JPH04277575A - Modifier for coating material - Google Patents
Modifier for coating materialInfo
- Publication number
- JPH04277575A JPH04277575A JP6388591A JP6388591A JPH04277575A JP H04277575 A JPH04277575 A JP H04277575A JP 6388591 A JP6388591 A JP 6388591A JP 6388591 A JP6388591 A JP 6388591A JP H04277575 A JPH04277575 A JP H04277575A
- Authority
- JP
- Japan
- Prior art keywords
- paint
- resin
- modifier
- polycyclic aromatic
- phenol
- 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.)
- Withdrawn
Links
- 239000003607 modifier Substances 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title abstract description 13
- 238000000576 coating method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 title abstract 5
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- 239000003973 paint Substances 0.000 claims description 57
- -1 polycyclic aromatic compound Chemical class 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 235000019256 formaldehyde Nutrition 0.000 claims description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 3
- 150000005205 dihydroxybenzenes Chemical class 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003367 polycyclic group Chemical group 0.000 abstract 3
- 239000004971 Cross linker Substances 0.000 abstract 2
- 230000007797 corrosion Effects 0.000 abstract 2
- 238000005260 corrosion Methods 0.000 abstract 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 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 3
- 238000007654 immersion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は塗料に配合してその特性
を改良するための塗料改質材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint modifier that is added to paints to improve their properties.
【０００２】0002
【従来の技術】エポキシ樹脂、ウレタン樹脂等の合成樹
脂塗料については、取り扱い作業性を改善したり、耐水
性、耐薬品性、耐候性等を改善したりする目的で塗料改
質材を使用することが行われている。この種の改質材と
してはコ−ルタ−ル、ピッチ、アスファルト、ギルソナ
イト等の瀝青物質の他、石油樹脂、クマロン樹脂、キシ
レン樹脂、スチレンオリゴマ−等が知られている（特開
昭６２−５３３８１号公報）が、いずれも一長一短があ
るものであった。また、多環芳香族化合物をフォルムア
ルデヒド類やジヒドロキシベンゼンで重縮合した樹脂も
知られている（特開昭６２−５７４１３号、同６２−５
２１号公報）が、これを塗料改質材とすることを教える
ものはない。[Prior Art] For synthetic resin paints such as epoxy resins and urethane resins, paint modifiers are used to improve handling workability, water resistance, chemical resistance, weather resistance, etc. things are being done. Known modifiers of this type include bituminous substances such as coal tar, pitch, asphalt, and gilsonite, as well as petroleum resins, coumaron resins, xylene resins, and styrene oligomers. No. 53381), but all of them had advantages and disadvantages. Furthermore, resins made by polycondensing polycyclic aromatic compounds with formaldehydes or dihydroxybenzene are also known (JP-A-62-57413, JP-A-62-5
No. 21), but there is nothing that teaches that this can be used as a paint modifier.
【０００３】0003
【発明が解決しようとする課題】本発明は防食性能及び
耐候性を改善する塗料改質材を提供することを目的とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a paint modifier that improves anticorrosion performance and weather resistance.
【０００４】0004
【課題を解決するための手段】本発明は、多環芳香族化
合物１００モルに対し、フェノ−ル類１０〜５０モル及
びホルムアルデヒド類又はジヒドロキシベンゼン５０〜
２００モルとを反応させて得られる平均分子量３００〜
１０００の熱可塑性多環芳香族樹脂からなる塗料改質材
である。[Means for Solving the Problems] The present invention provides 10 to 50 moles of phenols and 50 to 50 moles of formaldehyde or dihydroxybenzene to 100 moles of a polycyclic aromatic compound.
The average molecular weight obtained by reacting with 200 mol of
1000 is a paint modifier made of thermoplastic polycyclic aromatic resin.
【０００５】本発明の塗料改質材の原料として用いる多
環芳香族化合物としては、ナフタレン、アルキルナフタ
レン、ジフェニルエ−テル等の２環の化合物、アセナフ
テン、アントラセン、フェナントレン、ジフェニレンオ
キサイド等の３環の化合物、ピレン等の４環以上の化合
物等が挙げられるが、アセナフテン、ナフタレン、メチ
ルナフタレン、ピレン及びジフェニルエ−テルからなる
群れから選ばれた１種又は２種以上の化合物である。コ
−ルタ−ルから蒸留あるいは晶析等の手段により分離さ
れたこれらの化合物又はこれらの化合物を含有する留分
を使用することは極めて有利である。Polycyclic aromatic compounds used as raw materials for the paint modifier of the present invention include two-ring compounds such as naphthalene, alkylnaphthalene, and diphenyl ether, and three-ring compounds such as acenaphthene, anthracene, phenanthrene, and diphenylene oxide. Examples include ring compounds and compounds having four or more rings such as pyrene, and one or more compounds selected from the group consisting of acenaphthene, naphthalene, methylnaphthalene, pyrene, and diphenyl ether. It is extremely advantageous to use these compounds or fractions containing these compounds separated from coal tar by means such as distillation or crystallization.
【０００６】もう一つの原料として用いるフェノ−ル類
としては、フェノ−ルの他にクレゾ−ル、キシレノ−ル
、エチルフェノ−ル、プロピルフェノ−ル、ブチルフェ
ノ−ル、ペンチルフェノ−ル等各種のアルキルフェノ−
ルが挙げられるが、好ましくはフェノ−ル又はアルキル
フェノ−ルであり、より好ましくはフェノ−ル又は炭素
数３〜５のアルキルフェノ−ルである。フェノ−ル類は
前記多環芳香族化合物１００モルに対して１０〜５０モ
ル、好ましくは１５〜３０モル用いられる。フェノ−ル
類が多くても、少なくてもエポキシ樹脂、エポキシ樹脂
等の塗料用樹脂との相溶性が低下したり、塗料に配合し
たとき耐水性が低下する。[0006] In addition to phenol, phenols used as another raw material include cresol, xylenol, ethylphenol, propylphenol, butylphenol, pentylphenol, etc. Alkylphenol
Among them, phenol or alkylphenol is preferable, and phenol or alkylphenol having 3 to 5 carbon atoms is more preferable. Phenols are used in an amount of 10 to 50 moles, preferably 15 to 30 moles, per 100 moles of the polycyclic aromatic compound. Whether the amount of phenols is large or small, the compatibility with epoxy resins and paint resins such as epoxy resins decreases, and when blended into paints, water resistance decreases.
【０００７】架橋剤としてはフォルムアルデヒド類又は
ジヒドロキシベンゼンが使用される。ホルムアルデヒド
類としては、ホルマリン、トリオキサン、パラフォルム
アルデヒド等が挙げられるが、好ましくはパラフォルム
アルデヒドである。ジヒドロキシベンゼンとしては、パ
ラキシリレングリコ−ルが好ましい。架橋剤は前記多環
芳香族化合物１００モルに対して５０〜２００モル、好
ましくは８０〜１５０モル用いられる。なお、このモル
比はパラフォルムアルデヒド等の多量体については、フ
ォルムアルデヒドに換算して計算したものである。架橋
剤が多くても、少なくても適当な分子量の多環芳香族樹
脂が得られず、相溶性が低下したり、防食効果が発揮さ
れないなどの問題を生ずる。多環芳香族化合物、フェノ
−ル類と架橋剤との反応は、有機スルフォン酸、硫酸、
しゅう酸、塩酸等のプロトン酸の存在下、９０〜２００
℃で行うことができる。反応終了後、水洗、蒸留等によ
り酸触媒や未反応原料を分離して平均分子量３００〜１
０００の熱可塑性多環芳香族樹脂を得る。この熱可塑性
多環芳香族樹脂は多環芳香族化合物１〜３個又は多環芳
香族化合物１〜３個とフェノ−ル類１〜２個がメチレン
基、ジメチレンエ−テル基又はキシリレン基を介して結
合したものであり、平均的な多環芳香族化合物とフェノ
−ル類の合計数は２〜４個である。Formaldehydes or dihydroxybenzene are used as crosslinking agents. Examples of formaldehydes include formalin, trioxane, and paraformaldehyde, with paraformaldehyde being preferred. As dihydroxybenzene, paraxylylene glycol is preferred. The crosslinking agent is used in an amount of 50 to 200 mol, preferably 80 to 150 mol, per 100 mol of the polycyclic aromatic compound. Note that this molar ratio is calculated in terms of formaldehyde for multimers such as paraformaldehyde. Even if the amount of crosslinking agent is large or small, a polycyclic aromatic resin having an appropriate molecular weight cannot be obtained, resulting in problems such as decreased compatibility and failure to exhibit anticorrosion effects. The reaction between polycyclic aromatic compounds, phenols and crosslinking agents can be performed using organic sulfonic acids, sulfuric acid,
In the presence of protonic acids such as oxalic acid and hydrochloric acid, 90 to 200
Can be done at ℃. After the reaction is completed, the acid catalyst and unreacted raw materials are separated by washing with water, distillation, etc., and the average molecular weight is 300 to 1.
000 thermoplastic polycyclic aromatic resin is obtained. This thermoplastic polycyclic aromatic resin is composed of 1 to 3 polycyclic aromatic compounds or 1 to 3 polycyclic aromatic compounds and 1 to 2 phenols via a methylene group, a dimethylene ether group, or a xylylene group. The average total number of polycyclic aromatic compounds and phenols is 2 to 4.
【０００８】本発明の塗料改質材は、エポキシ樹脂塗料
、ウレタン樹脂塗料等の各種の樹脂に配合して改質する
ことが可能であるが、防食効果を改善する目的からする
とエポキシ樹脂塗料、ウレタン樹脂塗料等の防食塗料に
配合することが適当である。特に、重防食塗料として知
られているエポキシ樹脂塗料、ウレタン樹脂塗料に配合
すると、防食効果がより一層向上する。塗料改質材の配
合量は、塗料改質材を含む塗料中の全樹脂分の１〜７０
重量％、好ましくは３０〜６０重量％の範囲である。
また、当然のことであるが塗料にはこの塗料改質材の他
に、顔料、充填材、溶剤等の配合材を配合することがで
きる。The paint modifier of the present invention can be blended with various resins such as epoxy resin paints and urethane resin paints to modify them; however, for the purpose of improving the anticorrosion effect, epoxy resin paints, It is appropriate to incorporate it into anticorrosive paints such as urethane resin paints. In particular, when it is added to epoxy resin paints and urethane resin paints, which are known as heavy anticorrosion paints, the anticorrosion effect is further improved. The blending amount of the paint modifier is 1 to 70% of the total resin content in the paint, including the paint modifier.
% by weight, preferably in the range 30-60% by weight. Furthermore, it goes without saying that in addition to this paint modifier, additives such as pigments, fillers, and solvents can be added to the paint.
【０００９】[0009]
【実施例】実施例１アセナフテン０．７０モル、パラ−
ｔ−ブチルフェノ−ル０．３０モル、パラフォルムアル
デヒド０．８０モルとを１０重量％のしゅう酸触媒の存
在下、約１１０℃で４時間反応したのち、トルエンを加
えて溶解させ、水洗して触媒を除去し、次いで減圧蒸留
して未反応原料を分離して熱可塑性多環芳香族樹脂を得
た。この熱可塑性多環芳香族樹脂は、蒸気圧浸透法によ
る平均分子量５３２、軟化点（Ｂ＆Ｒ）１１４℃であり
、これを塗料改質材とした。この塗料改質材をトルエン
／ＭＥＫ＝１：１のシンナ−に溶解させた５０％溶液６
．４４ｇを、エポキシ樹脂（ＡＥＲ６６４ 旭化成（
株）製 ６０％溶液）４．７５ｇ及び変性ポリアミン
系硬化剤（ラッカ−マイドＴＤ−９７３ＴＩ 大日本
インキ（株）製）０．７２ｇからなるエポキシ樹脂系塗
料樹脂と混合し、直径７５ｍｍの目皿に流し、２日間乾
燥後、相溶性を判定した。結果は樹脂ブリ−ドなく、塗
膜透明であり、塗料改質材として使用可能であることが
判明した。また、この塗料改質材をトルエン／ＭＥＫ＝
１：１のシンナ−に溶解させた５０％溶液１１．６ｇを
、１級ＯＨ含有エポキシポリオ−ル（ＥＰ−６０５０
旭電化（株）製）及びＴＤＩ系イソシアネ−ト（Ｄ−
１０３ 武田薬品（株）製）からなるウレタン樹脂系
塗料樹脂（イソシアネ−ト／エポキシポリオ−ル＝０．
８当量比）５．８ｇと混合し、上記と同様にして相溶性
を判定したところ、同様な優れた結果が得られた。また
、この塗膜について水蒸気透過度（１００μｍ 換算）
したところ、２５ｇ／ｍ２ ・ｄａｙであった。[Example] Example 1 Acenaphthene 0.70 mol, para-
After reacting 0.30 mol of t-butylphenol and 0.80 mol of paraformaldehyde at about 110°C for 4 hours in the presence of a 10% by weight oxalic acid catalyst, toluene was added to dissolve it, and the mixture was washed with water. The catalyst was removed, and unreacted raw materials were separated by distillation under reduced pressure to obtain a thermoplastic polycyclic aromatic resin. This thermoplastic polycyclic aromatic resin had an average molecular weight of 532 and a softening point (B&R) of 114° C. as measured by vapor pressure osmosis, and was used as a paint modifier. A 50% solution 6 of this paint modifier dissolved in a thinner of toluene/MEK=1:1.
．． 44g of epoxy resin (AER664 Asahi Kasei (
Co., Ltd., 60% solution) and 0.72 g of a modified polyamine curing agent (Laccamide TD-973TI, Dainippon Ink Co., Ltd.). After drying for 2 days, compatibility was determined. As a result, there was no resin bleed, the coating film was transparent, and it was found that it could be used as a paint modifier. In addition, this paint modifier is toluene/MEK=
11.6 g of a 50% solution dissolved in 1:1 thinner was added to a primary OH-containing epoxy polyol (EP-6050).
Asahi Denka Co., Ltd.) and TDI isocyanate (D-
103 Urethane resin-based paint resin (manufactured by Takeda Pharmaceutical Co., Ltd.) (isocyanate/epoxy polyol = 0.
When compatibility was determined in the same manner as above, similar excellent results were obtained. In addition, the water vapor permeability (100μm conversion) of this coating film
As a result, it was found to be 25 g/m2 ·day.
【００１０】実施例２アセナフテンとパラ−ｔ−ブチル
フェノ−ルのモル比を変えた他は実施例１に準じて塗料
改質材を得、これについて実施例１と同様にして相溶性
を判定した。エポキシ樹脂系塗料樹脂については、アセ
ナフテン／パラ−ｔ−ブチルフェノ−ルのモル比が９／
１及び８／２のとき、樹脂ブリ−ドなく、塗膜不透明で
あり、７／３のとき樹脂ブリ−ドなく、塗膜透明であっ
た。ウレタン樹脂系塗料樹脂については、モル比が９／
１のとき、樹脂ブリ−ドなく、塗膜不透明であり、８／
２及び７／３のとき樹脂ブリ−ドなく、塗膜透明であっ
た。いずれも、塗料改質材として使用可能であることが
判明した。しかし、モル比１０／０のときは、ウレタン
樹脂系塗料樹脂及びエポキシ樹脂系塗料樹脂についてい
ずれも樹脂ブリ−ド有りであり、塗料改質材として使用
不能であることが判明した。Example 2 A paint modifier was obtained in the same manner as in Example 1, except that the molar ratio of acenaphthene and para-t-butylphenol was changed, and the compatibility was determined in the same manner as in Example 1. . For epoxy resin paint resin, the molar ratio of acenaphthene/para-t-butylphenol is 9/
At 1 and 8/2, there was no resin bleed and the coating was opaque, and at 7/3, there was no resin bleed and the coating was transparent. For urethane resin-based paint resin, the molar ratio is 9/
When it is 1, there is no resin bleed and the coating film is opaque, and when it is 8/
At 2 and 7/3, there was no resin bleed and the coating film was transparent. All of them were found to be usable as paint modifiers. However, when the molar ratio was 10/0, resin bleed occurred in both the urethane resin-based paint resin and the epoxy resin-based paint resin, and it was found that they could not be used as paint modifiers.
【００１１】実施例３パラ−ｔ−ブチルフェノ−ルの代
わりにフェノ−ルを使用し、アセナフテンとフェノ−ル
のモル比を変えた他は実施例１に準じて塗料改質材を得
、これについて実施例１と同様にして相溶性を判定した
。エポキシ樹脂系塗料樹脂については、アセナフテン／
フェノ−ルのモル比が８／２のとき、樹脂ブリ−ドなく
、塗膜僅かに不透明であった。ウレタン樹脂系塗料樹脂
については、モル比が８／２のとき、樹脂ブリ−ドなく
、塗膜不透明であり、７／３のとき樹脂ブリ−ドなく、
塗膜透明であった。いずれも、塗料改質材として使用可
能であることが判明した。Example 3 A paint modifier was obtained according to Example 1 except that phenol was used instead of para-t-butylphenol and the molar ratio of acenaphthene and phenol was changed. The compatibility was determined in the same manner as in Example 1. For epoxy resin paint resin, acenaphthene/
When the molar ratio of phenol was 8/2, there was no resin bleed and the coating was slightly opaque. Regarding urethane resin paint resin, when the molar ratio is 8/2, there is no resin bleed and the coating film is opaque, and when the molar ratio is 7/3, there is no resin bleed,
The coating film was transparent. All of them were found to be usable as paint modifiers.
【００１２】実施例４表１に示す多環芳香族化合物、パ
ラ−ｔ−ブチルフェノ−ル及び架橋剤とを実施例１の方
法に準じて反応させて、表１に示す塗料改質材を得た。
架橋剤がパラフォルムアルデヒドのとき、多環芳香族化
合物／パラ−ｔ−ブチルフェノ−ルのモル比は８／２、
パラフォルムアルデヒド／多環芳香族化合物のモル比は
０．８〜１．５とし、架橋剤がパラキシリレングリコ−
ルのとき、多環芳香族化合物／パラ−ｔ−ブチルフェノ
−ルのモル比は７／３、キシリレングリコ−ル／多環芳
香族化合物のモル比は０．５５〜０．６とした。得られ
た塗料改質材について、実施例１と同様にして相溶性の
判定及び水蒸気透過度の測定を行った。結果は相溶性に
ついては、全ての塗料改質材がウレタン系塗料及びエポ
キシ系塗料の両者について、相溶性良好であった。その
他の結果を表１に示す。Example 4 A polycyclic aromatic compound shown in Table 1, para-t-butylphenol and a crosslinking agent were reacted according to the method of Example 1 to obtain a paint modifier shown in Table 1. Ta. When the crosslinking agent is paraformaldehyde, the molar ratio of polycyclic aromatic compound/para-t-butylphenol is 8/2,
The molar ratio of paraformaldehyde/polycyclic aromatic compound is 0.8 to 1.5, and the crosslinking agent is paraxylylene glyco-
When the polycyclic aromatic compound/para-t-butylphenol molar ratio was 7/3, and the xylylene glycol/polycyclic aromatic compound molar ratio was 0.55 to 0.6. Regarding the obtained paint modifier, the compatibility was determined and the water vapor permeability was measured in the same manner as in Example 1. The results showed that all paint modifiers had good compatibility with both urethane paints and epoxy paints. Other results are shown in Table 1.
【００１３】[0013]
【表１】[Table 1]
【００１４】次に、上記塗料改質材を配合したウレタン
樹脂系防食塗料をつくり、塗料性能を測定した。塗料は
主剤８５重量％と硬化剤１５重量％からなる２液型とし
、主剤中に上記塗料改質材（６０％トルエン溶液）２３
．８重量部、エポキシポリオ−ル（６０％エピクロンＨ
−２１５）２１．３重量部、タルカンパウダ−２５．３
重量部、酸化チタン５．０重量部、無水石膏２．５重量
部、よう変剤０．９重量部、シンナ−他６．２重量部を
配合し、硬化剤中にトリメチロ−ルプロパンアダクツＴ
ＤＩ（７５％タケネ−トＤ−１０３Ｈ）１１．４重量部
及びトルエン３．６重量部を配合した。この両者を混合
して塗膜を形成し、室温で７日間硬化、乾燥したのち、
塩水促進試験（基準値 ７日間浸漬後、ふくれの発生
など異常がないこと）、耐原油促進試験（基準値 ７
日間浸漬後の重量変化が０．５ｇ／ｄｃｍ２ 以下であ
ること）、塩水噴霧試験（３０日間噴霧後のクロスカッ
ト部のはくり巾ｍｍ）、温度勾配試験（塗膜側を６０℃
、鉄板側を１５℃としてふくれの発生が生じない期間ｄ
ａｙ）を行った。その他、耐侯性試験（ウエザ−メ−タ
−での上塗り塗料の黄変度）を行ったが、これはいずれ
も良好であった。また、比較として塗料改質材を配合し
ない塗料についても試験を行った。結果を表２に示す。[0014] Next, a urethane resin anticorrosive paint containing the above paint modifier was prepared, and the paint performance was measured. The paint is a two-component type consisting of 85% by weight of the main agent and 15% by weight of the curing agent, and the above paint modifier (60% toluene solution) 23% is added to the main agent.
．． 8 parts by weight, epoxy polyol (60% Epicron H
-215) 21.3 parts by weight, talcan powder -25.3
parts by weight, 5.0 parts by weight of titanium oxide, 2.5 parts by weight of anhydrite, 0.9 parts by weight of a modifier, 6.2 parts by weight of thinner, etc., and a trimethylolpropane adduct in the hardening agent. T
11.4 parts by weight of DI (75% Takenate D-103H) and 3.6 parts by weight of toluene were blended. After mixing these two to form a coating film, curing and drying at room temperature for 7 days,
Salt water acceleration test (standard value: no abnormalities such as blistering after 7 days immersion), crude oil resistance acceleration test (standard value: 7 days)
weight change after immersion for 1 day is 0.5 g/dcm2 or less), salt spray test (peeling width of cross-cut part after 30 days of immersion in mm), temperature gradient test (paint side 60℃
, period d when the iron plate side is set at 15℃ and no blistering occurs.
ay) was carried out. In addition, a weather resistance test (yellowing degree of the top coat using a weather meter) was conducted, and all results were good. For comparison, a test was also conducted on a paint that did not contain a paint modifier. The results are shown in Table 2.
【００１５】[0015]
【表２】[Table 2]
【００１６】[0016]
【発明の効果】本発明の塗料改質材は、これを配合する
ことにより防食性能を高めた塗料とすることができる。[Effects of the Invention] By blending the paint modifier of the present invention, a paint with improved anticorrosion performance can be obtained.
Claims (2)
フェノ−ル類１０〜５０モル並びにホルムアルデヒド類
及びジヒドロキシベンゼン類から選ばれる少なくとも１
種の架橋剤５０〜２００モルとを反応させて得られる平
均分子量３００〜１０００の熱可塑性多環芳香族樹脂か
らなることを特徴とする塗料改質材。Claim 1: For 100 mol of polycyclic aromatic compound,
10 to 50 moles of phenols and at least one selected from formaldehydes and dihydroxybenzenes
1. A paint modifier comprising a thermoplastic polycyclic aromatic resin having an average molecular weight of 300 to 1,000 obtained by reacting a seed crosslinking agent with 50 to 200 moles.
フタレン、メチルナフタレン、ピレン又はジフェニルエ
−テルである請求項１記載の塗料改質材。2. The paint modifier according to claim 1, wherein the polycyclic aromatic compound is acenaphthene, naphthalene, methylnaphthalene, pyrene or diphenyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6388591A JPH04277575A (en) | 1991-03-05 | 1991-03-05 | Modifier for coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6388591A JPH04277575A (en) | 1991-03-05 | 1991-03-05 | Modifier for coating material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04277575A true JPH04277575A (en) | 1992-10-02 |
Family
ID=13242192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6388591A Withdrawn JPH04277575A (en) | 1991-03-05 | 1991-03-05 | Modifier for coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04277575A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016199A1 (en) * | 1999-08-31 | 2001-03-08 | Nippon Steel Chemical Co., Ltd. | Aromatic oligomer and use thereof |
| JP2005133005A (en) * | 2003-10-31 | 2005-05-26 | Nippon Parkerizing Co Ltd | Coating composition and precoated steel sheet coated with the same |
-
1991
- 1991-03-05 JP JP6388591A patent/JPH04277575A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001016199A1 (en) * | 1999-08-31 | 2001-03-08 | Nippon Steel Chemical Co., Ltd. | Aromatic oligomer and use thereof |
| US6713591B1 (en) | 1999-08-31 | 2004-03-30 | Nippon Steel Chemicals Co., Ltd. | Aromatic oligomer and use thereof |
| KR100687395B1 (en) * | 1999-08-31 | 2007-02-27 | 신닛테츠가가쿠 가부시키가이샤 | Aromatic Oligomer and Use Thereof |
| JP2005133005A (en) * | 2003-10-31 | 2005-05-26 | Nippon Parkerizing Co Ltd | Coating composition and precoated steel sheet coated with the same |
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Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980514 |