JPH0120660B2 - - Google Patents
Info
- Publication number
- JPH0120660B2 JPH0120660B2 JP58068426A JP6842683A JPH0120660B2 JP H0120660 B2 JPH0120660 B2 JP H0120660B2 JP 58068426 A JP58068426 A JP 58068426A JP 6842683 A JP6842683 A JP 6842683A JP H0120660 B2 JPH0120660 B2 JP H0120660B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- component
- paint
- butyl rubber
- 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
- 229920000647 polyepoxide Polymers 0.000 claims description 82
- 239000003822 epoxy resin Substances 0.000 claims description 81
- 239000003973 paint Substances 0.000 claims description 69
- 229920005549 butyl rubber Polymers 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 31
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000010073 coating (rubber) Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 230000007613 environmental effect Effects 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- -1 seawall construction Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011271 tar pitch Substances 0.000 description 2
- 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 2
- 239000008096 xylene Substances 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
本発明は常温硬化型高固形分塗料に係り、更に
詳しくは(A)ブチルゴム塗料成分と、(B)エポキシ樹
脂及びエポキシ樹脂用硬化剤成分とから成る常温
硬化型高固形分塗料に関するものである。
本発明の特徴は、ブチルゴムに由来する優れた
環境遮断性、可撓性、耐衝撃性及び塗り重ね密着
性と、エポキシ樹脂及びエポキシ樹脂用硬化剤に
由来する強じん性、接着性、耐薬品性、幅広い物
性及び作業性制御性を併せ持ち、しかも、高固形
分とすることに依り、厚塗りが可能となり、防食
効果を高めるのみならず、所定の膜厚を得る為の
塗装回数を減少することに依る工期短縮及び経費
削減を可能とし、揮散する有機溶剤量を減少する
ことに依る作業環境の安全衛生面の改善を寄与す
ることである。
本発明の常温硬化型高固形分塗料の用途は、工
場プラント、船舶、橋梁、鋼管、港湾設備、海洋
構築物、護岸工事を始めとする防食用塗料、車輌
のアンダーコート、耐薬品床、工場床等多くの分
野がある。
従来、ゴム系塗料は特に常温に於て塗膜形成を
行なう場合は充分な塗膜強度及び接着強度を得る
架橋方法が無い、塗装性が悪い、塗膜の粘度安定
性が悪い、塗膜の粘着性が出やすい等の欠点が生
じやすく、実用化されているものはハイパロン、
塩化ゴム、環化ゴム等少数に限られていた。
一方、エポキシ系塗料は多くの実績が示す様
に、優れた接着性、強じん性、耐薬品性、幅広い
物性制御性及び作業性制御性等により多くの分野
に亘つて使用され好評を博して来たが、可撓性、
耐衝撃性、塗り重ね密着性、耐候性等に欠点があ
つた。
そこでそれ等欠点の解消を目的に、エポキシウ
レタン樹脂の開発、可撓性エポキシ樹脂の開発、
エポキシ樹脂硬化剤の開発、可撓性附与剤の開発
が活発に行なわれて来た。しかしながら、それ等
は経時変化による可撓性低下となつて耐久性の悪
いものや、塑性の強化のみに頼り単なる強じん性
の低下を招くものや、エポキシ系塗料の長所であ
る接着性を損うものや、高価であつて汎用に不適
当なものであつた。
そこで、本発明者等は、長期に亘り弾性を有す
る可撓性を保持し、耐衝撃性、屈曲性、塗り重ね
密着性、下地との密着性、強じん性及び環境遮断
性にすぐれ、厚塗りが可能で安価な常温硬化型高
固形分塗料を長期間にわたり鋭意研究を重ねた結
果、ブチルゴムとエポキシ樹脂とエポキシ樹脂用
硬化剤とから成る常温硬化型高固形分塗料が本発
明の目的に合致することを確認し、本発明を完成
するに至つた。
次に本発明の構成成分について説明する。
本発明で記載した(A)成分とは、ブチルゴム塗料
成分であり、以下順次説明する如く、展色剤、充
填剤、添加剤及び有機溶剤から成るブチルゴム塗
料である。
即ち、展色剤とは塗料の固体塗膜形成成分を指
し、本発明で使用出来るものとしては、ブチルゴ
ム、ブチル再生ゴム、ポリイソブチレン、テルペ
ン系樹脂、テルペン−フエノール系樹脂、フエノ
ール樹脂、芳香族系炭化水素樹脂、脂環族系炭化
水素樹脂、脂肪族系炭化水素樹脂、キシレン樹
脂、クマロン−インデン樹脂、ロジン及びロジン
変性樹脂、ストレートアスフアルト、ブロンアス
フアルト、タールピツチ等を挙げる事が出来る。
しかし、本発明に於ては展色剤の組成のうちブ
チルゴム成分が20〜80重量％含有される事が好ま
しい。尚、本発明に記載したブチルゴム成分とは
ブチルゴム、ブチル再生ゴム、ポリイソブチレン
を１種又は２種以上を併用して成る固体ゴム成分
を指す。ブチルゴム成分の特徴は、腐食性物質と
される酸素、塩素、亜硫酸ガス、水蒸気等の気体
遮断性、耐水性、耐塩水性、酸・アルカリに対す
る耐薬品性、耐候性、耐老化性、耐屈曲性、高い
電気絶縁抵抗性等優れた性質が挙げられ、環境遮
断能力に特に優れた成分である事は公知の通りで
ある。
ブチルゴムが(A)成分を構成する展色剤の組成の
うち20重量％以下の場合は、還境遮断性、可撓性
に劣る傾向があつた。
又、逆に80重量％以上の含有率の場合は、強じ
ん性、接着性、粘度安定性、塗装作業性に劣る傾
向が生じた。
その他に、ブチルゴム塗料成分について重要な
事は、可塑性調節をする必要がある点である。
即ち、従来ゴム系塗料が実用化されなかつた背
景の１つとして、ゴムの難溶性と溶解後の粘度安
定性とが挙げられるが、この難溶性及び粘度安定
性を解決する手段として、ポリマーの可塑度調節
を行なつた。可塑度が大きい場合は溶解性及び／
又は塗料粘度に難点が生じ、可塑度の小さいもの
では塗膜強度、塗膜表面の粘着性に悪影響を与え
た。
本発明に於ては最適ムーニー粘度はML1+4（100
℃）30〜50の範囲に調節し、充填剤、粘着附与樹
脂等との配合比率及びその種類及びそれ等の混合
溶解方法を改善する事で溶解性及び粘度安定性の
問題を解決するに至つた。
本発明の(A)成分であるブチルゴム塗料成分を構
成する展色剤として、前記ブチルゴム成分の他に
粘着附与樹脂成分と瀝青物が挙げられる。
粘着附与樹脂成分としては、テルペン系樹脂、
テルペンフエノール系樹脂、フエノール系樹脂、
クマロン−インデン樹脂、キシレン樹脂、ロジン
及びロジン変性樹脂、芳香族系炭化水素樹脂、脂
環族系炭化水素樹脂、脂肪族系炭化水素樹脂等が
１種又は２種以上併用して使用される。
粘着附与樹脂の使用効果は下地及び塗り重ね下
地との密着性、塗膜強度、溶解性、粘度安定性の
向上である。
瀝青物成分としては、ストレートアスフアル
ト、ブロンアスフアルト、タールピツチ等が１種
又は２種以上を併用して用いられる。
瀝青物の使用効果は、防食効果向上、充填剤の
充填性の向上、溶解性の向上、粘度安定性の向
上、コストダウン等である。
本発明に記載した充填剤としては、クレー、タ
ルク、マイカ、ホワイトカーボン、カーボン、ア
スベスト、硫酸バリウム、炭酸カルシウム、硅
砂、シラスバルーン、ガラスビーズ、酸化チタ
ン、酸化鉄、酸化亜鉛、鉛白、鉛丹、塩基性硫酸
鉛、ジンククロメート、リン酸亜鉛、モリブデン
酸亜鉛フエライト、金属亜鉛末等が１種又は２種
以上を併用して使用される。充填の使用効果は作
業性及び厚塗り時のダレ防止等の粘性の調整、製
品形態上の混合比率の調整、固形分の調整、溶解
性の向上、防食効果の向上、塗り床のスリツプ防
止等である。
本発明に記載した添加剤とは、可塑剤、消泡
剤、レベリング剤、滑剤、界面活性剤、カツプリ
ング剤等を言い、必要により選択して使用でき
る。
本発明で記載した有機溶剤とは、芳香族炭化水
素系、脂肪族炭化水素系、アルコール系、エーテ
ル系、エステル系等の有機溶剤を言い、使用に当
つてはそれ等の１種又は２種以上を併用する事が
できる。
本発明に於ても一般塗料と同様に溶剤の選択は
塗膜性能、作業性、塗膜外観に影響する為に、主
溶剤と助溶剤の組み合せは慎重に行なう必要があ
る。又、本発明は常温硬化反応を行ない、厚塗り
を行なう為に、沸点が150℃以上の高沸点溶剤を
主として用いると、溶剤抜けが悪く、接着性、耐
薬品性等に悪影響を与える恐れがある為、沸点が
100℃以下の低沸点溶剤及び／又は沸点が100℃〜
150℃の中沸点溶剤を主として用いる事が好まし
い。
本発明で記載した(B)成分とは、エポキシ樹脂及
びエポキシ樹脂用硬化剤である。
本発明で記載したエポキシ樹脂とは、１分子中
に２個以上のエポキシを有する化合物を言う。
エポキシ樹脂の例としては、ビスフエノールＡ
型エポキシ樹脂、ビスフエノールＦ型エポキシ樹
脂、ポリグリコール型エポキシ樹脂、ノボラツク
型エポキシ樹脂、過酢酸系エポキシ樹脂、ダイマ
ー酸型エポキシ樹脂等であり、１種又は２種以上
を併用して使う事ができる。
これ等のうち、ビスフエノールＡ型エポキシ樹
脂は汎用エポキシ樹脂として物性面、価格面を優
れて居り、単独で充分効果を発揮する事が出来る
が、粘度、塗装性を改善する為にはビスフエノー
ルＦ型エポキシ樹脂を単独で又はビスフエノール
Ａ型エポキシ樹脂と任意の比率で混合して使用す
る事が好ましい。
更に、粘度、塗装性、屈曲性を改善する為には
ポリグリコール型エポキシ樹脂をビスフエノール
Ａ型エポキシ樹脂又は、ビスフエノールＦ型エポ
キシ樹脂又はビスフエノールＡ型エポキシ樹脂と
ビスフエノールＦ型エポキシ樹脂の混合物と混合
して用いる事が好ましい。しかし乍ら、ポリグリ
コール型エポキシ樹脂は塗膜物性、接着性、硬化
遅延等の不都合が生じる為、エポキシ樹脂の中の
50重量％を越えない範囲で使用する事が好まし
い。又、本発明に於て、エポキシ樹脂は常温に於
て、液状である事が好ましい。
即ち、エポキシ樹脂が常温で固定である場合
は、高粘度となり塗装性、粘度安定性、可撓性が
劣り、塗料粘度が温度により大きく変化し、季節
及び地域により、エポキシ樹脂用硬化剤を添加し
た場合の撹拌効率及び塗装作業性が劣る。又、本
発明に於ては、エポキシ樹脂100重量部に対して
(A)成分であるブチル塗料を100〜400重量部含む事
が好ましい。
即ち、エポキシ樹脂100重量部に対し(A)成分量
が100重量部以下の場合は、可撓性、環境遮断性、
塗り重ね密着性、耐酸性、吹付け仕上りが劣り、
逆にエポキシ樹脂100重量部に対し(A)成分量が400
重量部以上の場合は、強じん性、下地密着性、吹
付塗装性に劣つた。
又、エポキシ系塗料の欠点であるチヨーキング
現象、ブラシング現象、及びエポキシ系塗料独特
の表面のへこみ現象はブチルゴム成分と併用する
事に依り長期間に亘つて発生する事が無かつた。
本発明に記載したエポキシ樹脂用硬化剤とは、
本発明の常温硬化型高固形分塗料が硬化反応を行
なう際に、エポキシ樹脂中のエポキシ基と硬化反
応を行なう官能基を有する化合物を指す。
エポキシ樹脂用硬化剤は公知の如く、化学構造
的に非常に多くの系列があり、又、同系列に属す
る化合物の間でも相溶性、吸水性、可撓性等に大
きな差が生じる為、個々のエポキシ樹脂用硬化剤
についてチエツクする必要がある。
本発明では常温硬化反応を行なう為、本発明に
適したエポキシ樹脂用硬化剤の例としては、ポリ
アミド、脂肪族アミン、脂肪族変性アミン、芳香
族変性アミン、ケテイミン等を挙げる事が出来、
それ等を１種又は２種以上を併用して使用する事
が出来る。
脂肪族アミンは可使時間、毒性、臭気、塗り重
ね接着性の点で、単独で使用する事は好ましくな
く、硬化促進剤として用いる事が好ましい。
本発明ではポリアミド、脂肪族変性アミン、芳
香族変性アミンを１種又は２種以上併用し、主た
るエポキシ樹脂用硬化剤として用いる事が好まし
い。又、エポキシ樹脂用硬化剤の量はエポキシ樹
脂との反応比率により決定し、その反応比率は
0.7〜1.0モルエポキシ樹脂用硬化剤／エポキシ樹
脂の範囲である事が好ましい。
即ち、反応比率が0.7モル以下の場合は環境遮
断性、耐衝撃性、耐屈曲性に劣り、逆に反応比率
が1.0モル以上の場合は塗り重ね密着性、下地と
の密着性、環境遮断性に劣り、反応比率は0.7〜
1.0モルの範囲を外れると特に防食用途には不適
当である。
硬化促進剤についてはトリエタノールアミン、
NN′−ジメチルピペラジン、ピリジン、キノリ
ン、テトラメチルグアニジン、フエノール、ビス
フエノールＡ、トリ（ジメチルアミノメチル）フ
エノール、DMP−30等があり何れも使用できる
が、本発明に於てはフエノール類が塗り重ね接着
性等への悪影響も少なく好ましい。
本発明の常温硬化型高固形分塗料の製造に際し
ては、ブチルゴム成分と充填剤及び添加剤の一部
或いは全部を加えてロール、ニーダー、バンバリ
ーミキサー等の汎用ゴム混練機を用いて混練し、
有機溶剤にて溶解しゴム溶液とした後、充填剤及
び添加剤の残りがある場合にはその残りとエポキ
シ樹脂若しくは、エポキシ樹脂用硬化剤を加えて
撹拌混合し、ペイントロールミルを通し、エポキ
シ樹脂含有塗料（以下主剤という）又はエポキシ
樹脂用硬化剤含有塗料（以下硬化剤という）を作
成する。
しかし、上記製造方法は一例に過ぎず、本発明
が何等限定されるものではない。本発明の常温硬
化型高固形分塗料の使用方法は、主剤と硬化剤を
所定の配合比率に計量し混合を充分行なつた後、
エアレススプレー、エアスプレー、刷毛塗り、ロ
ーラー塗り、コテ塗り等により常温硬化させる。
又、所定厚みとする為には所定硬化時間後に再
度塗装し常温硬化させる。本発明の常温硬化型高
固形分塗料の製品形態について述べると、
(1) ブチルゴム成分とエポキシ樹脂を含有する主
剤とエポキシ樹脂用硬化剤を含有する硬化剤か
ら成る二液型塗料。
(2) エポキシ樹脂を含有する主剤とブチルゴム成
分とエポキシ樹脂用硬化剤を含有する硬化剤か
ら成る液型塗料。
(3) ブチルゴム成分とエポキシ樹脂を含有する主
剤とブチルゴム成分とエポキシ樹脂用硬化剤を
含有する硬化剤から成る二液型塗料。
(4) ブチルゴム成分を含有するブチルゴム塗料と
エポキシ樹脂を含有する主剤とエポキシ樹脂用
硬化剤を含有する硬化剤から成る三液型塗料。
上記の４つの製品形態をとる事が出来、何れの
形態をとつても貯蔵安定性及び硬化塗膜物性は損
われない。
次に本発明の常温硬化型高固形分塗料の効果に
ついて説明する。
本発明の常温硬化型高固形分塗料はブチルゴム
成分の長所とエポキシ系塗料の長所を併せ持ち、
各々の欠点をカバーした塗料である。
即ち、ブチルゴム成分に由来する環境遮断性、
耐衝撃性、耐屈曲性、塗り重ね密着性の長所を有
し、エポキシ樹脂及びエポキシ樹脂用硬化剤に由
来する接着性、強じん性、耐薬品性の長所を有す
るのみならず、高固形分塗料に由来する厚塗り性
及び塗装回数軽減に伴う工程短縮、省力、省エネ
ルギー、コスト削減、防食性の改善、更には揮散
溶剤量の少なさから労働安全衛生面での改善、更
に塗料の価格が安価である点で多大のメリツトが
生じる丈でなく、ブチルゴム成分として自動車の
タイヤチユーブから再生処理して得られるブチル
再生ゴムを使用した場合は、資源の有効利用とい
うメリツトも加味される。
この様に本発明の常温硬化型高固形分塗料は従
来の塗料分野では見る事の出来なかつたブチルゴ
ムとエポキシ樹脂及びエポキシ樹脂用硬化剤の長
所を合体させた新規な分野の塗料であり、環境遮
断性及び耐衝撃性等を活かし被塗物のライフサイ
クルを大巾に伸ばす事により、各種の産業発展に
役立つものである。
次に本発明の実施例及び比較例により更に詳細
に説明するが、下記実施例により本発明は何等限
定されるものではない。
試験試料の作製方法
１ 常温硬化型高固形分塗料の作製
ブチルゴム成分と充填剤と粘着附与樹脂と瀝
青物とを加え、加圧ニーダーにて50〜70℃にて
充分均一になる様に混練を行ない、そのコンパ
ウンドを固形分80％になる量の有機溶剤にて充
分膨潤させてから撹拌溶解させ、充分均一にな
つた時点で、
インクロールにて処理した後、残りの有機溶
媒に添加し充分均一な状態にした。更に80メツ
シユの金網で過し、ゴム塗料を作製した。
２ 試料の作製
１−１により得られたゴム塗料に対し所定量
のエポキシ樹脂及び、所定量のエポキシ樹脂用
硬化剤を混合し充分均一とした後、エアレスス
プレー及びフイルムアプリケーターにより所定
量塗布し標準状態にて14日間養生した。
試験の測定方法
１ 環境遮断性の測定方法
１−１ 耐水性：JIS−Ｋ−5400（７、２項）に準
じ、条件は温度50±２℃、湿度98±２％、時
間96時間とした。
１−２ 耐塩水性：JIS−Ｋ−5400（７、６項）に
準じた。
１−３ 耐候性：JIS−Ｋ−5400（６、17項）に準
じ、条件は1000時間照射とした。
２ 接着性の測定方法
２−１ 下地密着性：JIS−Ｋ−5400（６、15項）
に準ずる。
２−２ 塗り重ね密着性：JIS−Ｋ−5400（６、10
項）に準じて塗り重ねを行ないJIS−Ｋ−
5400（６、15項）に準じて密着性を調べた。
３ 可撓性の測定方法
３−１ 耐衝撃性：JIS−Ｋ−5400（６、13、３
項）に準じる。
３−２ 耐屈曲性：JIS−Ｋ−5400（６、16項）に
準ずる。心棒の直径は６mmとした。
４ 強じん性の測定方法
４−１ 鉛筆硬度：JIS−Ｋ−5400（６、14項）に
準ずる。
５ 耐薬性の測定方法
５−１ 耐酸性：JIS−Ｋ−5400（７、５項）に準
ずる。
５−２ 耐アルカリ性：JIS−Ｋ−5400（７、４
項）に準ずる。
６ 塗装作業性の測定方法
６−１ 塗装作業性：吹き付け塗装を垂直に保つ
た鉄板面に約１mmの厚みに下記条件にて常温
硬化型高固形分塗料を吹き付け、硬化後の塗
膜の仕上り状態をチエツクした。
吹き付け条件 塗装機：エアレスガンALS
−122型（岩田塗装工業(株)製）
圧力倍率：１：20
空気圧：５Kg／cm2
ノズル径：0.4mm
７ 粘度安定性の測定方法
７−１ (A)成分とエポキシ樹脂との混合物
(A)成分とエポキシ樹脂の各々の所定量を加
え、充分混合し、充分均一になつた混合物を
作成し、常温で24時間静置後Ｂ型粘度計にて
貯蔵前の粘度を測定した。
次に３カ月間常温で貯蔵した後、貯蔵前と
同様に粘度の測定を行なつた。
貯蔵前後の粘度変化率を計算した。
７−２ (A)成分とエポキシ樹脂との混合物
７−１と同様な操作により測定し、貯蔵前
後の粘度変化率を計算した。尚、７−１及び
７−２で用いた粘度変化率の計算式は次の通
りである。
粘度変化率（％）＝貯蔵後の粘度／貯蔵前の粘度×10
0
試験結果の評価表示方法
１ 環境遮断性
１−１ 耐水性：JIS−Ｋ−5400（７、２項）の判
定で“水に浸しても異状がない”としたもの
は〇、その他を×とした。
１−２ 耐塩水性：JIS−Ｋ−5400（７、６項）の
判定で“塩化ナトリウム溶液に浸しても異常
がない”としたものは〇、その他を×とし
た。
１−３ 耐候性：見本品と比べて、しわ、ふく
れ、はがれ、われ、変色、チヨーキングに異
常のない場合を〇、その他を×とした。
２ 接着性
２−１ 下地密着性：JIS−Ｋ−5400（６、15碁盤
目試験）の判定で評価点数８以上を〇、６以
下を×とした。
２−２ 塗り重ね密着性：JIS−Ｋ−5400（６、10
重塗り適合性）の判定で“重塗りに支障がな
い”と判定されなかつたものは×、“重塗り
に支障がない”と判定され、かつJIS−Ｋ−
5400（６、15碁盤目試験）の判定で評価点数
８以上を〇、評価点数６以下を×とした。
３ 可懿性
３−１ 耐衝撃性：JIS−Ｋ−5400（６、13、３
項）の判定で、“衝撃による変形でわれ、は
がれができない”と判定されたものを〇、そ
の他を×とした。
３−２ 耐屈曲性：JIS−Ｋ−5400（６、16項）の
判定で“折り曲げに耐える”と判定されたも
のは〇、その他を×とした。
４ 強じん性
４−１ 鉛筆硬度：JIS−Ｋ−5400（６、14項）の
判定による鉛筆引つかき値が2H以上を〇、
Ｈ及びＦを△、HB以下を×とした。
５ 耐薬品性
５−１ 耐酸性：JIS−Ｋ−5400（７、５項）の判
定で“酸に浸しても異常がない”と判定され
たものは、その他を×とした。
５−２ 耐アルカリ性：JIS−5400（７、４項）の
判定で“アルカリに浸しても異状がない”と
判定されたものは〇、その他は×とした。
６ 塗装作業性：硬化後の仕上り状態で、ダレ、
表面凹凸等の美感上の異状のないものを〇、そ
の他を×とした。
７ 粘度安定性
７−１ (A)成分とエポキシ樹脂との混合溶液
(A)成分とエポキシ樹脂の各々の所定量を加
え、３カ月間、常温にて貯蔵し、貯蔵後の粘
度変化が±10％以内にあるものは〇、その他
のものは×とした。
７−１ (A)成分とエポキシ樹脂用硬化剤との混合
溶液
(A)成分とエポキシ樹脂用硬化剤の各々の所
定量を加え、３カ月間常温にて貯蔵し、貯蔵
後の粘度変化が±10％以内にあるものは〇、
その他のものは×とした。
The present invention relates to a room temperature curable high solid content paint, and more particularly to a room temperature curable high solid content paint comprising (A) a butyl rubber paint component, and (B) an epoxy resin and a curing agent component for the epoxy resin. . The characteristics of the present invention are excellent environmental barrier properties, flexibility, impact resistance, and recoat adhesion derived from butyl rubber, and toughness, adhesiveness, and chemical resistance derived from epoxy resin and curing agent for epoxy resin. It has a wide range of physical properties and workability controllability, and its high solids content makes it possible to apply thick coatings, which not only increases the anticorrosion effect but also reduces the number of coatings required to obtain the desired film thickness. This makes it possible to shorten the construction period and reduce costs, and contributes to improving the safety and health of the working environment by reducing the amount of organic solvent that evaporates. The room temperature curing high solid content paint of the present invention can be used for factory plants, ships, bridges, steel pipes, port facilities, marine structures, anti-corrosion paints including seawall construction, vehicle undercoats, chemical-resistant floors, and factory floors. There are many fields such as Traditionally, rubber-based paints have had problems such as lack of cross-linking method to obtain sufficient film strength and adhesive strength, poor paintability, poor viscosity stability of the paint film, especially when forming a film at room temperature. Hypalon, which tends to have disadvantages such as stickiness, has been put into practical use.
It was limited to a few products such as chlorinated rubber and cyclized rubber. On the other hand, epoxy paints are used in many fields and have gained popularity due to their excellent adhesion, toughness, chemical resistance, wide range of physical property control, and workability control, as shown by many achievements. It came with flexibility,
There were shortcomings in impact resistance, recoat adhesion, weather resistance, etc. Therefore, in order to eliminate these drawbacks, we developed epoxy urethane resin, flexible epoxy resin,
The development of epoxy resin curing agents and flexibility imparting agents has been actively carried out. However, some of these paints have poor durability due to a decrease in flexibility due to changes over time, others rely only on plastic reinforcement and simply cause a decrease in toughness, and some of them impair the adhesion that is the advantage of epoxy paints. It was expensive and unsuitable for general use. Therefore, the inventors of the present invention have developed a material that maintains elasticity and flexibility over a long period of time, has excellent impact resistance, flexibility, adhesion to recoating, adhesion to the base, toughness and environmental barrier properties, and is thick. As a result of extensive research over a long period of time into a room-temperature-curing, high-solids paint that can be applied and is inexpensive, the object of the present invention is a room-temperature-curing, high-solids paint consisting of butyl rubber, epoxy resin, and a curing agent for epoxy resin. It was confirmed that they matched, and the present invention was completed. Next, the constituent components of the present invention will be explained. Component (A) described in the present invention is a butyl rubber paint component, which is a butyl rubber paint consisting of a color vehicle, a filler, an additive, and an organic solvent, as explained in sequence below. That is, the color vehicle refers to a solid film-forming component of a paint, and those that can be used in the present invention include butyl rubber, recycled butyl rubber, polyisobutylene, terpene resin, terpene-phenol resin, phenol resin, and aromatic resin. Examples include hydrocarbon resins, alicyclic hydrocarbon resins, aliphatic hydrocarbon resins, xylene resins, coumaron-indene resins, rosin and rosin-modified resins, straight asphalt, blown asphalt, and tar pitch. However, in the present invention, it is preferable that the color vehicle contains 20 to 80% by weight of the butyl rubber component. The butyl rubber component described in the present invention refers to a solid rubber component made of one or more of butyl rubber, recycled butyl rubber, and polyisobutylene. The characteristics of the butyl rubber component are gas barrier properties against corrosive substances such as oxygen, chlorine, sulfur dioxide, and water vapor, water resistance, salt water resistance, chemical resistance against acids and alkalis, weather resistance, aging resistance, and bending resistance. It is well known that it has excellent properties such as high electrical insulation resistance, and is a component that has particularly excellent environmental shielding ability. When butyl rubber was 20% by weight or less of the composition of the color vehicle constituting component (A), there was a tendency for poor return barrier properties and flexibility. Conversely, when the content was 80% by weight or more, toughness, adhesiveness, viscosity stability, and painting workability tended to be poor. Another important thing about butyl rubber paint components is the need to adjust their plasticity. In other words, one of the reasons why rubber-based paints have not been put to practical use is the poor solubility of rubber and the viscosity stability after dissolution.As a means of solving this poor solubility and viscosity stability, polymer Plasticity adjustment was performed. If the plasticity is high, the solubility and/or
Alternatively, problems occurred in the viscosity of the paint, and those with low plasticity had an adverse effect on the strength of the paint film and the adhesion of the surface of the paint film. In the present invention, the optimum Mooney viscosity is ML 1+4 (100
°C) within the range of 30 to 50, and improve the blending ratio with fillers, adhesion-imparting resins, etc., their types, and the method of mixing and dissolving them to solve the problems of solubility and viscosity stability. I've reached it. In addition to the above-mentioned butyl rubber component, examples of the color vehicle constituting the butyl rubber coating component which is component (A) of the present invention include a tackifying resin component and a bituminous material. The adhesion-imparting resin component includes terpene resin,
Terpene phenolic resin, phenolic resin,
Coumarone-indene resin, xylene resin, rosin and rosin-modified resin, aromatic hydrocarbon resin, alicyclic hydrocarbon resin, aliphatic hydrocarbon resin, etc. are used alone or in combination of two or more. The effects of using the adhesion-imparting resin are improvements in adhesion to the base and the base for recoating, coating film strength, solubility, and viscosity stability. As the bituminous component, straight asphalt, blown asphalt, tar pitch, etc. are used alone or in combination of two or more. The effects of using bituminous materials include improved corrosion protection, improved fillability of fillers, improved solubility, improved viscosity stability, and cost reduction. The fillers described in the present invention include clay, talc, mica, white carbon, carbon, asbestos, barium sulfate, calcium carbonate, silica sand, shirasu balloon, glass beads, titanium oxide, iron oxide, zinc oxide, white lead, and lead. Red, basic lead sulfate, zinc chromate, zinc phosphate, zinc molybdate ferrite, metal zinc powder, etc. are used alone or in combination of two or more. The effects of filling include adjusting workability and viscosity to prevent sagging during thick coating, adjusting the mixing ratio in product form, adjusting solid content, improving solubility, improving anti-corrosion effects, and preventing slipping of coated floors. It is. The additives described in the present invention include plasticizers, antifoaming agents, leveling agents, lubricants, surfactants, coupling agents, etc., and can be selected and used as necessary. The organic solvents described in the present invention refer to organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, and esters, and when used, one or two of them may be used. The above can be used together. In the present invention, as in general paints, the selection of solvent affects the coating performance, workability, and coating appearance, so the combination of the main solvent and co-solvent must be carefully selected. Furthermore, since the present invention performs a room-temperature curing reaction to achieve thick coating, if a high boiling point solvent with a boiling point of 150°C or higher is mainly used, the solvent will not come off easily and may adversely affect adhesive properties, chemical resistance, etc. Because of this, the boiling point
Low boiling point solvent below 100℃ and/or boiling point 100℃~
It is preferable to mainly use a solvent with a medium boiling point of 150°C. The component (B) described in the present invention is an epoxy resin and a curing agent for epoxy resin. The epoxy resin described in the present invention refers to a compound having two or more epoxies in one molecule. Examples of epoxy resins include bisphenol A
type epoxy resin, bisphenol F type epoxy resin, polyglycol type epoxy resin, novolac type epoxy resin, peracetic acid type epoxy resin, dimer acid type epoxy resin, etc., and they can be used alone or in combination of two or more types. can. Among these, bisphenol A type epoxy resin has excellent physical properties and price as a general-purpose epoxy resin, and can be sufficiently effective alone, but in order to improve viscosity and paintability, bisphenol It is preferable to use the F-type epoxy resin alone or in combination with the bisphenol A-type epoxy resin in any ratio. Furthermore, in order to improve viscosity, paintability, and flexibility, polyglycol type epoxy resin can be replaced with bisphenol A type epoxy resin, bisphenol F type epoxy resin, or bisphenol A type epoxy resin and bisphenol F type epoxy resin. It is preferable to use it in combination with a mixture. However, polyglycol type epoxy resin has disadvantages such as physical properties of coating film, adhesion, curing delay, etc.
It is preferable to use it within a range not exceeding 50% by weight. Further, in the present invention, the epoxy resin is preferably liquid at room temperature. In other words, if the epoxy resin is fixed at room temperature, it will have a high viscosity and poor paintability, viscosity stability, and flexibility.The viscosity of the paint will change greatly depending on the temperature, and depending on the season and region, hardening agents for epoxy resin may be added. When this happens, the stirring efficiency and painting workability are poor. In addition, in the present invention, based on 100 parts by weight of epoxy resin,
It is preferable to contain 100 to 400 parts by weight of the butyl paint as component (A). That is, when the amount of component (A) is 100 parts by weight or less for 100 parts by weight of the epoxy resin, flexibility, environmental barrier properties,
Poor recoat adhesion, acid resistance, and spray finish.
Conversely, the amount of component (A) is 400 parts by weight for 100 parts by weight of epoxy resin.
When the amount was more than 1 part by weight, the toughness, adhesion to the base, and spray coating properties were poor. Moreover, the shortcomings of epoxy paints, such as the yoking phenomenon, the brushing phenomenon, and the surface denting phenomenon unique to epoxy paints, do not occur for a long period of time due to the combined use with the butyl rubber component. The curing agent for epoxy resin described in the present invention is
It refers to a compound having a functional group that undergoes a curing reaction with an epoxy group in an epoxy resin when the cold-curable high solids paint of the present invention undergoes a curing reaction. As is well known, there are many chemical structures of curing agents for epoxy resins, and there are large differences in compatibility, water absorption, flexibility, etc. even between compounds belonging to the same series. It is necessary to check the curing agent for epoxy resin. In the present invention, since the curing reaction is carried out at room temperature, examples of curing agents for epoxy resins suitable for the present invention include polyamides, aliphatic amines, aliphatic modified amines, aromatic modified amines, keteimine, etc.
They can be used alone or in combination of two or more. It is not preferable to use aliphatic amine alone in terms of pot life, toxicity, odor, and recoat adhesion, and it is preferable to use it as a curing accelerator. In the present invention, it is preferable to use one or more of polyamide, aliphatic modified amine, and aromatic modified amine as the main curing agent for epoxy resin. In addition, the amount of curing agent for epoxy resin is determined by the reaction ratio with the epoxy resin, and the reaction ratio is
The range is preferably 0.7 to 1.0 mol epoxy resin curing agent/epoxy resin. In other words, if the reaction ratio is 0.7 mol or less, the environmental barrier properties, impact resistance, and bending resistance will be poor, whereas if the reaction ratio is 1.0 mol or more, the recoat adhesion, adhesion to the base, and environmental barrier properties will be poor. The reaction ratio is 0.7~
If the amount is outside the 1.0 mol range, it is particularly unsuitable for anticorrosion purposes. For curing accelerators, triethanolamine,
NN'-dimethylpiperazine, pyridine, quinoline, tetramethylguanidine, phenol, bisphenol A, tri(dimethylaminomethyl)phenol, DMP-30, etc. can be used, but in the present invention, phenols are used as coating materials. It is also preferable since it has little adverse effect on stack adhesion. When producing the room-temperature-curing high-solids paint of the present invention, the butyl rubber component and part or all of the filler and additives are added and kneaded using a general-purpose rubber kneading machine such as a roll, kneader, or Banbury mixer.
After dissolving in an organic solvent to form a rubber solution, if there are any remaining fillers and additives, add epoxy resin or a curing agent for epoxy resin, stir and mix, pass through a paint roll mill, and make the epoxy resin. A paint containing a curing agent for epoxy resin (hereinafter referred to as a hardening agent) is prepared. However, the above manufacturing method is only an example, and the present invention is not limited in any way. The method for using the room-temperature-curing high solids paint of the present invention is to measure the base agent and curing agent to a predetermined mixing ratio, mix thoroughly, and then
Cure at room temperature using airless spray, air spray, brush coating, roller coating, trowel coating, etc. Further, in order to obtain a predetermined thickness, the coating is coated again after a predetermined curing time and cured at room temperature. The product form of the room temperature curing high solid content paint of the present invention is as follows: (1) A two-component paint consisting of a main agent containing a butyl rubber component and an epoxy resin, and a curing agent containing an epoxy resin curing agent. (2) A liquid paint consisting of a base agent containing an epoxy resin, a butyl rubber component, and a curing agent containing a curing agent for epoxy resin. (3) A two-component paint consisting of a base agent containing a butyl rubber component and an epoxy resin, and a curing agent containing a butyl rubber component and an epoxy resin curing agent. (4) A three-component paint consisting of a butyl rubber paint containing a butyl rubber component, a base agent containing an epoxy resin, and a curing agent containing a curing agent for epoxy resin. The product can take the above four forms, and the storage stability and physical properties of the cured coating are not impaired in any of the forms. Next, the effects of the room temperature curing high solid content paint of the present invention will be explained. The room temperature curing high solids paint of the present invention has both the advantages of a butyl rubber component and the advantages of an epoxy paint.
It is a paint that covers each drawback. That is, environmental barrier properties derived from the butyl rubber component,
It has the advantages of impact resistance, bending resistance, and recoat adhesion, and has the advantages of adhesion, toughness, and chemical resistance derived from epoxy resins and curing agents for epoxy resins, as well as high solid content. The thick coating properties derived from the paint and the reduction in the number of coats reduce the number of coats, which shortens the process, saves labor, saves energy, reduces costs, improves corrosion resistance, and also improves occupational safety and health due to the small amount of volatile solvent, and reduces the price of the paint. If recycled butyl rubber, which is obtained by recycling automobile tire tubes, is used as the butyl rubber component, instead of having a large advantage in terms of low cost, it also has the advantage of effective use of resources. As described above, the room temperature curing high solids content paint of the present invention is a paint in a new field that combines the advantages of butyl rubber, epoxy resin, and curing agent for epoxy resin, which have not been seen in the conventional paint field, and is environmentally friendly. It is useful for the development of various industries by greatly extending the life cycle of coated objects by taking advantage of its barrier properties and impact resistance. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited in any way by the following Examples. Preparation method of test sample 1 Preparation of room temperature curing high solid content paint Add the butyl rubber component, filler, adhesion imparting resin and bituminous material, and knead with a pressure kneader at 50 to 70°C until sufficiently uniform. The compound is sufficiently swollen with an amount of organic solvent to give a solid content of 80%, stirred and dissolved, and when it becomes sufficiently homogeneous, it is treated with an ink roll and then added to the remaining organic solvent. It was made completely uniform. The mixture was further filtered through an 80-mesh wire mesh to produce a rubber paint. 2 Preparation of sample After mixing a specified amount of epoxy resin and a specified amount of curing agent for epoxy resin into the rubber paint obtained in 1-1 and making it sufficiently uniform, apply the specified amount with an airless sprayer and film applicator to obtain a standard It was cured for 14 days under these conditions. Test measurement method 1 Environmental barrier measurement method 1-1 Water resistance: According to JIS-K-5400 (section 7, 2), the conditions were: temperature 50 ± 2 ° C, humidity 98 ± 2%, time 96 hours. . 1-2 Salt water resistance: According to JIS-K-5400 (sections 7 and 6). 1-3 Weather resistance: According to JIS-K-5400 (paragraphs 6 and 17), the conditions were irradiation for 1000 hours. 2 Adhesion measurement method 2-1 Substrate adhesion: JIS-K-5400 (paragraph 6, 15)
According to. 2-2 Recoat adhesion: JIS-K-5400 (6, 10
JIS-K-
Adhesion was examined according to 5400 (section 6, 15). 3 Flexibility measurement method 3-1 Impact resistance: JIS-K-5400 (6, 13, 3
Section). 3-2 Flexibility: Conforms to JIS-K-5400 (items 6 and 16). The diameter of the mandrel was 6 mm. 4 Toughness measurement method 4-1 Pencil hardness: According to JIS-K-5400 (items 6 and 14). 5 Measuring method for chemical resistance 5-1 Acid resistance: According to JIS-K-5400 (section 7, 5). 5-2 Alkali resistance: JIS-K-5400 (7, 4
Section). 6 Method for Measuring Painting Workability 6-1 Painting Workability: Spray room temperature curing high solid content paint to a thickness of approximately 1 mm on the iron plate surface held vertically under the following conditions, and check the finish of the paint film after curing. I checked the condition. Spraying conditions Painter: Airless gun ALS
-122 type (manufactured by Iwata Painting Co., Ltd.) Pressure ratio: 1:20 Air pressure: 5 Kg/cm 2 Nozzle diameter: 0.4 mm 7 Viscosity stability measurement method 7-1 Mixture of component (A) and epoxy resin ( Predetermined amounts of each of component A) and epoxy resin were added and thoroughly mixed to create a sufficiently homogeneous mixture. After standing at room temperature for 24 hours, the viscosity before storage was measured using a B-type viscometer. Next, after storing at room temperature for 3 months, the viscosity was measured in the same manner as before storage. The viscosity change rate before and after storage was calculated. 7-2 Mixture of component (A) and epoxy resin Measurement was performed in the same manner as in 7-1, and the rate of viscosity change before and after storage was calculated. The calculation formula for the viscosity change rate used in 7-1 and 7-2 is as follows. Viscosity change rate (%) = Viscosity after storage / Viscosity before storage x 10
0 How to evaluate and display test results 1 Environmental barrier properties 1-1 Water resistance: ○ indicates that there is no abnormality when immersed in water according to JIS-K-5400 (paragraph 7, 2), otherwise × And so. 1-2 Salt water resistance: Items that were determined to be ``no abnormality even when immersed in sodium chloride solution'' according to JIS-K-5400 (items 7 and 6) were evaluated as ○, and others were evaluated as ×. 1-3 Weather resistance: Comparing with the sample product, cases where there were no wrinkles, blisters, peeling, cracks, discoloration, or yoking were rated as ○, and other cases were rated as ×. 2 Adhesion 2-1 Base adhesion: Judgment based on JIS-K-5400 (6, 15 grid test), evaluation scores of 8 or more were rated as ○, and scores of 6 or less were rated as ×. 2-2 Recoat adhesion: JIS-K-5400 (6, 10
If it is determined that there is no hindrance to overpainting in the judgment of ``overpainting suitability'', it is ×, if it is determined that there is no hindrance to overpainting, and JIS-K-
5400 (6th and 15th grid test), evaluation scores of 8 or more were marked as ○, and evaluation scores of 6 or less were marked as ×. 3 Flexibility 3-1 Impact resistance: JIS-K-5400 (6, 13, 3
Items that were judged to be "deformed by impact and cannot be peeled off" were marked as ○, and others were marked as ×. 3-2 Bending resistance: Items judged to be "resistant to bending" according to JIS-K-5400 (items 6 and 16) were marked as ○, and others were marked as ×. 4 Toughness 4-1 Pencil hardness: Pencil drag value determined by JIS-K-5400 (items 6 and 14) is 2H or more.
H and F were rated △, and HB and below were rated ×. 5 Chemical Resistance 5-1 Acid Resistance: Items that were determined to be ``no abnormality even when immersed in acid'' according to JIS-K-5400 (items 7 and 5) were marked as x for the others. 5-2 Alkali resistance: Items that were judged as "no abnormality even when immersed in alkali" according to JIS-5400 (items 7 and 4) were rated as ○, and others were rated as ×. 6 Paint workability: Finished condition after curing, no sagging,
Those with no aesthetic abnormalities such as surface irregularities were rated as ○, and the others were rated as ×. 7 Viscosity Stability 7-1 Mixed solution of component (A) and epoxy resin Add the prescribed amounts of component (A) and epoxy resin, store at room temperature for 3 months, and confirm that the viscosity change after storage is ± Items within 10% were marked as ○, and other items were marked as ×. 7-1 Mixed solution of component (A) and curing agent for epoxy resin Add the prescribed amounts of component (A) and curing agent for epoxy resin, store at room temperature for 3 months, and check the viscosity change after storage. Those within ±10% are 〇,
Other items were marked as ×.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
法に示した。
[Table] Shown in the law.
【表】
表２及び表３の試験結果より明らかな如く、実
施例１〜４は耐水性、耐塩水性、耐候性に代表さ
れた環境遮断性、下地密着性、塗り重ね密着性に
代表された接着性、耐衝撃性、耐屈曲性に代表さ
れた可撓性、鉛筆硬度に代表された強じん性、耐
酸・耐アルカリ性に代表された耐薬品性、粘度安
定性、塗装作業性に代表された塗装作業性に優
れ、本発明の目的にかなうものであつた。
比較例１は本発明の(B)成分を構成するエポキシ
樹脂が、常温に於て固体である場合であり、粘度
安定性、吹付塗装性、可撓性に劣つた。
比較例２は本発明のＢ成分を構成するエポキシ
樹脂100重量部に対して、(A)成分が100重量部以下
含有される場合であり、環境遮断性、塗り重ね密
着性、可撓性、耐酸性、塗装作業性に劣り、価格
面でも高価となる。
比較例３は本発明の(B)成分を構成するエポキシ
樹脂100重量部に対して、(A)成分が400重量部以上
含有される場合であり、強じん性、下地密着性、
塗装作業性に劣つた。
以上より、本発明の常温硬化型高固形分塗料は
ブチルゴム塗料成分の長所とエポキシ系塗料成分
の長所を併せ持ち、各々の欠点をカバーした塗料
である事が判る。即ち、ブチルゴム成分に由来す
る環境遮断性、耐衝撃性、耐屈曲性、塗り重ね密
着性の長所を有し、エポキシ樹脂及びエポキシ樹
脂用硬化剤に由来する接着性、強じん性、耐薬品
性の長所を有するのみならず、高固形分塗料に由
来する厚塗り性、及び塗装回数軽減に伴う工程短
縮、省力、省エネルギー、コスト削減、防食性の
改善、更には揮散溶剤量の少なさから労働安全衛
生面での改善、更に塗料の価格が安価である点で
多大のメリツトが生じる丈でなく、ブチルゴム成
分として自動車のタイヤチユーブから再生処理し
て得られるブチル再生ゴムを使用した場合は、資
源の有効利用というメリツトも加味される。
この様に、本発明の常温硬化型高固形分塗料
は、従来の塗料分野では見る事の出来なかつたブ
チルゴムとエポキシ樹脂及びエポキシ樹脂用硬化
剤の長所を合体させた新規な分野の塗料であり、
環境遮断性及び耐衝撃性等を活かし被塗物のライ
フサイクルを大巾に伸ばす事により、各種の産業
発展に役立つものである。[Table] As is clear from the test results in Tables 2 and 3, Examples 1 to 4 had excellent water resistance, salt water resistance, environmental barrier properties represented by weather resistance, base adhesion, and recoat adhesion. Flexibility as represented by adhesion, impact resistance, and bending resistance, toughness as represented by pencil hardness, chemical resistance as represented by acid and alkali resistance, viscosity stability, and painting workability. It had excellent coating workability and met the object of the present invention. Comparative Example 1 was a case in which the epoxy resin constituting component (B) of the present invention was solid at room temperature, and was inferior in viscosity stability, spray coating properties, and flexibility. Comparative Example 2 is a case in which the component (A) is contained in an amount of 100 parts by weight or less per 100 parts by weight of the epoxy resin constituting the B component of the present invention, and has excellent environmental barrier properties, recoating adhesion, flexibility, It has poor acid resistance and paint workability, and is also expensive. Comparative Example 3 is a case in which the component (A) is contained in an amount of 400 parts by weight or more based on 100 parts by weight of the epoxy resin constituting the component (B) of the present invention.
Paint workability was poor. From the above, it can be seen that the room temperature curing high solid content paint of the present invention is a paint that has both the advantages of the butyl rubber paint component and the advantages of the epoxy paint component, and covers the drawbacks of each. In other words, it has the advantages of environmental barrier properties, impact resistance, bending resistance, and recoat adhesion derived from the butyl rubber component, and the adhesiveness, toughness, and chemical resistance derived from the epoxy resin and curing agent for epoxy resin. Not only does it have the advantages of high solid content paint, it can be coated thickly, it reduces the number of coats, which reduces the number of coats, saves labor, saves energy, reduces costs, improves corrosion resistance, and reduces labor costs due to the small amount of volatile solvent. In addition to improving safety and health, as well as reducing the cost of paint, the use of recycled butyl rubber obtained from automobile tire tubes as a butyl rubber component reduces resource consumption. This also has the advantage of effective use of resources. In this way, the room-temperature-curing high-solids paint of the present invention is a paint in a new field that combines the advantages of butyl rubber, epoxy resin, and curing agent for epoxy resin, which have not been seen in the conventional paint field. ,
It is useful for the development of various industries by greatly extending the life cycle of coated objects by taking advantage of its environmental barrier properties and impact resistance.
Claims (1)
ら成るブチルゴム塗料成分の固形分中の展色剤
が20〜50重量％であり、展色剤を構成する固体
ブチル成分が展色剤の20〜80重量％であるブチ
ルゴム塗料成分と、 (B) エポキシ樹脂及びエポキシ樹脂用硬化剤成分
とから成り、 (B)成分を構成するエポキシ樹脂100重量部に対
して(A)成分であるブチルゴム塗料成分を100〜400
重量部含み、全塗料成分中の固形分が10重量％以
上であることを特徴とする常温硬化型高固形分塗
料。 ２ 前記(A)成分を構成する展色剤の組成のうちブ
チルゴム成分がブチルゴム、ブチル再生ゴムを１
種又は２種を併用して成ることを特徴とする特許
請求の範囲第１項記載の常温硬化型高固形分塗
料。 ３ 前記(A)成分を構成する展色剤の組成のうちブ
チルゴム成分がブチル再生ゴムであることを特徴
とする特許請求の範囲第１項記載の常温硬化型高
固形分塗料。 ４ 前記(B)成分を構成するエポキシ樹脂が、常温
に於て液状を呈するエポキシ樹脂であることを特
徴とする特許請求の範囲第１項記載の常温硬化型
高固形分塗料。[Scope of Claims] 1 (A) The color vehicle in the solid content of a butyl rubber coating component consisting of a color vehicle, a filler, an additive, and an organic solvent is 20 to 50% by weight, and constitutes the color vehicle. It consists of a butyl rubber coating component in which the solid butyl component is 20 to 80% by weight of the vehicle, and (B) an epoxy resin and a curing agent component for epoxy resin, based on 100 parts by weight of the epoxy resin constituting component (B). The butyl rubber paint component (A) is 100 to 400%
A room temperature curing high solid content paint characterized by a solid content of 10% by weight or more in all paint components, including parts by weight. 2 In the composition of the color vehicle constituting component (A), the butyl rubber component is 1% butyl rubber and 1% butyl recycled rubber.
2. The room-temperature-curing high solid content paint according to claim 1, characterized in that the paint is made of one or two types in combination. 3. The room-temperature curable high solid content paint according to claim 1, wherein the butyl rubber component in the composition of the vehicle constituting component (A) is recycled butyl rubber. 4. The room-temperature-curing high solid content paint according to claim 1, wherein the epoxy resin constituting the component (B) is an epoxy resin that is liquid at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6842683A JPS59193966A (en) | 1983-04-20 | 1983-04-20 | Room temperature curing high-solid coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6842683A JPS59193966A (en) | 1983-04-20 | 1983-04-20 | Room temperature curing high-solid coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193966A JPS59193966A (en) | 1984-11-02 |
| JPH0120660B2 true JPH0120660B2 (en) | 1989-04-18 |
Family
ID=13373348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6842683A Granted JPS59193966A (en) | 1983-04-20 | 1983-04-20 | Room temperature curing high-solid coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59193966A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4496335B2 (en) | 2003-06-26 | 2010-07-07 | 独立行政法人海上技術安全研究所 | Cover for crack inspection of structures |
| JP5415698B2 (en) * | 2008-01-07 | 2014-02-12 | 日東電工株式会社 | Damping and reinforcing sheet and method for damping and reinforcing thin plate |
| KR102161813B1 (en) * | 2012-08-29 | 2020-10-05 | 헴펠 에이/에스 | Anti-corrosive zinc primer coating compositions comprising hollow glass spheres and a conductive pigment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167331A (en) * | 1974-12-06 | 1976-06-10 | Mitsuboshi Belting Ltd | TOMAKUBOSUIYOEKIJOHORIKUROPURENGOMUSOSEIBUTSU |
-
1983
- 1983-04-20 JP JP6842683A patent/JPS59193966A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5167331A (en) * | 1974-12-06 | 1976-06-10 | Mitsuboshi Belting Ltd | TOMAKUBOSUIYOEKIJOHORIKUROPURENGOMUSOSEIBUTSU |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59193966A (en) | 1984-11-02 |
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