that is maintained at a temperature above the melting temperature. The molten epoxy resin is simultaneously fed quantitatively to a kneader equipped with one or more screws at 120 to 150°C.
A method for producing a polyester resin composition for powder coatings, which comprises continuously mixing and dispensing at a temperature of .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP167780A JPS5699264A (en) | 1980-01-10 | 1980-01-10 | Production of polyester resin composition for powder paint |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP167780A JPS5699264A (en) | 1980-01-10 | 1980-01-10 | Production of polyester resin composition for powder paint |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5699264A JPS5699264A (en) | 1981-08-10 |
JPS6317105B2 true JPS6317105B2 (en) | 1988-04-12 |
Family
ID=11508136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP167780A Granted JPS5699264A (en) | 1980-01-10 | 1980-01-10 | Production of polyester resin composition for powder paint |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5699264A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5994462A (en) * | 1998-06-11 | 1999-11-30 | The Dexter Corporation | Solid coating compositions for powder and extrusion applications |
CN108624200B (en) * | 2018-06-06 | 2020-07-24 | 宁波派特勒新材料股份有限公司 | High-temperature-resistant powder coating and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5380429A (en) * | 1976-12-27 | 1978-07-15 | Kansai Paint Co Ltd | Polyester resin composition for powder coating |
-
1980
- 1980-01-10 JP JP167780A patent/JPS5699264A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5380429A (en) * | 1976-12-27 | 1978-07-15 | Kansai Paint Co Ltd | Polyester resin composition for powder coating |
Also Published As
Publication number | Publication date |
---|---|
JPS5699264A (en) | 1981-08-10 |
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