JPH0237369B2 - - Google Patents
Info
- Publication number
- JPH0237369B2 JPH0237369B2 JP55074741A JP7474180A JPH0237369B2 JP H0237369 B2 JPH0237369 B2 JP H0237369B2 JP 55074741 A JP55074741 A JP 55074741A JP 7474180 A JP7474180 A JP 7474180A JP H0237369 B2 JPH0237369 B2 JP H0237369B2
- Authority
- JP
- Japan
- Prior art keywords
- melt
- synthetic wax
- binder composition
- aliphatic hydrocarbon
- parts
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000003973 paint Substances 0.000 claims description 26
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012943 hotmelt Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 dicyclopentadiene Chemical class 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000010734 process oil 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
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003813 thin hair Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は新規な熱溶融型トラフイツクペイント
用粘結剤組成物の製造法に関し、さらに詳しく
は、作業性及び塗膜性能に優れた熱溶融型トラフ
イツクペイントを調製可能な粘結剤組成物の製造
法に関する。
従来、横断歩道、中央線、外側線などの路面標
示用に使用される材料として粘結剤及び顔料を必
須成分とし、その他必要に応じて可塑剤、安定
剤、酸化防止剤、骨材、ガラスビーズなどを含有
する熱溶融型のトラフイツクペイントが知られて
いる。
かかるトラフイツクペイントは一般に各成分を
ミキサーで混合することによつて調製され、それ
を加熱溶融せしめて施工に供されるが、その際に
顔料や充填剤の沈降が生じやすく、そのため施工
性が損なわれたり、塗膜の汚染やヘアークラツク
の発生をもたらす原因となつていた。とくに粘結
剤として脂肪族系炭化水素樹脂を用いる場合にそ
の傾向が強く、その改善が望まれていた。
そこでかかる欠点を改良するために、従来から
適量の沈降防止剤を配合する方策が提案されてい
る。例えば特開昭52−71533号公報によれば、合
成微粉シリカ系、アスベスト粉、クレー、タル
ク、金属石鹸類、合成ワツクス系などの沈降防止
剤をトラフイツクペイント中に0.1〜10重量％、
好ましくは0.5〜３重量％程度配合することが有
効とされている。
而して本発明者らが脂肪族系炭化水素樹脂を粘
結剤とする系における前記公報に記載された方法
の効果を確認すべく種々検討を行つたところ、一
般の沈降防止剤では塗膜性能を改良しようとする
と作業性が大巾に低下するのに対して、合成ワツ
クス系沈降防止剤の場合には作業性を低下させる
ことなしに塗膜性能を改良しうることが判明し
た。しかし、合成ワツクス系沈降防止剤にはかか
る利点の反面、工業的規模でトラフイツクペイン
トを製造する際に効果のバラツキが大きく、再現
性に欠けるきらいがあり、実用に供するうえで大
きな障害となつていた。とくにこの欠点はロジン
系樹脂を粘結剤とする場合には見られない脂肪族
系炭化水素樹脂を粘結剤とする系における特有の
現象であり、この点の改良が強く望まれていた。
そこで本発明者らは従来技術のかかる欠点を改
良すべく鋭意検討を進めた結果、脂肪族系炭化水
素樹脂と合成ワツクス系沈降防止剤との組合せの
場合であつても、両者を特定な手法で配合すると
改良効果が再現性よく得られることを見い出し、
本発明を完成するに到つた。
すなわち本発明の目的は、作業性及び塗膜性能
に優れた熱溶融型トラフイツクペイントを再現性
よく調製可能な熱溶融型トラフイツクペイント用
粘結剤組成物を提供することにあり、かかる本発
明の目的は、脂肪族系炭化水素樹脂100重量部と
合成ワツクス系沈降防止剤0.1〜1.0重量部を予め
溶融混合し、その混合物を熱溶融型トラフイツク
ペイント用の粘結剤成分とすることによつて達成
される。
本発明において使用される粘結剤は、石油類の
熱分解の際に得られる沸点範囲が−20℃ないし＋
100℃の任意の脂肪族系不飽和炭化水素含有留分
を通常の方法に従つてカチオン重合することによ
つて得られる脂肪族系炭化水素樹脂である。かか
る留分には、たとえばC4〜5留分、C5留分、シクロ
ペンタジエンを除去したC5留分、イソプレンを
除去したC5留分などがある。
また本発明で使用される脂肪族系炭化水素樹脂
は、上記留分とカチオン重合可能な純粋なモノマ
ー、たとえばエチレン、ブテン―１、イソブテ
ン、ブタジエン、ジイソブチレン、ピペリレン、
ジシクロペンタジエンなどの不飽和脂肪族または
脂環族化合物、あるいはスチレン、ビニルトルエ
ン、α―メチルスチレン、インデンなどの不飽和
芳香族化合物とを同様な方法で共重合して得られ
る樹脂であつてもよい。これらの共重合成分は全
体の50重量％以下であることが好ましく、とくに
芳香族系モノマー成分は溶融時の流動性、耐候性
などの点からできるだけ少量であることが好まし
い。
これらの脂肪族系炭化水素樹脂は未変性のもの
でも、また適宜変性したものでもよく、なかでも
軟化点（環球法）が70〜130℃、ガードナー色度
14以下、酸価0.2〜50、ヨウ素価（ウイス法）200
以下のものが好ましい。
一方、本発明で使用される合成ワツクス系沈降
防止剤は、分子量1000〜5000、好ましくは1500〜
4000の常温で固形のワツクス状物であり、例えば
ポリエチレンワツクス、ポリプロピレンワツクス
等を挙げることができる。またこれらのワツクス
をさらに酸化、塩素化、スルホン化したものや、
ワツクス中にカルボキシル基、水酸基、エステル
基を導入したものでもよく、二種以上の混合物で
用いることも出来る。
本発明においては、脂肪族系炭化水素樹脂100
重量部と合成ワツクス系沈降防止剤0.1〜1.0重量
部を適宜溶融混合することによつて脂肪族系炭化
水素樹脂中に合成ワツクス系沈降防止剤が均一に
分散された粘結剤組成物が得られる。混合に際し
ての条件は適宜選択されるが、通常は140〜250
℃、好ましくは160〜240℃の温度で10分〜５時間
加熱撹拌することによつて行われる。この際、合
成ワツクス系沈降防止剤の配合量が少ないとトラ
フイツクペイントを調製したときの沈降防止効果
が充分でなく、逆に過度に多くなると揺変性が大
きくなり流動性に支障をきたす結果となる。また
合成ワツクス系沈降防止剤は粉末または粒状の形
状を有するものであることが好ましく、これらの
場合にはブロツク状のものを使用する場合に比較
して分散状態が均一な組成物を容易に得ることが
できる。
かくして得られる粘結剤組成物は多量の脂肪族
系炭化水素樹脂と微量の合成ワツクス系沈降防止
剤とから成るため、脂肪族系炭化水素樹脂とほゞ
同等の性状を有しており、熱溶融型トラフイツク
ペイントの粘結剤成分として好適に使用される。
すなわち、かかる粘結剤成分と通常使用される配
合剤（例えば体質顔料、着色顔料、可塑剤、滑
剤、ガラスビーズなど）とを常法に従つて配合す
ることによりトラフイツクペイントが得られる。
この際、ペイント中に占める粘結剤組成物の割
合は通常10〜30重量％であり、沈降防止剤の割合
としては0.01〜0.3重量％、さらには0.02〜0.2重
量％で充分である。
かかる本発明によれば、作業性及び塗膜性能に
優れた熱溶融型トラフイツクペイントを再現性よ
く調製することができる。かかる本発明の効果は
特定な粘結剤と特定な沈降防止剤との組み合わせ
において初めて見い出されるものであり、粘結剤
としてロジン系樹脂を使用する場合には沈降防止
効果が充分でなく、また沈降防止剤として従来か
ら賞用されている合成微粉シリカ系やアスベスト
粉を使用しても本発明の効果を期待することはで
きない。
以下に実施例を挙げて本発明をさらに具体的に
説明する。なお、実施例、比較例及び参考例中に
表示されている部及び％はすべて重量基準であ
る。また測定および評価は以下の方法によつた。
熱溶融型トラフイツクペイントの物性
(a) 流動性
配合物を約200℃で30分間加熱溶融して均一
な混合物とし、これを31mmφ×24mmのひしやく
にとり、ただちに高さ4.5cmの位置からアルミ
ニウム板に落下させる。落下した配合物の広が
りの長径及び短径を測定し、その平均値によつ
て流動性の良否を判定する。
(b) 溶融粘度及び揺変性
配合物を約200℃で30分間加熱溶融して均一
な混合物とし、BM型粘度計（ブルツクワール
ド社製）により４番ローターを使用し、回転数
を6rpmと60rpmの２点について溶融粘度を測
定した。揺変性については6rpmの粘度と
60rpmの粘度との比で表わす。
T.I値（チキソトロピーインデツクス揺変性の指表）
＝6rpmの粘度／60rpmの粘度
(c) 骨材沈降性
約200℃で溶融し均一な混合物としたものを
50mlのビーカーに満たし、250℃で１時間静置
した後、冷却、硬化させ、垂直面で切断し、切
断面における骨材（ガラスビースと粗粒炭酸カ
ルシウム）の沈降率（％）によつて表わす。
(d) 塗膜の黄色度
JIS Ｋ 5665
(e) 塗膜のヘアークラツク
JIS Ｋ 5665によつて調整した塗料パネルを
サンシヤインウエザオメーター（スガ試験機社
製）によつてブラツクパネル温度63±３℃、ス
プレー18分／120分、相対湿度約50％、照射時
間60時間なる条件下で劣化促進試験を行つた。
その後における外観の変化を次の３段階で評価
した。
Ａ：変化なし、Ｂ：細いヘアークラツクが発
生、Ｃ：太いヘアークラツクが発生
実施例 １
脂肪族系炭化水素樹脂（クイントンＣ―200S、
軟化点96℃、酸価1.7、日本ゼオン社製）100部と
粉末状の合成ワツクス系沈降防止剤（デイスパロ
ンTP202、融点97℃、楠本化成社製）0.5部を230
℃で30分間、撹拌下に溶融混合し、合成ワツクス
系沈降防止剤が樹脂中に均一に分散した粘結剤組
成物を得た。この粘結剤組成物の性状を測定した
ところ、軟化点は94.0℃、溶融粘度は155センチ
ポイズ（60rpm）であり、原料樹脂の溶融粘度
160センチポイズ（60rpm）とほゞ同等であつた。
次いでこの粘結剤組成物15部、重質炭酸カルシ
ウム30部、粗粒炭酸カルシウム32部、酸化チタン
８部、ガラスビーズ15部、可塑性（ナフテンプロ
セス油と綿実油の等量混合物）２部をミキサーで
混合してトラフイツクペイントを調製したのち、
３個の試料を採取してその性能を評価した。結果
を第１表に示す。
比較例 １
脂肪族系炭化水素樹脂と合成ワツクス系沈降防
止剤の溶融混合を行わずに他の配合剤とともに直
接混合すること以外は実施例１に準じてトラフイ
ツクペイントを調製し、３個の試料を採取してそ
の性能を評価した。また合成ワツクス系沈降防止
剤を配合しない系についても同様にして試験を行
つた。結果を第１表に示す。
The present invention relates to a method for producing a novel binder composition for hot-melt type traffic paint, and more specifically, to a binder composition capable of preparing a hot-melt type traffic paint with excellent workability and coating performance. Concerning the manufacturing method. Conventionally, materials used for road markings such as crosswalks, center lines, and outside lines have had binders and pigments as essential ingredients, and other materials such as plasticizers, stabilizers, antioxidants, aggregates, and glass as necessary. Heat-melting type traffic paint containing beads and the like is known. Such traffic paints are generally prepared by mixing each component in a mixer, and then heated and melted for application. However, during this process, pigments and fillers tend to settle, resulting in poor workability. This caused damage, contamination of the paint film, and the occurrence of hair cracks. This tendency is particularly strong when an aliphatic hydrocarbon resin is used as a binder, and an improvement has been desired. In order to improve this drawback, methods have been proposed to include an appropriate amount of anti-settling agent. For example, according to JP-A No. 52-71533, 0.1 to 10% by weight of anti-settling agents such as synthetic fine silica, asbestos powder, clay, talc, metal soaps, and synthetic wax are added to traffic paint.
It is said that it is effective to incorporate preferably about 0.5 to 3% by weight. The present inventors conducted various studies to confirm the effectiveness of the method described in the above publication in a system using an aliphatic hydrocarbon resin as a binder, and found that the coating film was It has been found that, while attempts to improve performance significantly reduce workability, in the case of synthetic wax-based antisettling agents, coating film performance can be improved without reducing workability. However, despite these advantages of synthetic wax-based antisettling agents, when producing traffic paints on an industrial scale, the effects vary widely and tend to lack reproducibility, which is a major obstacle to putting them into practical use. was. In particular, this drawback is a phenomenon peculiar to systems using an aliphatic hydrocarbon resin as a binder, which is not observed when a rosin resin is used as a binder, and there has been a strong desire to improve this point. Therefore, the present inventors conducted intensive studies to improve such drawbacks of the conventional technology, and as a result, even in the case of a combination of aliphatic hydrocarbon resin and synthetic wax-based anti-settling agent, a specific method for combining both of them was found. We discovered that the improvement effect can be obtained with good reproducibility when mixed with
The present invention has now been completed. That is, an object of the present invention is to provide a binder composition for hot-melt traffic paint that can prepare hot-melt traffic paint with excellent workability and coating film performance with good reproducibility. The object of the invention is to melt-mix 100 parts by weight of an aliphatic hydrocarbon resin and 0.1 to 1.0 parts by weight of a synthetic wax-based anti-settling agent in advance, and use the mixture as a binder component for hot-melt traffic paint. achieved by. The binder used in the present invention has a boiling point range of -20℃ to +20℃ obtained during thermal decomposition of petroleum.
It is an aliphatic hydrocarbon resin obtained by cationic polymerization of any aliphatic unsaturated hydrocarbon-containing fraction at 100°C according to a conventional method. Such fractions include, for example, a C4-5 fraction, a C5 fraction, a C5 fraction from which cyclopentadiene has been removed, a C5 fraction from which isoprene has been removed, and the like. The aliphatic hydrocarbon resin used in the present invention is a pure monomer that can be cationically polymerized with the above fraction, such as ethylene, butene-1, isobutene, butadiene, diisobutylene, piperylene,
A resin obtained by copolymerizing an unsaturated aliphatic or alicyclic compound such as dicyclopentadiene, or an unsaturated aromatic compound such as styrene, vinyltoluene, α-methylstyrene, or indene in a similar manner. Good too. The content of these copolymer components is preferably 50% by weight or less of the total weight, and it is particularly preferable that the amount of the aromatic monomer component is as small as possible from the viewpoint of melt fluidity, weather resistance, etc. These aliphatic hydrocarbon resins may be unmodified or appropriately modified, with a softening point (ring and ball method) of 70 to 130°C and a Gardner chromaticity.
14 or less, acid value 0.2-50, iodine value (Wiss method) 200
The following are preferred. On the other hand, the synthetic wax-based antisettling agent used in the present invention has a molecular weight of 1000 to 5000, preferably 1500 to 5000.
It is a wax-like material that is solid at room temperature of 4,000 °C, and examples thereof include polyethylene wax and polypropylene wax. In addition, these waxes are further oxidized, chlorinated, and sulfonated,
A wax having a carboxyl group, a hydroxyl group, or an ester group introduced therein may be used, or a mixture of two or more thereof may be used. In the present invention, aliphatic hydrocarbon resin 100
A binder composition in which the synthetic wax-based anti-settling agent is uniformly dispersed in the aliphatic hydrocarbon resin can be obtained by suitably melt-mixing 0.1 to 1.0 parts by weight of the synthetic wax-based anti-settling agent. It will be done. The mixing conditions are selected appropriately, but usually 140 to 250
This is carried out by heating and stirring at a temperature of 160 to 240°C, preferably 10 minutes to 5 hours. At this time, if the amount of the synthetic wax-based anti-settling agent is too small, the anti-settling effect will not be sufficient when preparing the traffic paint, and if it is too large, the thixotropy will increase and flowability will be affected. Become. Furthermore, it is preferable that the synthetic wax-based antisettling agent has a powder or granular form; in these cases, it is easier to obtain a composition with a more uniform dispersion than when using a block-like agent. be able to. The binder composition thus obtained consists of a large amount of aliphatic hydrocarbon resin and a small amount of synthetic wax-based anti-settling agent, so it has properties almost the same as aliphatic hydrocarbon resin, and is heat resistant. It is suitably used as a binder component in melt-type traffic paints.
That is, a traffic paint can be obtained by blending such a binder component with commonly used compounding agents (for example, extender pigments, coloring pigments, plasticizers, lubricants, glass beads, etc.) according to a conventional method. At this time, the proportion of the binder composition in the paint is usually 10 to 30% by weight, and the proportion of the antisettling agent is preferably 0.01 to 0.3% by weight, more preferably 0.02 to 0.2% by weight. According to the present invention, a heat-melting type traffic paint having excellent workability and coating film performance can be prepared with good reproducibility. Such effects of the present invention are first found in the combination of a specific binder and a specific anti-settling agent, and when a rosin resin is used as a binder, the anti-settling effect is insufficient, and Even if synthetic fine silica powder or asbestos powder, which has been used conventionally as an anti-settling agent, is used, the effects of the present invention cannot be expected. The present invention will be explained in more detail with reference to Examples below. Note that all parts and percentages shown in Examples, Comparative Examples, and Reference Examples are based on weight. Measurement and evaluation were conducted using the following methods. Physical properties of heat-melting type traffic paint (a) Fluidity Melt the mixture by heating at approximately 200℃ for 30 minutes to form a homogeneous mixture.Take this into a 31mmφ x 24mm cube and immediately apply aluminum from a height of 4.5cm. Drop it onto the board. The long axis and short axis of the spread of the fallen mixture are measured, and the quality of the fluidity is determined based on the average value. (b) Melt viscosity and thixotropy The mixture was heated and melted at approximately 200°C for 30 minutes to form a homogeneous mixture, and measured using a BM type viscometer (manufactured by Burtsk World) using a No. 4 rotor at a rotation speed of 6 rpm. Melt viscosity was measured at two points at 60 rpm. For thixotropy, the viscosity at 6 rpm and
Expressed as a ratio to the viscosity at 60 rpm. TI value (thixotropy index thixotropy)
= Viscosity at 6rpm/Viscosity at 60rpm (c) Aggregate sedimentation ability Melt at approximately 200℃ to form a homogeneous mixture.
Fill a 50ml beaker, let it stand at 250℃ for 1 hour, cool it, harden it, cut it on a vertical plane, and calculate the sedimentation rate (%) of the aggregate (glass beads and coarse calcium carbonate) on the cut surface. represent (d) Yellowness of the paint film JIS K 5665 (e) Hair crack of the paint film The paint panel adjusted according to JIS K 5665 was measured with a Sunshine Weatherometer (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63±. An accelerated deterioration test was conducted under the following conditions: 3°C, spraying for 18 minutes/120 minutes, relative humidity of approximately 50%, and irradiation time for 60 hours.
Changes in appearance thereafter were evaluated on the following three levels. A: No change, B: Thin hair cracks occur, C: Thick hair cracks occur Example 1 Aliphatic hydrocarbon resin (Quinton C-200S,
Softening point 96℃, acid value 1.7, Nippon Zeon Co., Ltd.) 100 parts and powdered synthetic wax-based antisettling agent (Disparon TP202, melting point 97℃, Kusumoto Kasei Co., Ltd.) 0.5 parts at 230%
The mixtures were melt-mixed at ℃ for 30 minutes with stirring to obtain a binder composition in which the synthetic wax-based anti-settling agent was uniformly dispersed in the resin. When the properties of this binder composition were measured, the softening point was 94.0°C, the melt viscosity was 155 centipoise (60 rpm), and the melt viscosity of the raw resin was
It was almost equivalent to 160 centipoise (60 rpm). Next, 15 parts of this binder composition, 30 parts of ground calcium carbonate, 32 parts of coarse calcium carbonate, 8 parts of titanium oxide, 15 parts of glass beads, and 2 parts of plasticizer (equal mixture of naphthenic process oil and cottonseed oil) were mixed in a mixer. After mixing to prepare traffic paint,
Three samples were taken to evaluate their performance. The results are shown in Table 1. Comparative Example 1 A traffic paint was prepared according to Example 1, except that the aliphatic hydrocarbon resin and the synthetic wax-based antisettling agent were not melt-mixed but directly mixed with other compounding ingredients. Samples were taken and their performance evaluated. A similar test was also conducted on a system that did not contain a synthetic wax-based anti-settling agent. The results are shown in Table 1.
【表】【table】
【表】
第１表の結果から、本発明の場合には適度な溶
融粘度を有しているため作業性に優れており、ま
た黄色度、耐候性の面でも良好な性能を示すこと
がわかる。また実験番号１〜３のいずれの場合に
もほゞ同等の性能を示しており、効果の再現性に
も優れていることがわかる。一方、従来技術によ
れば、同一配合であつても効果のバラツキが大き
く、例えば実験番号４では良好な耐候性を示すも
のの作業性に劣り、実験番号５では全体的に良好
な性能を有するがやや流動性に劣り、さらに実験
番号６では溶融粘度が低すぎるため沈降防止効果
に劣つている。
参考例 １
合成ワツクス系沈降防止剤に代えて微粉シリカ
系沈降防止剤（ニプシルVN―３、日本シリカ社
製）1.5部を用いること以外は実施例１と同様に
して粘結剤組成物を調製した。得られた組成物の
軟化点は96.0℃、溶融粘度は165センチポイズで
あつた。
次いでこの粘結剤組成物を用いて実施例１に準
じてトラフイツクペイントを調製し、３個の試料
を採取してその性能を評価した。また比較のた
め、微粉シリカ系沈降防止剤を予備混合せずに調
製したトラフイツクペイントについても同様にし
てその性能を評価した。結果を第２表に示す。[Table] From the results in Table 1, it can be seen that the present invention has an appropriate melt viscosity and therefore has excellent workability, and also exhibits good performance in terms of yellowness and weather resistance. . Moreover, it can be seen that almost the same performance was shown in all cases of experiment numbers 1 to 3, and the reproducibility of the effect was excellent. On the other hand, according to the conventional technology, even if the formulation is the same, the effects vary widely; for example, experiment No. 4 shows good weather resistance but has poor workability, and experiment No. 5 shows good performance overall, but The fluidity was slightly inferior, and furthermore, in Experiment No. 6, the melt viscosity was too low, so the anti-sedimentation effect was poor. Reference Example 1 A binder composition was prepared in the same manner as in Example 1, except that 1.5 parts of a finely divided silica-based anti-settling agent (Nipsil VN-3, manufactured by Nippon Silica Co., Ltd.) was used in place of the synthetic wax-based anti-settling agent. did. The resulting composition had a softening point of 96.0°C and a melt viscosity of 165 centipoise. Next, a traffic paint was prepared using this binder composition according to Example 1, and three samples were taken to evaluate its performance. For comparison, the performance of a traffic paint prepared without premixing a finely divided silica anti-settling agent was also evaluated in the same manner. The results are shown in Table 2.
【表】
この結果から、微粉シリカ系沈降防止剤を用い
る場合には、配合方法の如何に拘らず効果のバラ
ツキは少ないが、塗膜性能の改良効果が充分でな
いことがわかる。なお、塗膜性能をより改良する
ために沈降防止剤を増量すると、溶融粘度が著し
く高くなり作業性が大巾に低下した。
実施例 ２
合成ワツクス系沈降防止剤の配合量を変えるこ
と以外は実施例１と同様にして粘結剤組成物を調
製した。得られた組成物の性状を第３表に示す。
次いで、この粘結剤組成物を用いて実施例１に準
じてトラフイツクペイントを調製し、３個の試料
を採取してその性能を評価した。結果を第３表に
示す。[Table] From the results, it can be seen that when a finely divided silica-based antisettling agent is used, there is little variation in effectiveness regardless of the blending method, but the effect of improving coating film performance is not sufficient. In addition, when the amount of anti-settling agent was increased in order to further improve the coating film performance, the melt viscosity increased significantly and the workability decreased significantly. Example 2 A binder composition was prepared in the same manner as in Example 1 except that the amount of the synthetic wax-based antisettling agent was changed. The properties of the obtained composition are shown in Table 3.
Next, a traffic paint was prepared using this binder composition according to Example 1, and three samples were taken to evaluate the performance. The results are shown in Table 3.
【表】
この結果から、合成ワツクス系沈降防止剤を過
度に配合した粘結剤組成物を使用する場合（実験
番号20〜22）には、溶融粘度が高すぎるため実用
に供しえないことがわかる。
比較例 ２
脂肪族系炭化水素樹脂に代えてマレイン化ロジ
ン樹脂（エステルガムＭ―90、軟化点92℃、荒川
林産(株)製）100部を用いること以外は実施例１と
同様にして粘結剤組成物を得た。次いでこの粘結
剤組成物を第４表に示す所定の割合で用い、実施
例１と同様にしてトラフイツクペイントを調製
し、その性能を評価した。結果を第４表に示す。[Table] From this result, when using a binder composition containing an excessive amount of synthetic wax-based anti-settling agent (experiment numbers 20 to 22), the melt viscosity is too high and it cannot be put to practical use. Recognize. Comparative Example 2 A viscosity was prepared in the same manner as in Example 1, except that 100 parts of maleated rosin resin (Ester Gum M-90, softening point 92°C, manufactured by Arakawa Forestry Co., Ltd.) was used in place of the aliphatic hydrocarbon resin. A binder composition was obtained. Next, a traffic paint was prepared in the same manner as in Example 1 using this binder composition in the predetermined proportions shown in Table 4, and its performance was evaluated. The results are shown in Table 4.
【表】【table】
【表】
第４表より、ロジン系樹脂を用いた場合には流
動性が充分でなく（実験番号23）、流動性改良の
ために粘結剤組成物の配合量を増やすと沈降防止
効果が充分でなくなる（実験番号24）ことがわか
る。[Table] From Table 4, fluidity was insufficient when rosin-based resin was used (experiment number 23), and increasing the blending amount of the binder composition to improve fluidity improved the anti-settling effect. It can be seen that it is not sufficient (experiment number 24).
Claims (1)
クス系沈降防止剤0.1〜1.0重量部を溶融混合する
ことを特徴とする熱溶融型トラフイツクペイント
用粘結剤組成物の製造法。1. A method for producing a binder composition for hot-melt traffic paint, which comprises melt-mixing 100 parts by weight of an aliphatic hydrocarbon resin and 0.1 to 1.0 parts by weight of a synthetic wax-based antisettling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7474180A JPS57174A (en) | 1980-06-03 | 1980-06-03 | Preparation of binder composition for traffic paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7474180A JPS57174A (en) | 1980-06-03 | 1980-06-03 | Preparation of binder composition for traffic paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57174A JPS57174A (en) | 1982-01-05 |
| JPH0237369B2 true JPH0237369B2 (en) | 1990-08-23 |
Family
ID=13555962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7474180A Granted JPS57174A (en) | 1980-06-03 | 1980-06-03 | Preparation of binder composition for traffic paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57174A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5271533A (en) * | 1975-12-12 | 1977-06-15 | Hitachi Chem Co Ltd | Hot-melt type traffic paint compositions |
| JPS53114842A (en) * | 1977-03-18 | 1978-10-06 | Mitsui Petrochem Ind Ltd | Production of composition for hot-melt type traffic paint |
-
1980
- 1980-06-03 JP JP7474180A patent/JPS57174A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5271533A (en) * | 1975-12-12 | 1977-06-15 | Hitachi Chem Co Ltd | Hot-melt type traffic paint compositions |
| JPS53114842A (en) * | 1977-03-18 | 1978-10-06 | Mitsui Petrochem Ind Ltd | Production of composition for hot-melt type traffic paint |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57174A (en) | 1982-01-05 |
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