JPS624424B2 - - Google Patents
Info
- Publication number
- JPS624424B2 JPS624424B2 JP4844281A JP4844281A JPS624424B2 JP S624424 B2 JPS624424 B2 JP S624424B2 JP 4844281 A JP4844281 A JP 4844281A JP 4844281 A JP4844281 A JP 4844281A JP S624424 B2 JPS624424 B2 JP S624424B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- weight
- resin composition
- parts
- curing
- 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
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 229920006305 unsaturated polyester Polymers 0.000 claims description 21
- 238000001723 curing Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000013035 low temperature curing Methods 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- -1 amine compound Chemical class 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- XQFJDFIHJKPUEL-UHFFFAOYSA-N 2-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=CC=C1N(C)C XQFJDFIHJKPUEL-UHFFFAOYSA-N 0.000 description 1
- ZTKDMNHEQMILPE-UHFFFAOYSA-N 4-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=C(N(C)C)C=C1 ZTKDMNHEQMILPE-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本願発明は低温硬化特性の経日変化の少ない速
硬化性不飽和ポリエステル樹脂組成物に関するも
のである。更に詳しくは、貯蔵安定性に優れ、低
温硬化特性の経日変化の少ない、アミン化合物を
含有する速硬化性不飽和ポリエステル樹脂組成物
に関するものである。
一般にジメチルアニリン等の芳香族第三級アミ
ンを含有した不飽和ポリエステル樹脂組成物は、
ベンゾイルパーオキサイドの如きジアシルパーオ
キサイドを硬化剤として使用することにより低温
に於ても極めて速やかに硬化する為、低温速硬化
性不飽和ポリエステル樹脂組成物として広く利用
されている。ところが、このようなアミン化合物
含有不飽和ポリエステル樹脂組成物はその貯蔵安
定性が悪く、そのため使用条件に制限を受けてい
るのが現状である。
本願発明者らはかゝる点の改良を種々検討した
結果、低温に於て速硬化性であり、しかも硬化特
性の経日変化が実質的になく、且つ貯蔵安定性の
良好なる不飽和ポリエステル樹脂組成物を開発す
るに至つたものである。
即ち本願発明は、不飽和ポリエステルＡ、重合
性単量体Ｂ、アミン化合物Ｃ、スズ化合物Ｄおよ
び重合禁止剤Ｅからなり、不飽和ポリエステルＡ
の酸価が６以下であり、アミン化合物Ｃが下記一
般式（）で示される化合物からなる群より選ば
れる少なくとも１種であり、不飽和ポリエステル
Ａと重合性単量体Ｂの合計を100重量部としてア
ミン化合物Ｃが0.01〜2.0重量部、スズ化合物Ｄ
が0.05〜3.0重量部および重合禁止剤Ｅが0.005〜
0.5重量部の比率であることを特徴とする低温硬
化特性の経日変化の少ない速硬化性不飽和ポリエ
ステル樹脂組成物に関するものである。
一般式（）
（但し、式中R1は−Ｈ、−CH3又は−OCH3を
表わし、R2およびR3はいずれもＣ1〜4のアルキル
基を表わし、R2とR3とは同一でも異なつていて
もよい。）
本発明に用いられる不飽和ポリエステルＡは、
α，β−不飽和二塩基酸を必須とし必要により芳
香族飽和二塩基酸や脂肪族飽和二塩基酸を併用す
る酸成分と、グリコールやエポキシ化合物等のア
ルコール成分とから得られるものである。勿論、
二塩基塩の一部に代えて一塩基酸や３価以上の多
塩基酸を用いてもよく、またグリコールやエポキ
シ化合物の一部に代えて１価や３価以上のアルコ
ールを用いてもよい。不飽和ポリエステルＡの酸
価は６以下でなければならない。酸価が６を超え
ると低温硬化特性の経日変化が大きくなる。不飽
和ポリエステルＡの酸価を６以下とするために
は、原料である酸成分とアルコール成分との比率
を選ぶことによつて達成される。
重合性単量体Ｂとしては、スチレン、ビニルト
ルエン、α−メチルスチレン、ジアリルフタレー
ト、メチルメタクリレート等の、不飽和ポリエス
テル樹脂に通常用いられるものを用いることがで
きる。
不飽和ポリエステルＡと重合性単量体Ｂとは、
不飽和ポリエステル樹脂を構成するものである
が、この両者の比率は重量比で10：90〜90：10の
範囲とすることができる。
アミン化合物Ｃは、前記一般式（）で示され
る化合物からなる群より選ばれる少なくとも１種
である。一般式（）で示される化合物として
は、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチ
ルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジ
ン、Ｎ，Ｎ−ジメチル−ｍ−トルイジン、Ｎ，Ｎ
−ジエチル−ｐ−トルイジン、Ｎ，Ｎ−ジメチル
−ｐ−アニシジン、Ｎ，Ｎ−ジメチル−ｏ−アニ
シジン等を挙げることができる。
アミン化合物Ｃの使用量は、不飽和ポリエステ
ルＡと重合性単量体Ｂの合計を100重量部として
0.01〜2.0重量部の比率の範囲である。0.01重量部
より少ないと硬化時に速硬化性にならず、また
2.0重量部を超える多量を用いる場合には保存安
定性が悪くなる。
スズ化合物Ｄとしては、水酸化物、炭酸塩、硫
酸塩、硼酸塩等の無機化合物；ナフテン酸塩、オ
クテン酸塩、芳香族カルボン酸塩等の有機酸塩；
ジブチルチンオキサイド等の有機スズ化合物等を
挙げることができ、これらのなかから１種又は２
種以上を用いることができる。
スズ化合物Ｄの使用量は、不飽和ポリエステル
Ａと重合性単量体Ｂの合計を100重量部として
0.05〜3.0重量部の比率の範囲である。この範囲
をはずれると、得られる不飽和ポリエステル樹脂
組成物の貯蔵安定性が悪くなる。
重合禁止剤Ｅとしては、ハイドロキノン、ｐ−
ベンゾキノン、テトラクロルベンゾキノン、ｔ−
ブチルハイドロキノン等のキノン類；ｐ−ｔ−ブ
チルカテコール等のカテコール類；２，４−ジニ
トロフエノール等のフエノール類等を挙げること
ができ、これらのなかから１種又は２種以上を用
いることができる。
これらの中でも、本発明ではテトラクロルベン
ゾキノンが重合禁止剤Ｅとして特に好ましいもの
である。
重合禁止剤Ｅの使用量は、不飽和ポリエステル
Ａと重合性単量体Ｂの合計を100重量部として
0.005〜0.5重量部の比率の範囲である。0.005重量
部より少ないと保存安定性が悪くなり、0.5重量
部を超える多い量を用いると硬化時に硬化しにく
くなる。
本発明の速硬化性不飽和ポリエステル樹脂組成
物は、このように不飽和ポリエステルＡ、重合性
単量体Ｂ、アミン化合物Ｃ、スズ化合物Ｄおよび
重合禁止剤Ｅの特定比率からなるものであり、こ
れらの各成分が一体不可分に作用し合つて本発明
の優れた作用効果を発揮するものである。これら
の各成分はいかなる順序で混合してもよく、混合
の方法および装置は不飽和ポリエステル樹脂の業
界で通常用いられている方法および装置を用いる
ことができる。またスズ化合物Ｄと重合禁止剤Ｅ
とについては、これらの全量または一部を、酸成
分とアルコール成分とから不飽和ポリエステルＡ
を製造する工程において添加してもよい。
このようにして得られた本発明の不飽和ポリエ
ステル樹脂組成物には、必要に応じて炭酸カルシ
ウム、クレー、タルタ、硅砂、ガラス粉末等の充
填剤；着色剤；無水硅酸微粉末等の揺変剤；銅化
合物や鉄化合物等の安定剤等を添加して使用する
こともできる。
本発明の速硬化性不飽和ポリエステル樹脂組成
物を硬化するには、不飽和ポリエステル樹脂の業
界で通常用いられている有機過酸化物触媒を用い
ることができる。これらのなかでも、ベンゾイル
パーオキサイド等のジアシル系有機過酸化物を用
いると、優れた低温速硬化性を示し、本発明の速
硬化性不飽和ポリエステル樹脂組成物の特徴を発
揮することができる。
また、本発明の速硬化性不飽和ポリエステル樹
脂組成物は、アミン化合物を含有しているにもか
かわらず、優れた貯蔵安定性を示し、またその低
温硬化特性の経日変化も少ないものである。
以下、実施例および比較例により本発明を更に
詳細に説明する。尚、例中の部および％は特にこ
とわりのない限り重量部および重量％を表わすも
のとする。
参考例 １
無水フタル酸0.5モル、無水マレイン酸0.5モ
ル、プロピレングリコール0.5モル及びエチレン
グリコール0.7モルの比率で４つ口フラスコに仕
込み、常法通り窒素気流中200℃で脱水縮合反応
して酸価５の不飽和ポリエステル（）を得た。
参考例 ２
無水フタル酸0.5モル、無水マレイン酸0.5モ
ル、プロピレングリコール0.5モル及びエチレン
グリコール0.7モルの比率で４つ口フラスコに仕
込み、更にジブチルチンオキサイドを原料仕込み
量100部に対して0.1部の比率で使用して、常法通
り窒素気流中200℃で脱水縮合反応して酸価２の
不飽和ポリエステル（）を得た。
参考例 ３
無水フタル酸0.5モル、無水マレイン酸0.5モ
ル、プロピレングリコール0.5モル及びエチレン
グリコール0.6モルの比率で４つ口フラスコに仕
込み、常法通り窒素気流中200℃で脱水縮合反応
して酸価11の不飽和ポリエステル（）を得た。
参考例 ４
参考例１〜３で得た不飽和ポリエステル（）
〜（）を使つて第１表に示す組成の不飽和ポリ
エステル樹脂組成物Ａ〜Ｋをそれぞれ得た。
The present invention relates to a fast-curing unsaturated polyester resin composition whose low-temperature curing properties show little change over time. More specifically, the present invention relates to a fast-curing unsaturated polyester resin composition containing an amine compound that has excellent storage stability and little change over time in its low-temperature curing properties. Generally, unsaturated polyester resin compositions containing aromatic tertiary amines such as dimethylaniline,
By using diacyl peroxide such as benzoyl peroxide as a curing agent, it cures extremely quickly even at low temperatures, so it is widely used as a low-temperature, rapid-curing unsaturated polyester resin composition. However, such amine compound-containing unsaturated polyester resin compositions have poor storage stability, and as a result, the conditions of use are currently limited. The inventors of the present application have conducted various studies to improve these points, and as a result, they have developed an unsaturated polyester that cures quickly at low temperatures, has virtually no change in curing characteristics over time, and has good storage stability. This led to the development of a resin composition. That is, the present invention consists of an unsaturated polyester A, a polymerizable monomer B, an amine compound C, a tin compound D, and a polymerization inhibitor E;
has an acid value of 6 or less, the amine compound C is at least one selected from the group consisting of compounds represented by the following general formula (), and the total of the unsaturated polyester A and the polymerizable monomer B is 100% by weight 0.01 to 2.0 parts by weight of amine compound C, tin compound D
is 0.05 to 3.0 parts by weight and polymerization inhibitor E is 0.005 to 3.0 parts by weight.
The present invention relates to a fast-curing unsaturated polyester resin composition with low temperature curing properties and little change over time, characterized by a ratio of 0.5 parts by weight. General formula () (However, in the formula, R 1 represents -H, -CH 3 or -OCH 3 , R 2 and R 3 both represent a C 1-4 alkyl group, and R 2 and R 3 may be the same or different. ) The unsaturated polyester A used in the present invention is
It is obtained from an acid component which is essentially an α,β-unsaturated dibasic acid and optionally an aromatic saturated dibasic acid or an aliphatic saturated dibasic acid, and an alcohol component such as a glycol or an epoxy compound. Of course,
A monobasic acid or a trivalent or higher polybasic acid may be used in place of a portion of the dibasic salt, and a monovalent or trivalent or higher valence alcohol may be used in place of a portion of the glycol or epoxy compound. . The acid value of unsaturated polyester A must be 6 or less. When the acid value exceeds 6, the change in low temperature curing properties over time becomes large. Setting the acid value of unsaturated polyester A to 6 or less can be achieved by selecting the ratio of the acid component and alcohol component as raw materials. As the polymerizable monomer B, those commonly used for unsaturated polyester resins, such as styrene, vinyltoluene, α-methylstyrene, diallyl phthalate, and methyl methacrylate, can be used. Unsaturated polyester A and polymerizable monomer B are:
This constitutes an unsaturated polyester resin, and the ratio of the two can be in the range of 10:90 to 90:10 by weight. The amine compound C is at least one selected from the group consisting of compounds represented by the general formula (). Compounds represented by the general formula () include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine,
-diethyl-p-toluidine, N,N-dimethyl-p-anisidine, N,N-dimethyl-o-anisidine, and the like. The amount of amine compound C used is based on the total of unsaturated polyester A and polymerizable monomer B being 100 parts by weight.
The ratio ranges from 0.01 to 2.0 parts by weight. If it is less than 0.01 part by weight, it will not cure quickly during curing, and
If a large amount exceeding 2.0 parts by weight is used, storage stability will deteriorate. Examples of the tin compound D include inorganic compounds such as hydroxides, carbonates, sulfates, and borates; organic acid salts such as naphthenates, octenoates, and aromatic carboxylates;
Examples include organic tin compounds such as dibutyltin oxide, and one or two of these can be used.
More than one species can be used. The amount of tin compound D used is based on the total of unsaturated polyester A and polymerizable monomer B being 100 parts by weight.
The ratio ranges from 0.05 to 3.0 parts by weight. If it deviates from this range, the storage stability of the resulting unsaturated polyester resin composition will deteriorate. As the polymerization inhibitor E, hydroquinone, p-
benzoquinone, tetrachlorobenzoquinone, t-
Examples include quinones such as butylhydroquinone; catechols such as pt-butylcatechol; and phenols such as 2,4-dinitrophenol; one or more of these may be used. . Among these, tetrachlorobenzoquinone is particularly preferred as the polymerization inhibitor E in the present invention. The amount of polymerization inhibitor E used is based on the total of unsaturated polyester A and polymerizable monomer B being 100 parts by weight.
The proportion ranges from 0.005 to 0.5 parts by weight. If the amount is less than 0.005 part by weight, storage stability will be poor, and if the amount is more than 0.5 part by weight, it will be difficult to cure during curing. The fast-curing unsaturated polyester resin composition of the present invention is thus composed of a specific ratio of unsaturated polyester A, polymerizable monomer B, amine compound C, tin compound D and polymerization inhibitor E, These components work together inseparably to exert the excellent effects of the present invention. These components may be mixed in any order, and any mixing method and equipment commonly used in the industry of unsaturated polyester resins can be used. Also, tin compound D and polymerization inhibitor E
As for the unsaturated polyester A, all or a part of these can be converted into unsaturated polyester A from the acid component and the alcohol component.
It may be added in the process of manufacturing. The thus obtained unsaturated polyester resin composition of the present invention may optionally contain fillers such as calcium carbonate, clay, tarta, silica sand, glass powder, etc.; coloring agents; Modifiers; stabilizers such as copper compounds and iron compounds can also be added and used. To cure the fast-curing unsaturated polyester resin composition of the present invention, organic peroxide catalysts commonly used in the unsaturated polyester resin industry can be used. Among these, when diacyl organic peroxides such as benzoyl peroxide are used, they exhibit excellent low-temperature fast curing properties and can exhibit the characteristics of the fast-curing unsaturated polyester resin composition of the present invention. Furthermore, the fast-curing unsaturated polyester resin composition of the present invention exhibits excellent storage stability despite containing an amine compound, and its low-temperature curing properties show little change over time. . Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Incidentally, parts and percentages in the examples represent parts by weight and percentages by weight unless otherwise specified. Reference Example 1 A ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.7 mol of ethylene glycol was charged into a four-necked flask, and a dehydration condensation reaction was performed at 200°C in a nitrogen stream as usual to determine the acid value. An unsaturated polyester () of No. 5 was obtained. Reference Example 2 A 4-necked flask was charged with a ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.7 mol of ethylene glycol, and 0.1 part of dibutyltin oxide per 100 parts of the raw material charged. A dehydration condensation reaction was carried out at 200° C. in a nitrogen stream in a conventional manner to obtain an unsaturated polyester (2) having an acid value of 2. Reference Example 3 A ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.6 mol of ethylene glycol was charged into a four-necked flask, and the acid value was determined by dehydration condensation reaction at 200°C in a nitrogen stream as usual. 11 unsaturated polyesters () were obtained. Reference Example 4 Unsaturated polyester obtained in Reference Examples 1 to 3 ()
-() were used to obtain unsaturated polyester resin compositions A to K having the compositions shown in Table 1, respectively.
【表】【table】
【表】
実施例 １
参考例４で得た不飽和ポリエステル樹脂組成物
Ａ〜Ｋを用い、貯蔵安定性、低温硬化特性及び低
温硬化特性の経日変化を調べた。結果を第２表に
示す。
尚、各特性は、以下のようにして調べた。
（貯蔵安定性）
外径12mmφ、高さ120mmの試験管に上部空間の
高さが５mmになるまで各不飽和ポリエステル樹脂
組成物を入れ、アルミ箔でフタをした後、セロハ
ンテープでシールし、60℃恒温槽中に静置し、24
時間毎に試験管を転倒して、泡が上昇しなくなる
までの日数を測定した。
（低温硬化特性）
ポリプロピレン製コツプに各不飽和ポリエステ
ル樹脂組成物30ｇを取り、５℃の冷水浴で冷却し
ながらBPO50％ペーストを不飽和ポリエステル
樹脂組成物に対して６％添加し、30秒間混合した
のち外径18mmφ、高さ180mmの試験管に高さ100mm
まで該触媒混合樹脂組成物を入れ、更にJIS Ｋ
6911記載のサーミスタ温度計を挿入したのち、該
試験管を５℃冷水浴中に浸漬して発熱曲線をと
り、ゲル化時間（以下、GTと記す。）、最小硬化
時間（以下、MCTと記す。）及び最高発熱温度
（以下、METと記す。）を測定した。また反応性
を計算した。尚、GT，MCT及び反応性は以下の
通りである。
GT：触媒を添加し、30秒間混合した直後（以
下、測定開始時という。）から発熱曲線が10℃
になるまでに要した時間を分で表わす。
MCT：測定開始時から最高発熱温度（MET）に
達するまでに要した時間を分で表わす。
反応性：ＭＥＴ（℃）／ＭＣＴ（分）−ＧＴ（分）で
表わす。
（低温硬化特性の経日変化）
室温で保存した各不飽和ポリエステル樹脂組成
物について、樹脂組成物調製直後、10日後、40日
又は50日後にそれぞれ低温硬化特性を調べた。[Table] Example 1 Using the unsaturated polyester resin compositions A to K obtained in Reference Example 4, storage stability, low-temperature curing properties, and changes over time in low-temperature curing properties were investigated. The results are shown in Table 2. In addition, each characteristic was investigated as follows. (Storage stability) Put each unsaturated polyester resin composition into a test tube with an outer diameter of 12 mmφ and a height of 120 mm until the height of the upper space is 5 mm, cover with aluminum foil, and then seal with cellophane tape. Leave it in a constant temperature bath at 60℃ for 24 hours.
The test tube was inverted every hour and the number of days until bubbles stopped rising was measured. (Low temperature curing properties) Take 30g of each unsaturated polyester resin composition in a polypropylene cup, cool it in a 5℃ cold water bath, add 6% of BPO50% paste to the unsaturated polyester resin composition, and mix for 30 seconds. After that, the height is 100mm in a test tube with an outer diameter of 18mmφ and a height of 180mm.
Add the catalyst mixed resin composition until the JIS K
After inserting the thermistor thermometer described in 6911, the test tube was immersed in a 5°C cold water bath and the exothermic curve was taken to determine the gelation time (hereinafter referred to as GT), minimum curing time (hereinafter referred to as MCT). ) and maximum exothermic temperature (hereinafter referred to as MET) were measured. The reactivity was also calculated. In addition, GT, MCT, and reactivity are as follows. GT: Immediately after adding the catalyst and mixing for 30 seconds (hereinafter referred to as the start of measurement), the exothermic curve changes to 10℃.
The time required to reach the goal is expressed in minutes. MCT: The time required from the start of measurement to reach the maximum exothermic temperature (MET) in minutes. Reactivity: Expressed as MET (°C)/MCT (min) - GT (min). (Change in low-temperature curing properties over time) The low-temperature curing properties of each unsaturated polyester resin composition stored at room temperature were examined immediately after preparation of the resin composition, 10 days later, 40 days, or 50 days later.
【表】【table】
【表】
結果を第２表に示した如く、実施例１〜８にお
いてはいずれも貯蔵安定性に優れ且つ低温硬化特
性も良好でしかも低温硬化特性の経日変化も少な
いことがわかる。
一方、比較例１においては貯蔵安定性が悪く、
また比較例２及び３においては反応性が低いこと
が明らかである。[Table] As shown in Table 2, Examples 1 to 8 all had excellent storage stability and good low-temperature curing properties, with little change over time in the low-temperature curing properties. On the other hand, in Comparative Example 1, the storage stability was poor;
Furthermore, it is clear that in Comparative Examples 2 and 3, the reactivity is low.
Claims (1)
ミン化合物Ｃ、スズ化合物Ｄおよび重合禁止剤Ｅ
からなり、不飽和ポリエステルＡの酸価が６以下
であり、アミン化合物Ｃが下記一般式（）で示
される化合物からなる群より選ばれる少なくとも
１種であり、不飽和ポリエステルＡと重合性単量
体Ｂの合計を100重量部としてアミン化合物Ｃが
0.01〜2.0重量部、スズ化合物Ｄが0.05〜3.0重量
部および重合禁止剤Ｅが0.005〜0.5重量部の比率
であることを特徴とする低温硬化特性の経日変化
の少ない速硬化性不飽和ポリエステル樹脂組成
物。 一般式（） （但し、式中R1は−Ｈ、−CH3又は−OCH3を
表わし、R2およびR3はいずれもＣ1〜4のアルキル
基を表わし、R2とR3は同一でも異なつていても
よい。） ２ 重合禁止剤Ｅがテトラクロルベンゾキノンで
ある特許請求の範囲第１項記載の低温硬化特性の
経日変化の少ない速硬化性不飽和ポリエステル樹
脂組成物。[Claims] 1. Unsaturated polyester A, polymerizable monomer B, amine compound C, tin compound D, and polymerization inhibitor E
The unsaturated polyester A has an acid value of 6 or less, the amine compound C is at least one selected from the group consisting of compounds represented by the following general formula (), and the unsaturated polyester A and the polymerizable monomer Amine compound C is
A fast-curing unsaturated polyester with low temperature curing properties and little change over time, characterized by a ratio of 0.01 to 2.0 parts by weight, 0.05 to 3.0 parts by weight of tin compound D, and 0.005 to 0.5 parts by weight of polymerization inhibitor E. Resin composition. General formula () (However, in the formula, R 1 represents -H, -CH 3 or -OCH 3 , R 2 and R 3 both represent a C 1-4 alkyl group, and R 2 and R 3 may be the same or different. 2. The fast-curing unsaturated polyester resin composition of claim 1, wherein the polymerization inhibitor E is tetrachlorobenzoquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4844281A JPS57164113A (en) | 1981-04-02 | 1981-04-02 | Rapid-curing unsaturated polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4844281A JPS57164113A (en) | 1981-04-02 | 1981-04-02 | Rapid-curing unsaturated polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57164113A JPS57164113A (en) | 1982-10-08 |
| JPS624424B2 true JPS624424B2 (en) | 1987-01-30 |
Family
ID=12803461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4844281A Granted JPS57164113A (en) | 1981-04-02 | 1981-04-02 | Rapid-curing unsaturated polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57164113A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63146915A (en) * | 1986-07-18 | 1988-06-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Easily dyeable thermosetting resin composition having excellent yellowing resistance |
| NZ226008A (en) * | 1987-09-21 | 1990-11-27 | Ici Plc | Process for manufacture of polyurethane foams using methylene diphenyl isocyanates and optionally water as blowing agent |
-
1981
- 1981-04-02 JP JP4844281A patent/JPS57164113A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57164113A (en) | 1982-10-08 |
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