JPS6337141B2 - - Google Patents
Info
- Publication number
- JPS6337141B2 JPS6337141B2 JP60272476A JP27247685A JPS6337141B2 JP S6337141 B2 JPS6337141 B2 JP S6337141B2 JP 60272476 A JP60272476 A JP 60272476A JP 27247685 A JP27247685 A JP 27247685A JP S6337141 B2 JPS6337141 B2 JP S6337141B2
- Authority
- JP
- Japan
- Prior art keywords
- inorganic material
- unsaturated polyester
- scale
- weight
- resin
- 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
- 229910010272 inorganic material Inorganic materials 0.000 claims description 23
- 239000011147 inorganic material Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 5
- 229920006305 unsaturated polyester Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- -1 acetal compound Chemical class 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は、耐水性、耐蝕性に優れ、特に塗料お
よびライニングに適する不飽和ポリエステル樹脂
コンパウンドの製造方法に関する。
〔従来の技術〕
従来、塗膜の耐水性、耐蝕性を改良するため
に、不飽和ポリエステル等の硬化性樹脂にガラス
繊維あるいはフレーク状の無機質材料を添加した
ライニング用樹脂組成物については知られてい
る。かかる場合にライニング層の特性は、樹脂と
ガラス繊維あるいはフレーク状の無機質材料との
結合状態によつて左右される。すなわち、結合力
強化がライニング層の特性を改善することは云う
までもない。
樹脂とガラス繊維あるいはフレーク状の無機質
材料との結合力を強化するために、樹脂と無機質
材料を混合する際に単にシランカツプリング剤を
同時に混合する方法（“インテグラル法”と云わ
れる）が知られている。しかし、その効果は常に
安定して発揮させるまでに至つていない。
また、樹脂に添加する鱗片状の無機質材料を、
予めシランカツプリング剤の水またはアルコール
希釈液で濡らして処理する方法についてもよく知
られている。しかし、この場合には乾燥工程にお
いて鱗片状無機質材料が凝集するか、材料内の希
釈液が残留して塗膜またはライニング層の特性に
悪影響を与え、また必要以上の乾燥はシランカツ
プリング剤の。飛散ロスを伴い実用的でない。
〔発明が解決しようとする問題点〕
本発明者らは、前記情勢に鑑み、不飽和ポリエ
ステル樹脂を用いた耐水性、耐蝕性の優れた防蝕
性樹脂塗料およびライニングを得るべく鋭意検討
を重ねた結果、特定方法で処理したフレーク状の
無機質材料を不飽和ポリエステル樹脂に添加混合
して樹脂コンパウンドを製造することによつて、
耐水性および耐蝕性に優れた塗料およびライニン
グが得られることを見出し、本発明に到達した。
〔問題点を解決するための手段〕
即ち、本発明方法は、重合性単量体にシランカ
ツプリング剤を、鱗片状の無機質材料の100重量
部当り0.5〜５重量部に相当する範囲で溶解また
は乳化分散させた130℃以下の溶液に、その径が
３mmφ以下、厚さ１〜10ミクロンの鱗片状の無機
質材料を130℃以下で浸漬して得られる、未だ湿
潤状態にある無機質材料を、不飽和ポリエステル
と重合性単量体よりなる樹脂液に、樹脂液に対し
20〜50重量％の範囲で添加混合することを特徴と
する、不飽和ポリエステル樹脂コンパウンドの製
造方法である。
〔作用〕
本発明方法においては、重合性単量体が完全に
乾燥飛散しない状態即ち湿潤状態にある無機質材
料が樹脂液と混合されるので、樹脂中での無機質
材料の凝集が防止され、また無機質材料中に吸着
残留している0.1％以下の微量の水分がカツプリ
ング反応を促進するものと考えられる。
本発明に用いられるシランカツプリング剤を溶
解または乳化分散させる重合性単量体と不飽和ポ
リエステルを溶解するために用いられる重合性単
量体とは同一物であることが望ましいが、別の重
合性単量体を希釈剤として併用することもでき
る。かかる重合性単量体の例としては、スチレン
が一般的であるが、クロルスチレン、ビニルトル
エン、トリエチレングリコールジメタクリレート
なども有用である。
本発明に用いられるシランカツプリング剤は、
ビニルトリエトキシシラン、ビニルトリス（β−
メトキシエトキシ）シラン、γ−グリシドキシプ
ロピルトリメトキシシラン、γ−メタアクリロキ
シプロピルトリメトキシシラン、Ｎ−β（アミノ
エチル）γ−アミノプロピルトリメトキシシラン
などであり、処理する無機質材料に応じて選択さ
れる。
本発明に用いられる鱗片状の無機質材料は、無
機質材料としてガラスフレーク、雲母、タルタ、
グラフアイト、人工雲母、アルミナなどから選択
され、鱗片状としてその径が３mmφ以下好ましく
は１〜３mmφ、厚さが１〜10μ範囲のものが挙げ
られる。
鱗片状の無機質材料を処理する際の重合性単量
体とシランカツプリング剤の量は、無機質材料の
種類、大きさなどにより異なるが、重合性単量体
は無機質材料を浸漬するに足る量以上あればよ
く、またシランカツプリング剤は無機質材料の
100重量部当り0.5〜５重量部の範囲で有効であ
る。処理温度は130℃以下好適には60〜130℃の範
囲が好ましく、60℃以下では処理に長時間を要
し、また130℃以上では単量体とシランカツプリ
ング剤との反応によるゲル化、シランカツプリン
グ剤の分解などを伴い好ましくない。処理時間は
室温の場合一週間、60〜130℃の場合５〜60分間
程度が必要である。
本発明に用いられる不飽和ポリエステルは重合
性単量体に溶解して用いられるが、この際に先に
カツプリング剤で処理された鱗片状の無機質材料
が添加される。重合性単量体を含む不飽和ポリエ
ステル樹脂に対する無機質材料の重量比は、80：
20〜50：50、好ましくは75：25〜60：40の範囲で
有効である。
不飽和ポリエステル樹脂に用いられる重合触媒
は、有機過酸化物たとえば過酸化ベンゾイル、メ
チルエチルケトンパーオキサイド、キユメンハイ
ドロパーオキサイドなどであり、目的に応じて選
択することができる。
その他の配合剤としては、商品価値を高めるた
めに遥変剤たとえば微粉シリカ、石綿粉末、有機
アミンを配合した粘土質（ベーカ社製“ベント
ン”）、脱水ヒマシ油、ソルビトールとベンズアル
デヒドの縮合アセタール化合物、金属キレートや
金属せつけんなど、また顔料たとえばチタン白、
補強材としてガラス繊維、合成繊維、硬化促進剤
たとえば金属せつけんん、ジメチルアニリン、ア
セチルアセトンなど空気乾燥剤としてパラフイ
ン、エチルセルロースなどを少量添加することが
できる。
〔実施例〕
次に本発明の理解を助けるために以下に実施例
を示す。
実施例 １
還流装置付のフラスコに、γ−メタクリロキシ
プロピルトリメトキシシランの１重量％スチレン
溶液700ｇ、ガラスフレーク（径１〜３mmφ、平
均厚さ3μ）300ｇを投入し、100℃で20分間熱処
理したる後、吸引ロートにて過剰のスチレンを除
去し未だ表面が湿潤状態にある該ガラスフレーク
を不飽和ポリエステル樹脂（昭和高分子(株)製“リ
ゴラツクLP−１”）700ｇに混合し、150mmHgの
減圧マーラーを用いて混練し、ガラスフレーク含
有率30重量％になるようにモノマー量を調節して
樹脂コンパウンド(A)を得た。該コンパウンド(A)を
用いた硬化物の吸水率特性を第１表に後記する。
実施例 ２
ビニルトリス（β−メトキシエトキシ）シラン
の0.6重量％スチレン溶液1500ｇにガラスフレー
ク（平均粒径１mmφ、厚さ3μ）300ｇを撹拌しな
がら投入し、室温で１週間放置した後、吸引ロー
トと紙を用いて過剰のスチレンを除去し、未だ
表面がスチレンで湿潤状態にあるガラスフレーク
を110℃のオーブン中で10分間熱処理したる後、
不飽和ポリエステル樹脂（昭和高分子(株)製“リゴ
ラツク2141”）700ｇに混合し、減圧ニーダーを用
いて150mmHg下で混練し、ガラスフレーク含有率
30重量％の樹脂コンパウンド(B)を得た。該コンパ
ウンド(B)を用いた硬化物の吸収率特性を第１表に
後記する。
比較例 １
不飽和ポリエステル樹脂（昭和高分子(株)製“リ
ゴラツクLP−１”）700ｇにγ−メタクリロキシ
プロピルトリメトキシシランの１重量％を加え、
しかる後ガラスフレーク300ｇを加えて、150mm
Hgの減圧マーラを用いて10分間混練し、ガラス
フレーク含有率30重量％の樹脂コンパウンド
（A′）を得た。該コンパウンド（A′）を用いた硬
化物の吸水率特性を第１表に後記する。
比較例 ２
不飽和ポリエステル樹脂（昭和高分子(株)製“リ
ゴラツク2141”）700ｇにビニルトリス（β−メト
キシエトキシ）シランの0.6重量％を加え、さら
にガラスフレーク300ｇを添加し、150mmHgの減
圧ニーダーを用いて10分間混練し、ガラスフレー
ク含有率30重量％の樹脂コンパウンド（B′）を
得た。該コンパウンド（B′）を用いた硬化物の
吸水率特性を第１表に後記する。
以上の実施例１〜２、比較例１〜２の樹脂コン
パウンド、各100重量部に、それぞれ重量部でメ
チルエチルケトンパーオキサイド（55％フタル酸
ジメチル溶液として）1.0部、ナフテン酸コバル
ト（コバルト含有率６％の溶液）0.5部、ジメチ
ルアニリン0.02部を添加し、厚さ1.0mmの試験片
をコテ塗工法により成形し、120℃、２時間の後
硬化を行つた。かくして得られた試験片を沸騰水
中に150時間浸漬した場合の吸水率特性を次の第
１表に示す。本発明方法の効果が認められた。
[Industrial Application Field] The present invention relates to a method for producing an unsaturated polyester resin compound that has excellent water resistance and corrosion resistance and is particularly suitable for paints and linings. [Prior Art] Hitherto, there has been no known lining resin composition in which glass fiber or flake-like inorganic material is added to a curable resin such as unsaturated polyester in order to improve the water resistance and corrosion resistance of the coating film. ing. In such cases, the properties of the lining layer depend on the bonding state between the resin and the glass fiber or flaky inorganic material. That is, it goes without saying that strengthening the bonding strength improves the properties of the lining layer. In order to strengthen the bond between resin and glass fiber or flake-like inorganic material, there is a method (referred to as the "integral method") in which a silane coupling agent is simply mixed at the same time as the resin and inorganic material are mixed. Are known. However, this effect has not yet been achieved consistently and consistently. In addition, the scale-like inorganic material added to the resin,
A method of pre-wetting a silane coupling agent with a diluted solution of water or alcohol is also well known. However, in this case, the scale-like inorganic material aggregates during the drying process, or the diluted liquid in the material remains, which adversely affects the properties of the coating film or lining layer. . It is not practical due to scattering loss. [Problems to be Solved by the Invention] In view of the above situation, the present inventors have conducted extensive studies in order to obtain a corrosion-resistant resin paint and lining that uses unsaturated polyester resin and has excellent water resistance and corrosion resistance. As a result, by adding and mixing flake-like inorganic material treated with a specific method to unsaturated polyester resin to produce a resin compound,
It was discovered that a paint and lining with excellent water resistance and corrosion resistance can be obtained, and the present invention was achieved. [Means for solving the problem] That is, the method of the present invention involves dissolving a silane coupling agent in a polymerizable monomer in an amount corresponding to 0.5 to 5 parts by weight per 100 parts by weight of the scale-like inorganic material. Alternatively, a scale-like inorganic material with a diameter of 3 mmφ or less and a thickness of 1 to 10 microns is immersed at 130°C or less in an emulsified and dispersed solution at 130°C or less, which is still in a wet state. For resin liquid made of unsaturated polyester and polymerizable monomer,
This is a method for producing an unsaturated polyester resin compound, characterized by adding and mixing in a range of 20 to 50% by weight. [Function] In the method of the present invention, since the inorganic material in which the polymerizable monomer is not completely dried and scattered, that is, in a wet state, is mixed with the resin liquid, aggregation of the inorganic material in the resin is prevented, and It is thought that a trace amount of moisture of 0.1% or less adsorbed and remaining in the inorganic material promotes the coupling reaction. It is desirable that the polymerizable monomer for dissolving or emulsifying and dispersing the silane coupling agent used in the present invention and the polymerizable monomer used for dissolving the unsaturated polyester are the same; A monomer can also be used in combination as a diluent. As an example of such a polymerizable monomer, styrene is generally used, but chlorostyrene, vinyltoluene, triethylene glycol dimethacrylate, and the like are also useful. The silane coupling agent used in the present invention is
Vinyltriethoxysilane, vinyltris (β-
methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, etc., depending on the inorganic material being treated. selected. The scale-like inorganic material used in the present invention includes glass flakes, mica, tarta,
It is selected from graphite, artificial mica, alumina, etc., and has a scale-like shape with a diameter of 3 mmφ or less, preferably 1 to 3 mmφ, and a thickness in the range of 1 to 10 μm. The amount of polymerizable monomer and silane coupling agent when treating scale-like inorganic materials varies depending on the type and size of the inorganic material, but the amount of polymerizable monomer is sufficient to soak the inorganic material. or more is sufficient, and the silane coupling agent is suitable for inorganic materials.
A range of 0.5 to 5 parts by weight per 100 parts by weight is effective. The treatment temperature is preferably 130°C or lower, preferably in the range of 60 to 130°C. At 60°C or lower, the treatment takes a long time, and at 130°C or higher, gelation occurs due to the reaction between the monomer and the silane coupling agent. This is undesirable as it causes decomposition of the silane coupling agent. The processing time is one week at room temperature, and about 5 to 60 minutes at 60 to 130°C. The unsaturated polyester used in the present invention is used after being dissolved in a polymerizable monomer, and at this time, a scale-like inorganic material that has been previously treated with a coupling agent is added. The weight ratio of the inorganic material to the unsaturated polyester resin containing the polymerizable monomer is 80:
A range of 20-50:50, preferably 75:25-60:40 is effective. The polymerization catalyst used for the unsaturated polyester resin is an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, kyumene hydroperoxide, etc., and can be selected depending on the purpose. Other additives that can be used to increase commercial value include finely powdered silica, asbestos powder, clay containing organic amines (Bentone manufactured by Beca), dehydrated castor oil, and a condensed acetal compound of sorbitol and benzaldehyde. , such as metal chelates and metal soaps, and also pigments such as titanium white,
Glass fibers, synthetic fibers, curing accelerators such as metal soap, dimethylaniline, acetylacetone, and air drying agents such as paraffin and ethyl cellulose may be added in small amounts as reinforcing materials. [Examples] Next, examples will be shown below to help understand the present invention. Example 1 700 g of a 1% by weight styrene solution of γ-methacryloxypropyltrimethoxysilane and 300 g of glass flakes (diameter 1 to 3 mmφ, average thickness 3 μ) were placed in a flask equipped with a reflux device, and heat treated at 100°C for 20 minutes. After that, excess styrene was removed using a suction funnel, and the glass flakes, whose surfaces were still wet, were mixed with 700 g of unsaturated polyester resin ("Rigorakku LP-1" manufactured by Showa Kobunshi Co., Ltd.) and heated at 150 mmHg. A resin compound (A) was obtained by kneading the mixture using a vacuum muller and adjusting the amount of monomer so that the glass flake content was 30% by weight. The water absorption characteristics of the cured product using the compound (A) are listed in Table 1 below. Example 2 300 g of glass flakes (average particle size 1 mmφ, thickness 3 μ) were added to 1500 g of a 0.6% by weight styrene solution of vinyltris(β-methoxyethoxy)silane with stirring, and after being left at room temperature for one week, a suction funnel was added. Excess styrene was removed using paper, and the glass flakes, whose surfaces were still wet with styrene, were heat-treated in an oven at 110°C for 10 minutes.
It was mixed with 700 g of unsaturated polyester resin (“Rigorak 2141” manufactured by Showa Kobunshi Co., Ltd.) and kneaded at 150 mmHg using a vacuum kneader to determine the glass flake content.
A 30% by weight resin compound (B) was obtained. The absorption characteristics of the cured product using the compound (B) are listed in Table 1 below. Comparative Example 1 1% by weight of γ-methacryloxypropyltrimethoxysilane was added to 700 g of unsaturated polyester resin (“Rigorak LP-1” manufactured by Showa Kobunshi Co., Ltd.),
After that, add 300g of glass flakes and make it 150mm.
The mixture was kneaded for 10 minutes using a Hg vacuum mala to obtain a resin compound (A') with a glass flake content of 30% by weight. The water absorption characteristics of the cured product using the compound (A') are shown in Table 1 below. Comparative Example 2 0.6% by weight of vinyl tris (β-methoxyethoxy) silane was added to 700 g of unsaturated polyester resin (“Rigorak 2141” manufactured by Showa Kobunshi Co., Ltd.), 300 g of glass flakes were added, and the mixture was heated in a vacuum kneader at 150 mmHg. A resin compound (B') having a glass flake content of 30% by weight was obtained by kneading for 10 minutes. The water absorption characteristics of the cured product using the compound (B') are listed in Table 1 below. To 100 parts by weight of each of the resin compounds of Examples 1 and 2 and Comparative Examples 1 and 2, 1.0 part of methyl ethyl ketone peroxide (as a 55% dimethyl phthalate solution) and cobalt naphthenate (cobalt content 6) were added. % solution) and 0.02 part of dimethylaniline were added, a test piece with a thickness of 1.0 mm was formed by a trowel coating method, and post-curing was performed at 120°C for 2 hours. Table 1 below shows the water absorption characteristics when the test piece thus obtained was immersed in boiling water for 150 hours. The effect of the method of the present invention was recognized.
本発明方法で得られる不飽和ポリエステル樹脂
コンパウンドは、耐水性および耐蝕性にすぐれた
塗料およびライニングとした有用である。
The unsaturated polyester resin compounds obtained by the method of the present invention are useful as coatings and linings with excellent water resistance and corrosion resistance.
Claims (1)
片状の無機質材料の100重量部当り0.5〜５重量部
に相当する範囲で溶解または乳化分散させた溶液
に、その径が３mmφ以下、厚さ１〜10ミクロンの
鱗片状の無機質材料を130℃以下で浸漬して得ら
れる、未だ湿潤状態にある鱗片状の無機質材料
を、不飽和ポリエステルと重合性単量体よりなる
樹脂液に添加混合することを特徴とする耐水性、
耐蝕性の優れた塗料およびライニングに適する不
飽和ポリエステル樹脂コンパウンドの製造方法。1. In a solution in which a silane coupling agent is dissolved or emulsified in a polymerizable monomer in an amount equivalent to 0.5 to 5 parts by weight per 100 parts by weight of a scale-like inorganic material, the diameter is 3 mmφ or less and the thickness is The still-wet scale-like inorganic material obtained by soaking the scale-like inorganic material of 1 to 10 microns at 130°C or lower is added to and mixed with a resin liquid consisting of unsaturated polyester and a polymerizable monomer. Water resistance, characterized by
A method for producing an unsaturated polyester resin compound suitable for coatings and linings with excellent corrosion resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27247685A JPS61166851A (en) | 1985-12-05 | 1985-12-05 | Production of resin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27247685A JPS61166851A (en) | 1985-12-05 | 1985-12-05 | Production of resin compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10948376A Division JPS5335782A (en) | 1976-09-14 | 1976-09-14 | Preparation of resin compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61166851A JPS61166851A (en) | 1986-07-28 |
| JPS6337141B2 true JPS6337141B2 (en) | 1988-07-22 |
Family
ID=17514453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27247685A Granted JPS61166851A (en) | 1985-12-05 | 1985-12-05 | Production of resin compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61166851A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04259420A (en) * | 1991-02-14 | 1992-09-16 | Matsushita Electric Ind Co Ltd | Coffee extractor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5020928A (en) * | 1987-05-25 | 1991-06-04 | Seiko Epson Corporation | Ribbon guiding mechanism |
| US5052832A (en) * | 1987-05-25 | 1991-10-01 | Seiko Epson Corporation | Print head and roller biasing mechanism for a hand held thermal printer |
| CN103772925B (en) * | 2013-12-11 | 2015-10-14 | 浙江南益生物科技有限公司 | A kind of liquid nano mica modification agent for PLA |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5054634A (en) * | 1973-09-14 | 1975-05-14 | ||
| JPS5335782A (en) * | 1976-09-14 | 1978-04-03 | Showa Highpolymer Co Ltd | Preparation of resin compounds |
-
1985
- 1985-12-05 JP JP27247685A patent/JPS61166851A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5054634A (en) * | 1973-09-14 | 1975-05-14 | ||
| JPS5335782A (en) * | 1976-09-14 | 1978-04-03 | Showa Highpolymer Co Ltd | Preparation of resin compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04259420A (en) * | 1991-02-14 | 1992-09-16 | Matsushita Electric Ind Co Ltd | Coffee extractor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61166851A (en) | 1986-07-28 |
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