JPH01221469A - Powder coating resin composition - Google Patents
Powder coating resin compositionInfo
- Publication number
- JPH01221469A JPH01221469A JP4841288A JP4841288A JPH01221469A JP H01221469 A JPH01221469 A JP H01221469A JP 4841288 A JP4841288 A JP 4841288A JP 4841288 A JP4841288 A JP 4841288A JP H01221469 A JPH01221469 A JP H01221469A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyester
- formula
- resin
- units
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims description 26
- 239000011248 coating agent Substances 0.000 title claims description 19
- 239000000843 powder Substances 0.000 title claims description 18
- 239000011342 resin composition Substances 0.000 title claims description 6
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 229920001225 polyester resin Polymers 0.000 claims abstract description 19
- 239000004645 polyester resin Substances 0.000 claims abstract description 19
- -1 isocyanate compound Chemical class 0.000 claims abstract description 10
- 125000006850 spacer group Chemical group 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 150000002148 esters Chemical group 0.000 claims abstract description 6
- 229920003180 amino resin Polymers 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims abstract description 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 69
- 229920000728 polyester Polymers 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 27
- 238000005809 transesterification reaction Methods 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WXYTXCXWNITTLN-UHFFFAOYSA-N 3-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCCC(C(O)=O)C1C(O)=O WXYTXCXWNITTLN-UHFFFAOYSA-N 0.000 description 1
- BJDDKZDZTHIIJB-UHFFFAOYSA-N 4,5,6,7-tetrafluoro-2-benzofuran-1,3-dione Chemical compound FC1=C(F)C(F)=C2C(=O)OC(=O)C2=C1F BJDDKZDZTHIIJB-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- YWVFNWVZBAWOOY-UHFFFAOYSA-N 4-methylcyclohexane-1,2-dicarboxylic acid Chemical compound CC1CCC(C(O)=O)C(C(O)=O)C1 YWVFNWVZBAWOOY-UHFFFAOYSA-N 0.000 description 1
- NNJMFJSKMRYHSR-UHFFFAOYSA-N 4-phenylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=CC=C1 NNJMFJSKMRYHSR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 244000144992 flock Species 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は粉体塗料に使用せられる熱硬化性樹脂組成物に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a thermosetting resin composition used in powder coatings.
従 来 技 術
粉体塗料は通常、樹脂成分、顔料および添加剤を加熱溶
融混練した後、冷却して得られる固形分を粉砕して製造
される。従っで、使用する樹脂成分が熱硬化性の場合、
その樹脂成分は溶融混練時は安定であるが、逆に塗装後
の硬化工程ては加熱により充分に硬１ヒしなければなら
ないという厳しい性能か要求される、このため通常、溶
剤系塗料に用いられるポリエステル樹脂とメラミン樹脂
あるいはフロックイソシアナ−１へ化合物からなる組成
物を用いた場合、一般に樹脂の軟１ヒ点が低いた゛め、
粉体塗料は貯蔵中にフロノキンクを起こし易い。また軟
化点の高いものを用いた場合、これらは溶融混練中にケ
ル化し易いため粉体塗料の製造か極めて困難であり、ま
た粉体塗料か得られたとしても塗膜の平滑性、光沢に劣
る。ＵＳ４，３５２．９２４、ＥＰ Ｑ、０７Ｑ、ｌ１
８なとてはジカルボン酸としてテレフタル酸、イソフタ
ル酸、１．４−シクロヘキサンジカルホン酸とジオール
として１，４−フタンシオール、１．６−ヘキサンジオ
ールからなる結晶性ポリエステルを用いた熱硬化性粉体
塗料組成物が開示されているか、粉体塗料のフロラキン
ク性と硬化塗膜の平滑性の両立が未だ不十分てあった。PRIOR ART Powder coatings are usually produced by heating, melting, and kneading resin components, pigments, and additives, and then cooling and pulverizing the resulting solids. Therefore, if the resin component used is thermosetting,
The resin component is stable when melted and kneaded, but on the other hand, strict performance is required in the curing process after painting, in which it must be sufficiently hardened by heating.For this reason, it is usually used in solvent-based paints. When a composition consisting of a polyester resin and a melamine resin or a compound made of flock isocyanate-1 is used, since the softness point of the resin is generally low,
Powder coatings are prone to fluorokinking during storage. Furthermore, if a material with a high softening point is used, it is extremely difficult to produce a powder coating because it tends to kelp during melt-kneading, and even if a powder coating is obtained, the smoothness and gloss of the coating film may be affected. Inferior. US4,352.924, EP Q, 07Q, l1
8 Nate is a thermosetting powder using crystalline polyester consisting of terephthalic acid, isophthalic acid, and 1,4-cyclohexanedicarphonic acid as dicarboxylic acids and 1,4-phthanesiol and 1,6-hexanediol as diols. Although coating compositions have not yet been disclosed, it is still insufficient to achieve both the flora kink properties of powder coatings and the smoothness of cured coatings.
発明か解決しようとする問題点
そこてポリエステル樹脂とメラミン樹脂あるいはフロソ
クイゾシアナー１へからなる硬化剤系の粉体塗料であっ
で、貯蔵中にフロラキンクを起こすことがなく、安定性
に優れ、しかも溶融混練の通常手法で容易に製造するこ
とがてき、塗膜の平滑性、光沢に優れたものか要求され
ており、かかる粉体塗料用樹脂組成物を提供することか
本発明目的である。The problem to be solved by the invention is therefore a curing agent-based powder coating consisting of polyester resin and melamine resin or fluoroquizocyaner 1, which does not cause flora kink during storage and has excellent stability. Moreover, it is required that the resin composition can be easily produced by the usual method of melt-kneading and that the coating film has excellent smoothness and gloss. be.
問題点を解決するための手段
本発明に従えは、上記発明目的が、式
Ａ−Ｘ−Ｂ て示される繰り返し単位（Ｉ）（式中、
への１００〜５０モル％は２コ以上のベンゼン環かパラ
位で相互に結合されてなる基、２コ以上のベンゼン環が
パラ位でアゾ、アゾキシ、エステルあるいはトランスビ
ニレンにより結合されてなる基および２，６−ナフチレ
ン基からなる群より選ばれるメソゲン基で、５０モル％
未満はｐ−フェニレン基、■−フェニレフ基あるいはト
ランス１，４−シクロヘキシレン基てあってもがまわな
い：Ｂは−（ＣＨ２）、、−または−（ＣＨ２Ｃ）１２
０−）、Ｉ、−ＣＩＩ２Ｃ４１２−で表されるスペーサ
ー基；ｎは２〜２０、ｍは１〜１９の整数。Means for Solving the Problems According to the present invention, the above object of the invention is achieved by repeating unit (I) represented by the formula A-X-B (in the formula,
100 to 50 mol% is a group formed by two or more benzene rings bonded to each other at the para position, a group formed by two or more benzene rings bonded to each other at the para position by azo, azoxy, ester, or transvinylene. and a mesogenic group selected from the group consisting of 2,6-naphthylene group, 50 mol%
Less than or equal to p-phenylene group, ■-phenylev group, or trans-1,4-cyclohexylene group is acceptable: B is -(CH2), - or -(CH2C)12
0-), I, a spacer group represented by -CII2C412-; n is an integer of 2 to 20, and m is an integer of 1 to 19.
Ｘはエステル結合）
のみ、あるいは該単位（Ｉ）と式
Ｒて表される単位（ＩＩ）
（式中、Ｒは４コまでの０１４を含みうる２〜６価の脂
肪族、芳香族、脂環族炭化水素残基）とか（１）／（ｎ
）−９，９１０，１〜？’０／３０ノ重量比で任意順
位に組み合わされてなり、各隣接単位はエステル結合で
結合されていで、末端はＨＯあるいはその反応性誘導体
で、樹脂の０１１価が２０〜２００である異方性溶融相
を形成しうるポリエステル樹脂と（ｂ）ブロックイソシ
アネート化合物あるいはアミノプラス１へ樹脂
とからなる粉体塗料用樹脂組成物により達成せられる。X is an ester bond), or the unit (I) and a unit (II) represented by the formula cyclic hydrocarbon residue) or (1)/(n
)-9,910,1~? '0/30 weight ratio, each adjacent unit is bonded with an ester bond, the terminal is HO or its reactive derivative, and the 011 valence of the resin is 20 to 200. This can be achieved by using a resin composition for powder coatings comprising a polyester resin capable of forming a molten phase and (b) a blocked isocyanate compound or aminoplus 1 resin.
本発明で用いられるポリエステル樹脂は、式Ａ−Ｘ−ｎ
て示される繰り返し単位（１）（式中、人の１００
〜５０モル％は２コ以上のベンゼン環かパラ位て相互に
結合されてなる基、２コ以上のベンゼン環がパラ位てア
ゾ、アゾキシ、エステルあるいはトランスビニレンによ
り結合されてなる基および２，６−ナフチレン基からな
る群より選ばれるメソゲン基で、５０モル％未満はｐ−
フェニレン基、ｍ−フェニレン基あるいは１ヘランス１
，４−シクロヘキシレン基てあっオもがまわない；ｎは
−（ＣＨ２）ｎ−または−（ＣＨ２ＣＨ２０−） ｍ
−ＣＩｔ 。ＣＨ２−で表されるスペーサー基；ｎは２
〜２０、ｍは１〜１９の整数；Ｘはエステル結合）
からなり、各隣接単位かエステル結合で結合されていで
、末端はＨＯ基あるいはその反応性誘導体、例えばアセ
デルオキシ基なとで、樹脂のＯＨ価が２０〜２００であ
る異方性溶解相を形成しうるポリエステル樹脂、あるい
は上記式で示される単位（１）と、式
Ｒで表される単位（ＩＩ）
（式中、Ｒは４コまでの０１１を含みうる２〜６価の脂
肪族、芳香族、脂環族炭化水素残基〉とか（Ｉ ） ／
（ＩＩ ） −９９，９１０，１〜７０／ ３０の重
量比で任意順位に各々エステル結合で結合されてなり、
末端はＯＨ基あるいはその反応性誘導体で、樹脂のＯＨ
価が２０〜２００の範囲内にある、異方性溶解相を形成
しうるポリエステル樹脂である。かがる樹脂はその分子
中に、弐 八−Ｘ−Ｂ で表される単位、すなわち面
構造を有し剛直なメソケン基（Ａ）と屈曲性のスペーサ
ー基（Ｂ）かエステル結合（Ｘ）により結合されノご構
造を繰り返して有していで、所謂主鎖型高分子液晶化合
物を構成し、また液晶性を損なわぬ程度においで、特定
構造の芳香族環あるいは１〜ランスシクロヘキサン環が
含まれ、各隣接単位はエステル結合で結合され、末端が
囲碁あるいはその反応性誘導体で、樹脂のｌ個か２０〜
２００の範囲内にある新規な熱硬化性のポリエステル樹
脂である。The polyester resin used in the present invention has the formula A-X-n
repeating unit (1) (in the formula, 100 human
~50 mol% is a group in which two or more benzene rings are bonded to each other at the para position, a group in which two or more benzene rings are bonded to each other at the para position by azo, azoxy, ester, or transvinylene, and 2, A mesogenic group selected from the group consisting of 6-naphthylene groups, less than 50 mol% of which is p-
Phenylene group, m-phenylene group or 1 herans 1
,4-cyclohexylene group does not struggle; n is -(CH2)n- or -(CH2CH20-) m
-CIt. Spacer group represented by CH2-; n is 2
~20, m is an integer from 1 to 19; A polyester resin capable of forming an anisotropic dissolved phase having an OH value of 20 to 200, or a unit (1) represented by the above formula and a unit (II) represented by the formula R (wherein R is 4 units). (I) /
(II) -99,910, 1 to 70/30, each bonded by an ester bond in an arbitrary order,
The terminal end is an OH group or its reactive derivative, and the OH group of the resin
It is a polyester resin having a value within the range of 20 to 200 and capable of forming an anisotropic dissolved phase. Kagaru resin has a unit represented by 28-X-B in its molecule, that is, a rigid mesoken group (A) with a planar structure and a flexible spacer group (B) or an ester bond (X). It has a repeating chain structure, which is bonded by Each adjacent unit is connected by an ester bond, the terminal end is Go or its reactive derivative, and the resin is 1 or 20 to
It is a new thermosetting polyester resin within the range of 200.
本発明で使用せられるボリエスル樹脂中に八として組み
入れられる成分は、その１００〜５０モル％か２コ以上
のヘンセン環がパラ位で相互に結合さ４ 、４ ” −
ｐ−チルフェニレン沓◇ｘ召■など、２コ以上のベンゼ
ン環がパラ位てアゾ、アゾキシエステルあるいはトラン
スビニレンにより結合さ５０モル％未満はｐ−フェニレ
ン、ｍ−フェニレンアルいはｌ・ランス１，４−シクロ
ヘキシレン基てあってもよい。The component incorporated into the polyester resin used in the present invention is 100 to 50 mol%, or 2 or more Hensen rings are bonded to each other at the para position 4,4''-
When two or more benzene rings are bonded at the para position by azo, azoxy ester or transvinylene, such as p-tylphenylene, p-phenylene, m-phenylene al or l-lan A 1,4-cyclohexylene group may also be present.
上記人成分はポリエステルの酸成分としで、あるいは多
価アルコール成分として好都合に組み込まれるので、末
端がカルボキシル基、カルボン酸エステル、酸塩化物、
水酸基、アセチル基なとである化合物から誘導せられる
ことか好ましい。かかる代表的化合物としては下記のも
のが挙げられる。The above human component is conveniently incorporated as an acid component of polyester or as a polyhydric alcohol component, so that the terminal end is a carboxyl group, a carboxylic acid ester, an acid chloride,
Preferably, it is derived from a compound having a hydroxyl group or an acetyl group. Such representative compounds include the following.
メソゲン基として導入せられる場合。When introduced as a mesogenic group.
ＨＯ［相］−■−ゆｏＬ
ＣＨ，０ＯＣ−■ｆ−ＣＯＯＣＨ３、
Ｈ００Ｃ４４舎Ｃ００Ｌ
メソゲン基以外の構成成分として導入せられる場合
一９＝
０ トラフＸｌ、４−シクロヘキサンジカ
ルボン酸ジエステルこれらは勿論、本発明のＡ成分を導
入する目的で使用せられる具体的化合物の例示にすきず
、本発明はこれら化合物により何ら制限せられるもので
はない。HO[phase] -■-YoL CH,0OC-■f-COOCH3, H00C44C00L When introduced as a component other than mesogenic group -9 = 0 Trough Xl, 4-cyclohexanedicarboxylic acid diester These are of course main Although the specific compounds used for the purpose of introducing component A of the invention are exemplified, the present invention is not limited in any way by these compounds.
Ｂとして組み入れられる成分は式−（ＣＨ２）ｎ＝ある
いは−（ＣＨ２ＣＨ２０）、−ＣＨ２−ＣＨ２−テ示さ
れるスペーサー基であり、このスペーサー基は前述のＡ
成分と、また隣接する Ａ−Ｘ−Ｂ単位と各々エステル
結合により結合せられる。従ってががるスペーサー基を
導入するために使用せられる化合物も、末端が各々ＨＯ
あるいはＣＯ０＋１もしくはその反応性誘導体であるこ
とが好ましく、具体的には下記の如き化合物が使用せら
れる。The component incorporated as B is a spacer group of the formula -(CH2)n= or -(CH2CH20), -CH2-CH2-;
component and adjacent A-X-B units, respectively, by ester bonds. The compounds used to introduce the spacer groups thus also end with each terminal being HO.
Alternatively, CO0+1 or a reactive derivative thereof is preferable, and specifically, the following compounds are used.
−（ＣＨ□）、、−を有する化合物。A compound having -(CH□),,-.
エチレングリコール、１，３−プロパンジオール、１．
４−フタンジオール、１，５−ベンタンジオール、１゜
６−ヘキザンシオール、１，８−オクタンジオール、１
゜９−ノナンジオール、１．１０−デカンジオール、１
．１２−トチカンジオールなと、アジピン酸、セハチン
酸、アセライン酸なとの脂肪族ジカルボン酸なと−（Ｃ
ＩＩ□ＣＨ２０）ｌ、、−ＣＨ２−Ｃ１＋２−を有する
化合物：ンエヂレフクリコール、トリエチレンクリコー
ル、テトラエチレンクリコールなど。Ethylene glycol, 1,3-propanediol, 1.
4-phthanediol, 1,5-bentanediol, 1゜6-hexanediol, 1,8-octanediol, 1
゜9-nonanediol, 1.10-decanediol, 1
．． 12-Toticanediol, aliphatic dicarboxylic acids such as adipic acid, cehatic acid, acelaic acid, etc.
Compounds having -CH2-C1+2-: II□CH20)l, -CH2-C1+2-, such as glycol, triethylene glycol, and tetraethylene glycol.
本発明のポリエステル樹脂は上記の式
（式中、Ａはメソケン基、Ｂはスペーサー基、Ｘはエス
テル結合）
で表される単位（Ｉ）以外に所望により、式Ｒで表され
る単位（ＩＩ）
ずなわち、４コまてのＯｌｌ、含みうる２〜６価の脂肪
族、芳香族、脂環族炭化水素残基が（■）／（ＩＩ ）
＝９９．９１０．１〜７０ ／３０の重量比で含まれ
る。Ｒ単位も隣接する人、ＢあるいはＲと各々エステル
結合で結合せられるため原料化合物としては少なくとも
２コのＨＯｌＣｏｏｌ−１の如きエステル結合に関与し
うる官能基を有する化合物として用いられるのが好まし
く、具体的には下記の如き化合物を用い、ポリエステル
中に導入せられる。In addition to the unit (I) represented by the above formula (where A is a mesocene group, B is a spacer group, and X is an ester bond), the polyester resin of the present invention may optionally contain units represented by the formula R (II). ) That is, 4 Olls, the divalent to hexavalent aliphatic, aromatic, alicyclic hydrocarbon residues that can be contained are (■) / (II )
=99.910.1 to 70/30 weight ratio. Since the R unit is also bonded to an adjacent person, B or R, through an ester bond, it is preferable to use a compound having at least two functional groups capable of participating in an ester bond, such as HOlCool-1, as a raw material compound. Specifically, the following compounds are used and introduced into polyester.
ネオペンチルクリコール、ヒトロキシピハリック酸、シ
クロヘキサン１，４−ジオール、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、ソ
ルビトールなど；無水フタル酸無水トリメリット酸、無
水ピロメリット酸、テトラクロル無水フタル酸、テトラ
フロロ無水フタル酸、ｐ−ヒドロキシ安息香酸、ヘキサ
ヒドロ無水フタル酸、３−メチルへキサヒドロフタル酸
、４−メチルへキサヒドロフタル酸なと。上記はいずれ
も例示的なもので、限定的なものと解さるべきではない
。Neopentyl glycol, hydroxypihalic acid, cyclohexane 1,4-diol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrachlorophthalic anhydride , tetrafluorophthalic anhydride, p-hydroxybenzoic acid, hexahydrophthalic anhydride, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid. All of the above are illustrative and should not be construed as limiting.
本発明のポリエステル樹脂は上述のＡ、ＢおよびＲ成分
を導入するに適したアルコールあるいは酸原料化合物を
所定割合で使用し、通常のエステル形成手法により容易
に製造することが可能である。すなわち原料化合物中の
アルコール成分を過剰に用い、１３０〜３００°Ｃの温
度で常法によりエステル化反応あるいはエステル交換反
応で反応せしめる。反応は窒素カスなとの不活性気体を
通しつつ実施することか好ましく、また所望によりエス
テル化触媒あるいはエステル交換触媒を用いて行われる
。かかる触媒としては、鉛、亜鉛、マンカン、バリウム
、カルシウム、マグネシウム、リチウムケルマニウム、
アンチモンなどの金属の酸化物、酢酸塩などや、Ｐ−）
ルエンスルホン酸、チタン酸アルキルエステルなどや、
有機錫化合物などが好適で、通常酸成分に対し００１〜
０．５重量％程度の割合で使用せられる。アルコール成
分を過剰に用いることにより末端かヒドロキシル基ある
いはその反応性誘導体のポリエステルが得られる。The polyester resin of the present invention can be easily produced by a conventional ester formation method using alcohol or acid raw material compounds suitable for introducing the above-mentioned A, B, and R components in a predetermined ratio. That is, the alcohol component in the raw material compound is used in excess and reacted by an esterification reaction or transesterification reaction at a temperature of 130 to 300°C by a conventional method. The reaction is preferably carried out while passing an inert gas such as nitrogen gas, and optionally using an esterification catalyst or transesterification catalyst. Such catalysts include lead, zinc, mankanium, barium, calcium, magnesium, lithium kermanium,
Metal oxides such as antimony, acetate, etc., and P-)
Luenesulfonic acid, titanate alkyl ester, etc.
Organic tin compounds etc. are suitable, and usually 001~
It is used in a proportion of about 0.5% by weight. By using an excess of the alcohol component, a polyester having terminal hydroxyl groups or reactive derivatives thereof can be obtained.
すでに述へた如く本発明のポリエステル樹脂には面構造
を有する比較的剛直なメソゲン基（Ａ＞と屈曲性スペー
サー基（Ｂ）とがエステル結合て結合された単位（１）
と、所望により膜物性制御のための炭化水素残基である
Ｒて示される単位（ＩＩ）とか含まれ、液晶性、膜物性
の点から、（丁）／（ＩＩ ） −９９，９１０，１〜
７０／３０の範囲内に限定されており、また末端はＩ（
０基あるいはそれらの反応性誘導体であり、樹脂のＯＨ
価が２０〜２ｏｏ、好ましくは３０〜１００の間に制御
されていで、充分な熱硬化性を示しうる。分子量に関し
ては選択せられる各成分の種類によるが通常、数平均分
子量 ５００〜４０００で相転移温度は、約８０〜２３
０’Ｃの範囲内にある。尚、本発明者らは前記へで示さ
れるメソケン基の５０モル％未満を特定の芳香族環ある
いはシクロヘキサン環構造の有機基、すなわちｐ−）二
二しフ、ｍ−フェニレンあるいは１．４−シクロヘキシ
レンで置換しても所期の液晶性を損なうことな〈発明目
的に適したポリエステル樹脂組成物が得られることを見
出した。As already mentioned, the polyester resin of the present invention has a unit (1) in which a relatively rigid mesogenic group (A> having a planar structure and a flexible spacer group (B) are bonded through an ester bond).
and, if desired, a unit (II) represented by R, which is a hydrocarbon residue for controlling the physical properties of the film, is included. ~
It is limited within the range of 70/30, and the terminal is I (
0 groups or their reactive derivatives, and the OH of the resin
The value is controlled between 20 and 2oo, preferably between 30 and 100, and exhibits sufficient thermosetting properties. The molecular weight depends on the type of each component selected, but usually the number average molecular weight is 500-4000 and the phase transition temperature is about 80-23.
It is within the range of 0'C. In addition, the present inventors have determined that less than 50 mol% of the mesocene group shown above is a specific aromatic ring or an organic group having a cyclohexane ring structure, i.e., p-)22ph, m-phenylene, or 1,4- It has been found that even when substituted with cyclohexylene, a polyester resin composition suitable for the purpose of the invention can be obtained without impairing the desired liquid crystallinity.
本発明では上記の液晶性で且つ架橋官能基の）１０基を
多数有するポリエステル樹脂がプロ・ツクポリイソシア
ナート化合物あるいはアミノプラスト樹脂と組み合わさ
れて使用せられる。該ポリエステル樹脂は常温固体で結
晶性の剛直メソゲン基を含＝ １４−
むため、フロックポリイソシアナート化合物あるいはア
ミノプラスト樹脂と配合されても貯蔵中にフロラキンク
を起こすことかなく貯蔵安定性に優れており、また１１
０価か大て硬化剤との反応性に優れ、また液晶性の特性
の故に、加熱溶融時に一挙に粘性の低い液体に変しるた
め、フロー性に優れ塗膜外観に優れた非品性透明な硬化
塗膜を与えることかできる。さらにまた屈曲性に富み、
柔軟なスペーサー基あるいは膜物性改善に有用な炭化水
素残基Ｒを有するため、折曲は加工性その他の塗膜物性
にも優れているため、粉体塗料用の樹脂組成物として極
めて有用である。In the present invention, the above-mentioned polyester resin which is liquid crystalline and has a large number of 10 crosslinking functional groups is used in combination with a pro-polyisocyanate compound or an aminoplast resin. Since the polyester resin is solid at room temperature and contains crystalline rigid mesogenic groups, it does not cause flora kink during storage and has excellent storage stability even when blended with flocked polyisocyanate compounds or aminoplast resins. Hello, 11 again
It has excellent reactivity with the curing agent with a valence of 0 or more, and due to its liquid crystal properties, it instantly changes to a low viscosity liquid when heated and melted, so it has excellent flowability and excellent coating film appearance. It is possible to provide a transparent cured coating. Furthermore, it is highly flexible,
Because it has a flexible spacer group or a hydrocarbon residue R that is useful for improving film properties, bent resin has excellent processability and other coating film properties, making it extremely useful as a resin composition for powder coatings. .
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
（以下余白）
会戦ｍ
加熱装置、攪拌機、窒素導入管、および分留塔を有する
反応容器に４．４′−ジフェニルカルホン酸ジメチルエ
ステル１０モル、１，９−ノナンジオール１１モル、シ
ブデルスズオキサイＦ２．２ｇを仕込み、乾燥窒素上加
熱を開始し、原料を融解させた。次いて１３０℃〜２３
０℃の温度でエステル交換反応させてメタノールを留出
させた。２３０ ”Ｃで保温しメタノール７６０ｍ１を
捕集した後、エステル交換反応を完結させるためＩＯｍ
ｍＨｇの減圧下で１時間反応させてポリエステルＡを得
な。(Left below) Battle m In a reaction vessel equipped with a heating device, a stirrer, a nitrogen inlet pipe, and a fractionating column, 10 moles of 4,4'-diphenylcarphonic acid dimethyl ester, 11 moles of 1,9-nonanediol, and Sibdel were added. 2.2 g of tin oxide F was charged and heating over dry nitrogen was started to melt the raw material. Then 130℃～23
Methanol was distilled off by transesterification at a temperature of 0°C. After collecting 760ml of methanol by keeping it warm at 230"C, IOm was used to complete the transesterification reaction.
Polyester A was obtained by reacting for 1 hour under reduced pressure of mHg.
得られたポリエステルは水酸基価２５の硬化性官能基を
有しており、溶媒としてトリクロルベンゼン、カラム温
度１３５℃てＧ Ｐ Ｃ測定した結果、数平均分子量（
ポリスチレン換算）は６８００てあった。The obtained polyester has a curable functional group with a hydroxyl value of 25, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135°C, the number average molecular weight (
Polystyrene equivalent) was 6,800.
また、このポリエステルは毎分１０’ｃ昇温条件下での
示差走査熱量計（ＤＳＣ）測定て約１４８°Ｃにおいて
大きな鋭い吸熱ピークを示し、毎分１０℃冷却下で約１
１６℃において同しく大きな鋭い発熱ピークかＪ忍ぬら
れた。In addition, this polyester exhibits a large sharp endothermic peak at about 148°C when measured by differential scanning calorimetry (DSC) under heating conditions of 10'c/min, and about 1.
An equally large sharp exothermic peak was observed at 16°C.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下で
の観察により、光学異方性に基つくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
合載イ列−て
４．４′−ジフェニルカルホン酸ジメチルエステル３モ
ル、１，９−ノナンジオール４モル、シフチルスズオキ
サイト０８ｇを仕込み、乾燥窒素上加熱を開始し、原料
を融解さぜな。次いて１３０°Ｃ〜２３０℃の温度でエ
ステル交換反応させてメタノールを留出さぜた。２３０
°Ｃて保温しメタノール２３０ｍ１ を捕集した後、エ
ステル交換反応を完結させるため、１０ｍｍ１１ｇの減
圧下て］時間反応させてポリエステルＢを祠な。3 moles of 4,4'-diphenylcarphonic acid dimethyl ester, 4 moles of 1,9-nonanediol, and 08 g of cyphthyltin oxide were placed in a combined row, and heating over dry nitrogen was started to melt the raw materials. Zena. Then, a transesterification reaction was carried out at a temperature of 130°C to 230°C to distill off methanol. 230
After collecting 230 ml of methanol by keeping it warm at 10°C, the polyester B was reacted for 1 hour under a reduced pressure of 10 mm and 11 g to complete the transesterification reaction.
得られたポリエステルは水酸基価８２の硬化性官能基を
有しており、溶媒としてトリクロルベンゼン、カラム温
度１３５°ＣてＧＰＣ測定した結果、数平均分子量（ポ
リスチレン換算）は］５５０てあった。The obtained polyester had a curable functional group with a hydroxyl value of 82, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 550.
また、このポリエステルは毎分１０°Ｃ昇温条件下ての
示差走査熱量計（ＤＳＣ＞測定で約１３８°Ｃにおいで
、メイン吸熱ピークを示し、毎分１０°Ｃ冷却下て約９
５°Ｃにおいて同しくメイン発熱ピークが認められた。In addition, this polyester shows a main endothermic peak at about 138°C as measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and about 9
A main exothermic peak was also observed at 5°C.
さらに、ピー１−ステーシイ」顕微鏡を用いた直交偏光
下ての観察により、光学異方性に基つくテクスチャーを
確認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a P1-Stacy microscope.
会戦−例１
４．４′−ジフェニルカルホン酸ジメヂルエルテル７モ
ル、１．８−オクタンジオール７モル、ジエチレンクリ
コール１モル、シフチルスズオキサイＦ１．５ｇを仕込
み、乾燥窒素上加熱を開始し、原料を融解させた。次い
て１３０℃〜２３０°Ｃの温度でエステル交換反応させ
てメタノールを留出さぜな。２３０°Ｃて保温しメタノ
ール５３０ｍ１ を捕集した後、エステル交換反応を完
結さぜるため、］００ｍｍ１１の減圧下で１時間反応さ
せてポリエステルＣを得た。Battle-Example 1 7 moles of dimethyl erther 4.4'-diphenylcarphonate, 7 moles of 1.8-octanediol, 1 mole of diethylene glycol, and 1.5 g of cyphthyltin oxide F were charged and heating over dry nitrogen was started. The raw material was melted. Then, methanol is distilled off by transesterification at a temperature of 130°C to 230°C. After keeping the temperature at 230°C and collecting 530ml of methanol, in order to complete the transesterification reaction, the mixture was reacted for 1 hour under a reduced pressure of 00mm11 to obtain polyester C.
得られたポリエステルは水酸基価３７の硬化性官能基を
有しており、溶媒としてトリクロルヘンセン、カラム温
度１３５°ＣてＧＰＣ測定した結果、数平均分子量（ポ
リスチレン換算）は４０００てあった。The obtained polyester had a curable functional group with a hydroxyl value of 37, and as a result of GPC measurement using trichlorohensen as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 4,000.
また、このポリエステルは毎分１０°Ｃ昇温条件下での
示差走査熱量計（ＤＳＣ）測定で約１５２℃にメイン吸
熱ピークを示し、毎分１０°Ｃの冷却下で約＋１０°Ｃ
において同しくメイン発熱ピークか認められた。Additionally, this polyester exhibits a main endothermic peak at approximately 152°C when measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and approximately +10°C under cooling at 10°C per minute.
The main exothermic peak was also observed.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下で
の観察により、光学異方性に基づくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
罰」漣先
４．４′−ジフェニルカルホン酸ジメチルエルテル７モ
ル、１．６−ヘキサンジオール６モル、１〜リ工チレン
グリコール２モル、ジブチルススオキサイ１〜１．５ｇ
を仕込み、乾燥窒素上加熱を開始し、原料を融解さぜな
。次いて１３０°Ｃ〜２３０°Ｃの温度でエステル交換
反応させてメタノールを留出させた。"Punishment" Ren tip 4. 7 moles of dimethyl ester 4'-diphenylcarphonate, 6 moles of 1.6-hexanediol, 2 moles of 1~re-engineered ethylene glycol, 1~1.5 g of dibutylsulfur oxide
Start heating over dry nitrogen to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130°C to 230°C to distill methanol.
２３０°Ｃて保温しメタノール５３０ｍ１ を捕集した
後、エステル交換反応を完結させるため、ｌ０ｍｍ１１
ｇの減圧下で１時間反応させてポリエステルＤを得た。After incubating at 230°C and collecting 530ml of methanol, 10mm11 of methanol was collected to complete the transesterification reaction.
Polyester D was obtained by reacting for 1 hour under reduced pressure.
得られたポリエステルは水酸基価４０の硬化性官能基を
有しており、溶媒としてトリクロルヘンセン、カラム温
度１３５°ＣてＧＰＣ測定した結果、数平均分子量（ポ
リスチレン換算）は４２５０てあっな。The obtained polyester has a curable functional group with a hydroxyl value of 40, and as a result of GPC measurement using trichlorohensen as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 4250.
また、このポリエステルは毎分１０℃昇温条件下での示
差走査熱量計（ＤＳＣ）測定で約１５５℃においてメイ
ン吸熱ピークを示し、毎分１０°Ｃの冷却下で約８０°
Ｃにおいて同しくメイン発熱ピークが認められた。In addition, this polyester shows a main endothermic peak at about 155°C when measured by differential scanning calorimeter (DSC) under heating conditions of 10°C/min, and about 80°C under cooling at 10°C/min.
A main exothermic peak was also observed in C.
さらに、ビー１ヘステーシ付顕微鏡を用いた直交偏光下
での観察により、光学異方性に基づくテクスチャーを確
認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a B-1 Heistoscope.
斧玖雁ｊ
４．４−ジフェニルカルボン酸ジメチルエステル８モル
、テレフタル酸ジメチルエステル２モル、１．９−ノナ
ンジオール１１モル、ジブチルススオキサイＦ２．２ｇ
を仕込み、乾燥窒素上加熱を開始し、原料を融解させた
。次いで１３０℃〜２３０°Ｃの温度でエステル交換反
応させで、メタノールを留出させた。２３０°Ｃで保温
しメタノール７４５ｍ１を捕集した後、エステル交換反
応を完結させるため、ＩＯｍｍＨｇの減圧下で１時間反
応させてポリエステルＥを得た。得られたポリエステル
は水酸基価２６の硬化性官能基を有しており、溶媒とし
てトリクロルヘンセン、カラム温度１３５℃でＧＰＣ測
定した結果、数平均分子量（ポリスチレン換算）は６１
００であった。Ax Kuganj 4.4-diphenylcarboxylic acid dimethyl ester 8 mol, terephthalic acid dimethyl ester 2 mol, 1.9-nonanediol 11 mol, dibutylsuoxai F 2.2 g
was charged and heating over dry nitrogen was started to melt the raw materials. Next, a transesterification reaction was carried out at a temperature of 130° C. to 230° C., and methanol was distilled out. After keeping the temperature at 230°C and collecting 745 ml of methanol, polyester E was obtained by reacting for 1 hour under reduced pressure of IO mmHg to complete the transesterification reaction. The obtained polyester has a curable functional group with a hydroxyl value of 26, and as a result of GPC measurement using trichlorohensen as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 61.
It was 00.
また、このポリエステルは毎分１０°Ｃ昇温条件下での
示差走査熱量計（ＤＳＣ）測定で約１２５℃において大
きな吸熱ピークを示し、毎分１θ°Ｃ冷却下て約８３°
Ｃにおいて同しく大きな発熱ピークが認められた。In addition, this polyester showed a large endothermic peak at about 125°C when measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and about 83° when cooled by 1θ°C per minute.
A similarly large exothermic peak was observed in C.
さらに、ピー１−ステージ付顕微鏡を用いた直交偏光下
での観察により、光学異方性に基つくテクスチャーを確
認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a P1-stage microscope.
合減」［［
４，４″−ジフェニルカルボン酸ジメチルエステル６モ
ル、テレフタル酸ジメチルエステル４モル、１．９−ノ
ナンジオール１１モル、ジブチルススオキサイＦ２．Ｏ
ｇを仕込み、乾燥窒素上加熱を開始し、原料を融解させ
た。次いて１３０°Ｃ〜２３０°Ｃの温度てエステル交
換反応させで、メタノールを留出させた。２３０°Ｃで
保温しメタノール７６０ｍ１を捕集した後、エステル交
換反応を完結させるため、ｌ０ｍｍ１１ｇの減圧下で１
時間反応させてポリエステルＦを得た。 得られたポリ
エステルは水酸基価２７の硬化性官能基を有しており、
溶媒として１へリクロルベンゼン、カラム温度１３５°
Ｃ″′Ｃ″ＧＰＣ測定した結果、数平均分子量（ポリス
チレン換算）は５９００てあった。6 moles of 4,4''-diphenylcarboxylic acid dimethyl ester, 4 moles of terephthalic acid dimethyl ester, 11 moles of 1,9-nonanediol, dibutylsulfoxai F2.O
g was charged and heating over dry nitrogen was started to melt the raw materials. Next, methanol was distilled off by transesterification at a temperature of 130°C to 230°C. After collecting 760 ml of methanol while keeping the temperature at 230°C, 10 mm of 11 g of methanol was collected under reduced pressure to complete the transesterification reaction.
Polyester F was obtained by reacting for a period of time. The obtained polyester has a curable functional group with a hydroxyl value of 27,
1 helychlorobenzene as solvent, column temperature 135°
As a result of C'''C'' GPC measurement, the number average molecular weight (in terms of polystyrene) was 5900.
また、このポリエステルは毎分１０°Ｃ昇温条件下での
示差走査熱量計（ＤＳＣ＞測定で約９５°Ｃにおいてブ
ロードな吸熱ピークを示し、毎分１０°Ｃ冷却下て約８
３°Ｃにおいて同しくフロートな発熱ピークか認められ
た。In addition, this polyester shows a broad endothermic peak at approximately 95°C in differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and approximately 8°C under cooling at 10°C per minute.
A similar floating exothermic peak was observed at 3°C.
さらに、ビーｌ−ステージ付顕微鏡を用いた直交偏光下
での観察により、光学異方性に基つくテクスチャーを確
認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope with a Bee L-stage.
免魂隨り
反応溶媒としてトルエン１０００ｇ 、ピリジン１００
ｇを仕込んな反応容器に、２，６−ナツタレンジカルホ
ン酸りロライ１〜０．５モル、ジエチレンクリコール０
．５５モルを続いて仕込み、乾燥窒素上加熱を開始し１
００℃の温度で反応させた。ＩＲにより１７８０ｃｍの
カルホン酸クロライ１へに基つく吸収ピークか消失する
まで反応させた後、２０００ｍ１のメタノール中に滴下
／析出させ、濾過 乾燥してポリエステルＧを得た。1000g of toluene and 100g of pyridine as reaction solvents
In a reaction vessel containing g, 1 to 0.5 mol of 2,6-natuta dicarphonic acid, 0 mol of diethylene glycol,
．． 55 mol was subsequently charged and heating over dry nitrogen was started.
The reaction was carried out at a temperature of 00°C. After reacting until the absorption peak based on carbonic acid chloride 1 at 1780 cm disappeared by IR, it was dropped/precipitated in 2000 ml of methanol, filtered and dried to obtain polyester G.
得られたポリエステルは水酸基価３０の硬化性官能基を
有しており、溶媒としてトリクロルヘンセン、カラム温
度１３５°ＣてＧ Ｐ’ Ｃ測定した結果、数平均分子
量（ポリスチレン換算）は４９００であった。The obtained polyester has a curable functional group with a hydroxyl value of 30, and as a result of G P'C measurement using trichlorohensen as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 4900. Ta.
また、このポリエステルは毎分１０°Ｃ昇温条件下ての
示差走査熱量計（ＤＳＣ）測定て約１２５°Ｃにおいて
大きな鋭い吸熱ピークを示し、毎分１０°Ｃ冷却下で約
４８°Ｃにおいて同しく発熱ピークか認められた。Additionally, this polyester exhibits a large sharp endothermic peak at approximately 125°C as measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and at approximately 48°C under cooling of 10°C per minute. An exothermic peak was also observed.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下て
の観察により、光学異方性に基つくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
做【蝕影
反応溶媒として１〜ル工ン］０００ｇ 、ピリジン１０
０ｇを仕込んだ反応容器に、４−１４’−（カルボニル
クロライド）ヘンソイルオキシ］安息香酸クロライ１〜
０．５モル、１，９−ノナンジオール０．５５モルを続
いて仕込み、乾燥窒素上加熱を開始し １００°Ｃの温
度て反応させた。ＩＲにより１７８０ｃｍのカルボン酸
クロライドに基づく吸収ピークか消失するまて反応させ
た後、２０００ｍ１のメタノール中に滴下／析出させ、
濾過・乾燥してポリエステルＨを得た。做 [1~1 as a reaction solvent] 000g, pyridine 10
4-14'-(carbonyl chloride)hensoyloxy]benzoic acid chloride 1~
Subsequently, 0.5 mol of 1,9-nonanediol were charged, heating over dry nitrogen was started, and the reaction was carried out at a temperature of 100°C. After reacting until the absorption peak based on carboxylic acid chloride at 1780 cm disappeared by IR, it was dropped/precipitated into 2000 ml of methanol,
Polyester H was obtained by filtration and drying.
得られたポリエステルは水酸基価２７の硬化性官能基を
有しており、溶媒としてトリクロルヘンセン、カラム温
度１３５°ＣでＧＰＣ測定した結果、数平均分子量（ポ
リスチレン換算〉は５３００てあった。The obtained polyester had a curable functional group with a hydroxyl value of 27, and as a result of GPC measurement using trichlorohensen as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 5300.
また、このポリエステルは毎分１０°Ｃ昇温条件下ての
示差走査熱量計（ＤＳＣ）測定で約８９°Ｃにおいて大
きな鋭い吸熱ピークを示し、毎分１０°Ｃ冷却下て約３
４℃において同しく発熱ピーフカＩ２ぬられた。In addition, this polyester showed a large sharp endothermic peak at about 89°C in differential scanning calorimetry (DSC) measurement under heating conditions of 10°C per minute, and about 3
At 4° C., the same exothermic Pefuca I2 was applied.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下て
の観察により、光学異方性に基つくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
免透既Ｌ
１．１０−デカンジカルボン酸ジメチルエステル７モル
、４−ヒ１〜ロキシ安息香酸１モル、４，４−ヒフエノ
ール７５モル、トリメチロールプロパン０５モル、シフ
チルススオキサイＦ１．５ｇを仕込み、乾燥窒素上加熱
を開始し、原料を融解させた。次いて１３０°Ｃ〜２５
０°Ｃの温度でエステル交換反応させてメタノールを留
出さぜな。２５０°Ｃて保温しメタン−ル５００＋＋＋
１を捕集した後、エステル交換反応を完結さぜるなめ、
ｌ０ｍｍ１１ｇの減圧下で１時間反応させた。２００°
Ｃまて冷却した時点からＮ−メヂルピロリトン１０θＯ
ｇを徐々に加えなから冷却した。その後、メタノール５
０００ｍｌを入れた混合槽に攪拌しながら滴下した。こ
の混合槽内で析出した樹脂を濾過・乾燥してポリエステ
ル■を得た。Cleared L 1.7 moles of 10-decanedicarboxylic acid dimethyl ester, 1 mole of 4-hyaloxybenzoic acid, 75 moles of 4,4-hyphenol, 05 moles of trimethylolpropane, 1.5 g of sifthylstinoxai F. Charge and heat over dry nitrogen was started to melt the raw materials. Then 130°C ~ 25
Perform the transesterification reaction at a temperature of 0°C to distill methanol. Insulated at 250°C and methane 500++
After collecting 1, to complete the transesterification reaction,
The reaction was carried out for 1 hour under reduced pressure of 10 mm and 11 g. 200°
After cooling, N-medylpyrrolitone 10θO
g was gradually added and the mixture was cooled. Then methanol 5
000ml was added dropwise to a mixing tank with stirring. The resin precipitated in this mixing tank was filtered and dried to obtain polyester (2).
得られたポリエステルは水酸基価５２の硬化性官能基を
有し、溶媒としてトリクロルベンゼン、カラム温度＋３
５°ＣでＧＰＣ測定した結果、数平均分子量（ポリスチ
レン換算）は４６８０てあった。また、このポリエステ
ルは毎分１０℃昇温条件下での示差走査熱量計（ＤＳＣ
）測定て約１５５°Ｃにおいて大きな鋭い吸熱ピークを
示し、毎分１０℃冷却下で約１２３°Ｃにおいて同しく
大きな鋭い発熱ピークか認められた。The obtained polyester has a curable functional group with a hydroxyl value of 52, trichlorobenzene as a solvent, column temperature +3
As a result of GPC measurement at 5°C, the number average molecular weight (in terms of polystyrene) was 4680. In addition, this polyester was measured using a differential scanning calorimeter (DSC) under a temperature increase of 10°C per minute.
) It was measured to show a large sharp endothermic peak at about 155°C, and an equally large sharp exothermic peak was observed at about 123°C under cooling at 10°C per minute.
さらに、ビー１−ステージ付顕微鏡を用いた直交偏光下
ての観察により、光学異方性に基つくテクスチャーを確
認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope with a B1 stage.
倉滅千１刈
２．６−ナツタレンジカルホン酸１０モル、１，９−ノ
ナンジオール１１モル、シフデルススオキサイド２０ｇ
を仕込み、乾燥窒素上加熱を開始し、原料を融解させた
。次いで１３０℃〜２３０℃の温度でエステル化反応さ
せて水を留出させた。２３０°Ｃで保温し水３５０ｍ１
を捕集した後、エステル化反応を完結させるため、］０
０ｍｍ１の減圧下で１時間反応させてポリエステルＪを
得な。Kurametsu Sen1kari 2.6-natsutale dicarphonic acid 10 moles, 1,9-nonanediol 11 moles, Schifdelsus oxide 20 g
was charged and heating over dry nitrogen was started to melt the raw materials. Next, an esterification reaction was carried out at a temperature of 130°C to 230°C to distill off water. 350ml of water kept warm at 230°C
After collecting ]0 to complete the esterification reaction.
Polyester J was obtained by reacting for 1 hour under reduced pressure of 0 mm1.
得られたポリエステルは水酸基価３０の硬化性官能基を
有しており、溶媒として１〜リクロルベンゼン、カラム
温度１３５°Ｃ″ＣＧＰＣ測定した結果、数平均分子量
（ポリスチレン換算）は７６８０てあった。The obtained polyester had a curable functional group with a hydroxyl value of 30, and as a result of CGPC measurement using 1-lychlorobenzene as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 7680. .
また、このポリエステルは毎分ｌＯ°Ｃ昇温条件下での
示差走査熱量計（ＤＳＣ）測定て約１２５℃において大
きな鋭い吸熱ピークを示し、毎分１０°Ｃ冷却下て約４
９°Ｃにおいて同しく大きな鋭い発熱ピークが認められ
た。In addition, this polyester exhibits a large sharp endothermic peak at about 125°C when measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and about 4°C under cooling at 10°C per minute.
A similarly large sharp exothermic peak was observed at 9°C.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下で
の観察により、光学異方性に基つくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
鉦」昨Ｕ
２．６−ナフタレンジカルボン酸８モル、１，９−ノナ
ンジオール８４４モル、１−リメチロールプロパン０４
６モル、ジブチルススオキサイド１．５ｇを仕込み、乾
燥窒素上加熱を開始し、原料を融解させた。次いで１３
０°Ｃ〜２３０℃の温度でエステル化反応させて水を留
出させた。２３０°Ｃで保温し、水２８０ｍ１を捕集し
た後、エステル化反応を完結さぜるため、ｌＯ＋ｎｍＨ
ｇの減圧下て１時間反応させてポリエステルＫを得た。2.6-naphthalenedicarboxylic acid 8 mol, 1,9-nonanediol 844 mol, 1-limethylolpropane 04
6 mol and 1.5 g of dibutylsulfur oxide were charged, and heating over dry nitrogen was started to melt the raw materials. then 13
Esterification reaction was carried out at a temperature of 0°C to 230°C to distill water. After keeping the temperature at 230°C and collecting 280ml of water, 1O+nmH was added to complete the esterification reaction.
Polyester K was obtained by reacting for 1 hour under a reduced pressure of 100 g.
得られたポリエステルは水酸基価４２の硬化性官能基を
有し、溶媒として１〜リクロルベンセン、カラム温度１
３５°ＣてＧＰＣ測定した結果、数平均分子量（ポリス
チレン換算）は５６８０であった。The obtained polyester has a curable functional group with a hydroxyl value of 42, and the solvent is 1 to lychlorbenzene and the column temperature is 1.
As a result of GPC measurement at 35°C, the number average molecular weight (in terms of polystyrene) was 5,680.
また、このポリエステルは毎分１０°Ｃ昇温条件下ての
示差走査熱量計（ＤＳＣ）測定て約１２４°Ｃにおいて
大きな鋭い吸熱ピークを示し、毎分１０℃冷却下で約４
３℃において同しく大きな鋭い発熱ピークが認められた
。Additionally, this polyester exhibits a large sharp endothermic peak at about 124°C when measured using a differential scanning calorimeter (DSC) under heating conditions of 10°C per minute, and about 4°C under cooling at 10°C per minute.
A similarly large sharp exothermic peak was observed at 3°C.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下で
の観察により、光学異方性に基づくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
１殊叶Ｕ
４．４′−ジフェニルカルボン酸ジメチルエステル８モ
ル、１，９−ノナンジオール８４４モル、トリメチロー
ルプロパン０．４６モル、シブチルスズオキザイＦ］、
５ｇを仕込み、乾燥壁素下加熱を開始し、原料を融解さ
せた。次いで川３０℃〜２３０°Ｃの温度でエステル交
換反応させで、メタノールを留出させた。２３０°Ｃで
保温しメタノール６００ｍ１を捕集した後、エステル交
換反応を完結させるためＩＯｍｍＨｇの減圧下で１時間
反応させで、ポリエステルＬを得た。1 special leaf U 4.4'-diphenylcarboxylic acid dimethyl ester 8 mol, 1,9-nonanediol 844 mol, trimethylolpropane 0.46 mol, sibutyltin oxide F],
After charging 5 g, heating under the dry wall was started to melt the raw materials. Next, a transesterification reaction was carried out at a temperature of 30°C to 230°C, and methanol was distilled out. After keeping the temperature at 230° C. and collecting 600 ml of methanol, the mixture was reacted for 1 hour under a reduced pressure of IO mmHg to complete the transesterification reaction, to obtain polyester L.
得られたポリエステルは水酸基価４５の硬化性官能基を
有しており、溶媒としてトリクロルヘンセン、カラム温
度１３５°ＣｒＧＰＣ測定した結果、数平均分子量（ポ
リスチレン換算）は４５００てあった。The obtained polyester had a curable functional group with a hydroxyl value of 45, and as a result of CrGPC measurement using trichlorohensen as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 4,500.
また、このポリエステルは毎分１０℃昇温条件下の示差
走査熱量計（ＤＳＣ）測定て約１３８°Ｃにおいて大き
な鋭い吸熱ピークを示し、毎分１０°Ｃ冷却下て約１１
０°Ｃにおいて同しく大きな鋭い発熱ピークか認められ
た。Furthermore, this polyester exhibits a large sharp endothermic peak at approximately 138°C when measured using a differential scanning calorimeter (DSC) under heating conditions of 10°C per minute, and approximately 11°C under cooling at 10°C per minute.
An equally large sharp exothermic peak was observed at 0°C.
さらに、ヒートステージ付顕微鏡を用いた直交偏光下で
の観察により、光学異方性に基づくテクスチャーを確認
した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.
倉滅□但」ｙ
４．４′−シフェニルカルホ゛ン酸ジメチルエステル７
モル、１，９−ノナンジオール８４４モル、トリメチロ
ールプロパン０．４６モル、ｔｒａｎｓ−１，４−シク
ロヘキサンジカルボン酸ジメチルエステル１モル、ジブ
チルススオキサイド１．５ｇを仕込み、乾燥窒素上加熱
を開始し、原料を融解させた。次いて１３０°Ｃ〜２３
０°Ｃの温度てエステル交換反応させてメタノールを留
出さぜた。２３０°Ｃで保温し、メタノール６１０ｍ１
を捕集した後、エステル交換反応を完結さぜるなめＩＯ
ｍｍＨｇの減圧下で１時間反応させてポリエステルＭを
得た。4.4'-Cyphenylcarboxylic acid dimethyl ester 7
844 mol of 1,9-nonanediol, 0.46 mol of trimethylolpropane, 1 mol of trans-1,4-cyclohexanedicarboxylic acid dimethyl ester, and 1.5 g of dibutylsulfoxide were charged, and heating over dry nitrogen was started. The raw materials were melted. Then 130°C ~ 23
A transesterification reaction was carried out at a temperature of 0°C, and methanol was distilled off. Insulated at 230°C, methanol 610ml
After collecting the IO, the transesterification reaction is completed.
Polyester M was obtained by reacting for 1 hour under reduced pressure of mmHg.
得られたポリエステルは水酸基価４５の硬化性官能基を
有しており、溶媒として１−リクロルヘンゼン、カラム
温度１３５°ＣてＧＰＣ測定した結果、数平均分子量（
ポリスヂレフ換算）は４５００てあった。The obtained polyester has a curable functional group with a hydroxyl value of 45, and the number average molecular weight (
It was 4,500 (polizilev equivalent).
また、このポリエステルは毎分１０℃昇温条件下の示差
走査熱量計（ＤＳＣ＞測定で約１１３℃において吸熱ピ
ークを示し、毎分１０°Ｃ冷却下て約６８°Ｃにおいて
同しく発熱ピークが認められた。Additionally, this polyester exhibits an endothermic peak at approximately 113°C as measured by differential scanning calorimetry (DSC) under heating conditions of 10°C per minute, and an exothermic peak at approximately 68°C under cooling of 10°C per minute. Admitted.
さらに、ヒーＩ・ステージ付顕微鏡を用いた直交偏光下
での観察により、光学異方性に基づくテクスチャーを確
認した。Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope with a He I stage.
そし成ゴ列］ＬＬ〉１１７
表−１の配合に基つき反応容器に仕込み、反応融媒とし
てシフチルススオキサイ１〜０１部を加えで、２４０〜
２５０°Ｃてエステル化反応を行った。理論量の水を系
外へ除いた後、減圧度を１６〜２０ｍｍＨｇの範囲てコ
ントロールし約５時間反応させポリエルテル樹脂Ｖ〜Ｙ
を得た。得られた樹脂の特性値は表−２に示す。LL〉117 Based on the formulation shown in Table 1, it was charged into a reaction vessel, and 1 to 01 parts of sifthylstinoxane was added as a reaction melting medium to form a mixture of 240 to
The esterification reaction was carried out at 250°C. After removing the theoretical amount of water from the system, the degree of reduced pressure was controlled within the range of 16 to 20 mmHg and the reaction was carried out for about 5 hours to form polyester resins V to Y.
I got it. The characteristic values of the obtained resin are shown in Table-2.
針戒Ｉ上尺
表−１の配合に基づき反応容器に仕込み、反応融媒とし
てシブチルスズオキサイト０．１部を加えで、２２０〜
２３０°Ｃでエステル交換反応を行い理論量のメタノー
ルを系外へ除いた後、２４０〜２５０℃で減圧度を１６
〜２０ｍｍＨｇの範囲てコン１へロールし約５時間反応
させポリエルテル樹脂Ｚを得た。得られた樹脂の特性値
は表−２に示す。Charge the mixture into a reaction vessel based on the formulation in the Shinkai I Upper Scale Table-1, add 0.1 part of sibutyltin oxide as a reaction melting medium, and make 220~
After carrying out the transesterification reaction at 230°C and removing the theoretical amount of methanol from the system, the degree of vacuum was reduced to 16°C at 240-250°C.
The mixture was rolled into Con 1 at a temperature of ~20 mmHg and reacted for about 5 hours to obtain Polyerther Resin Z. The characteristic values of the obtained resin are shown in Table-2.
（以下余白）
実ＪＪＬＬご」ｌ
前記合成例で得られた樹脂Ａ〜Ｍを表−３に示す割合で
配合し予備混合した後、フス社製ＰＲ−４６型コニーダ
ーを用いて表−３に示した温度で溶融混練した。続いで
、これを冷却同化させてから粉砕し、１５０メツシユの
金網で分離して１５０メツシユ以下の粒径を有する粉体
塗料を得た。この粉体塗料を静電吹き付は塗装にて軟鋼
板に塗布し、２３０℃で５分間焼き付け、塗膜を得た。(Left space below) Resins A to M obtained in the above synthesis examples were blended and premixed in the proportions shown in Table 3, and then mixed as shown in Table 3 using a PR-46 co-kneader made by Fuss Co. Melt kneading was carried out at the indicated temperature. Subsequently, this was cooled and assimilated, pulverized, and separated using a wire mesh of 150 mesh to obtain a powder coating having a particle size of 150 mesh or less. This powder coating was applied to a mild steel plate by electrostatic spraying and baked at 230° C. for 5 minutes to obtain a coating film.
この粉体塗料の貯蔵安定性及び塗膜の性能を試験した結
果を表−４に示す。Table 4 shows the results of testing the storage stability and film performance of this powder coating.
比４岨例」−）」し
前記合成例で得られた樹脂＼ｒ−′−２を表−３に示す
割合で配合し、実施例と同様にして粉体塗料つづいて焼
き付は塗膜を得た。この粉体塗料の貯蔵安定性及び塗膜
の性能を試験した結果を表−４に示す。The resin \r-'-2 obtained in the synthesis example above was blended in the proportions shown in Table 3, and powder coating was applied in the same manner as in the example. I got it. Table 4 shows the results of testing the storage stability and film performance of this powder coating.
（以下余白）
本発明のポリエステル樹脂は、その構造的性質から低温
結晶性を有するため、粉体塗料として用いた時、従来得
られなかった優れた貯蔵安定性と平滑な塗膜外観を両立
しうるものであり、プレコートメタル用粉体塗料として
特に好適である。(Left below) The polyester resin of the present invention has low-temperature crystallinity due to its structural properties, so when used as a powder coating, it achieves both excellent storage stability and a smooth coating film appearance that were previously unobtainable. It is particularly suitable as a powder coating for pre-coated metal.
特許出願代理人patent application agent
Claims (1)
環がパラ位で相互に結合されてなる基、２コ以上のベン
ゼン環がパラ位でアゾ、アゾキシ、エステルあるいはト
ランスビニレンにより結合されてなる基および２，６−
ナフチレン基からなる群より選ばれるメソゲン基で、５
０モル％未満はｐ−フェニレン基、ｍ−フェニレン基あ
るいはトランス１，４−シクロヘキシレン基であっても
かまわない；Ｂは−（ＣＨ＿２）＿ｎ−または−（ＣＨ
＿２ＣＨ＿２Ｏ−）＿ｍ−ＣＨ＿２ＣＨ＿２−で表され
るスペーサー基；ｎは２〜２０、ｍは１〜１９の整数；
Ｘはエステル結合） のみ、あるいは該単位（ I ）と式 Ｒで表される単位（II） （式中、Ｒは４コまでのＯＨを含みうる２〜６価の脂肪
族、芳香族、脂環族炭化水素残基） とが（ I ）／（II）＝９９．９／０．１〜７０／３０
の重量比で任意順位に組み合わされてなり、各隣接単位
はエステル結合で結合されていて、末端はＨＯあるいは
その反応性誘導体で、樹脂のＯＨ価が２０〜２００であ
る異方性溶融相を形成しうるポリエステル樹脂と、 （ｂ）ブロックイソシアネート化合物あるいはアミノプ
ラスト樹脂 とからなる粉体塗料用樹脂組成物。[Claims] (a) Repeating unit (I) represented by the formula A-X-B (in the formula, 100 to 50 mol% of A is composed of two or more benzene rings bonded to each other at the para position) a group in which two or more benzene rings are bonded at the para position by azo, azoxy, ester or transvinylene, and a 2,6-
A mesogenic group selected from the group consisting of naphthylene groups, 5
Less than 0 mol% may be p-phenylene group, m-phenylene group or trans-1,4-cyclohexylene group; B is -(CH_2)_n- or -(CH
A spacer group represented by _2CH_2O-)_m-CH_2CH_2-; n is an integer of 2 to 20, m is an integer of 1 to 19;
X is an ester bond) alone, or the unit (I) and the unit (II) represented by the formula R (wherein R is a divalent to hexavalent aliphatic, aromatic, or aliphatic cyclic hydrocarbon residue) and (I)/(II) = 99.9/0.1 to 70/30
are combined in an arbitrary order in a weight ratio of A resin composition for powder coating comprising a polyester resin that can be formed and (b) a blocked isocyanate compound or an aminoplast resin.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4841288A JPH01221469A (en) | 1988-02-29 | 1988-02-29 | Powder coating resin composition |
| AU23620/88A AU612707B2 (en) | 1987-10-12 | 1988-10-11 | Thermosetting polyester resin and powder coating resinous composition containing the same |
| DE3853865T DE3853865T2 (en) | 1987-10-12 | 1988-10-12 | Thermosetting polyester resin and powder coating resin composition containing this polyester. |
| EP88309548A EP0312331B1 (en) | 1987-10-12 | 1988-10-12 | Thermosetting polyester resin and powder coating resinous composition containing the same |
| KR1019880013307A KR890006697A (en) | 1987-10-12 | 1988-10-12 | Thermosetting polyester resin and resin composition for powder coating containing this resin |
| US07/560,226 US5306806A (en) | 1987-10-12 | 1990-07-20 | Thermosetting polyester resin and powder coating resinous composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4841288A JPH01221469A (en) | 1988-02-29 | 1988-02-29 | Powder coating resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01221469A true JPH01221469A (en) | 1989-09-04 |
Family
ID=12802591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4841288A Pending JPH01221469A (en) | 1987-10-12 | 1988-02-29 | Powder coating resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01221469A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0450219A (en) * | 1990-06-18 | 1992-02-19 | Sekisui Chem Co Ltd | Polyester composition |
| JP2011233608A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | Heat sink made of thermoplastic resin with high thermal conductivity |
| JP2011231159A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | High thermoconductive thermoplastic resin composition |
| JP2011231158A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | Flame-retardant high-thermoconductive thermoplastic resin composition |
| JPWO2010050202A1 (en) * | 2008-10-30 | 2012-03-29 | 株式会社カネカ | High thermal conductivity thermoplastic resin composition and thermoplastic resin |
| JPWO2011033815A1 (en) * | 2009-09-16 | 2013-02-07 | 株式会社カネカ | Organic thermal conductive additive, resin composition and cured product |
| JP2015196794A (en) * | 2014-04-02 | 2015-11-09 | ポリプラスチックス株式会社 | Thermosetting liquid crystal polyester composition and cured product of the same |
| WO2021200716A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
| WO2021200715A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
-
1988
- 1988-02-29 JP JP4841288A patent/JPH01221469A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0450219A (en) * | 1990-06-18 | 1992-02-19 | Sekisui Chem Co Ltd | Polyester composition |
| JPWO2010050202A1 (en) * | 2008-10-30 | 2012-03-29 | 株式会社カネカ | High thermal conductivity thermoplastic resin composition and thermoplastic resin |
| JP5731199B2 (en) * | 2008-10-30 | 2015-06-10 | 株式会社カネカ | High thermal conductivity thermoplastic resin composition and molded article of thermoplastic resin |
| JP6133012B2 (en) * | 2009-09-16 | 2017-05-24 | 株式会社カネカ | Organic thermal conductive additive, resin composition and cured product |
| JPWO2011033815A1 (en) * | 2009-09-16 | 2013-02-07 | 株式会社カネカ | Organic thermal conductive additive, resin composition and cured product |
| JP2011231158A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | Flame-retardant high-thermoconductive thermoplastic resin composition |
| JP2011231159A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | High thermoconductive thermoplastic resin composition |
| JP2011233608A (en) * | 2010-04-26 | 2011-11-17 | Kaneka Corp | Heat sink made of thermoplastic resin with high thermal conductivity |
| JP2015196794A (en) * | 2014-04-02 | 2015-11-09 | ポリプラスチックス株式会社 | Thermosetting liquid crystal polyester composition and cured product of the same |
| WO2021200715A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
| WO2021200716A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
| JP7001208B1 (en) * | 2020-03-30 | 2022-01-19 | 東洋紡株式会社 | Polyester, film and adhesive compositions, as well as adhesive sheets, laminates and printed wiring boards |
| JP7024923B1 (en) * | 2020-03-30 | 2022-02-24 | 東洋紡株式会社 | Polyester, film and adhesive compositions, as well as adhesive sheets, laminates and printed wiring boards |
| JP2022050434A (en) * | 2020-03-30 | 2022-03-30 | 東洋紡株式会社 | Polyester, film and adhesive composition and adhesive sheet, laminate and printed wiring board |
| JP2022068240A (en) * | 2020-03-30 | 2022-05-09 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
| CN115298244A (en) * | 2020-03-30 | 2022-11-04 | 东洋纺株式会社 | Polyester, film, adhesive composition, adhesive sheet, laminate, and printed wiring board |
| CN115298245A (en) * | 2020-03-30 | 2022-11-04 | 东洋纺株式会社 | Polyester, film, adhesive composition, adhesive sheet, laminate, and printed wiring board |
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