JPS62169864A - Primer resin composition - Google Patents
Primer resin compositionInfo
- Publication number
- JPS62169864A JPS62169864A JP1115386A JP1115386A JPS62169864A JP S62169864 A JPS62169864 A JP S62169864A JP 1115386 A JP1115386 A JP 1115386A JP 1115386 A JP1115386 A JP 1115386A JP S62169864 A JPS62169864 A JP S62169864A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resistance
- primer
- appearance
- coating
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 10
- -1 polytetramethylene Polymers 0.000 claims abstract description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 43
- 239000011248 coating agent Substances 0.000 abstract description 39
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 27
- 239000000203 mixture Substances 0.000 abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 14
- 229920005749 polyurethane resin Polymers 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 53
- 229920003023 plastic Polymers 0.000 description 30
- 239000004033 plastic Substances 0.000 description 30
- 238000012360 testing method Methods 0.000 description 27
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 20
- 239000003973 paint Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000010422 painting Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 206010039509 Scab Diseases 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000002990 reinforced plastic Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 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 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 101000664887 Homo sapiens Superoxide dismutase [Cu-Zn] Proteins 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 102100038836 Superoxide dismutase [Cu-Zn] Human genes 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は電着塗装された自動車車体用鋼板および各種プ
ラスチック素材に対し、同時に適用可能なプライマー用
樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition for a primer that can be simultaneously applied to electrocoated steel plates for automobile bodies and various plastic materials.
（従来の技術）
従来、自動車車体用鋼板においては、鋼板、化成処理皮
膜、電着塗膜、部分的にチンピングプライマーまたはス
トーンガードコート、中塗り塗膜および上塗り塗膜がそ
れぞれ塗装されている。また各種プラスチック部品は、
車体の塗装とは別に、プラスチック素材の種類別に専用
プライマーを塗装したのち、ポリウレタン樹脂系、アミ
ノアルキド樹脂系、アミノアクリル樹脂系の塗料、から
な″る上塗り塗料が塗装されている。また車体と一体塗
装の場合は、ポリアミド樹脂、ポリブチレンテレフタレ
ート樹脂、ポリウレクン樹脂、ポリカーボネート樹脂お
よび、それらの強化プラスチック樹脂などに付着性を有
する専用プライマーを塗装し、次いで自動車の車体を構
成する鋼板に適した脂肪酸変性ポリエステル樹脂、オイ
ルフリーポリエステル樹脂、エポキシ変性ポリエステル
樹脂、メラミン樹脂などを主成分とする中塗り塗料が塗
装され、中塗り塗装後１３０〜１５０℃で１５〜４０分
間焼付が行なわれ、さらにアミノアルキド樹脂および／
またはアミノアクリル樹脂を主成分とする上塗り塗料を
塗装し、塗装後１３０〜１５０℃で１５〜４０分間焼付
が行なわれ塗膜が構成されている。(Prior art) Conventionally, steel sheets for automobile bodies have been coated with a chemical conversion coating, an electrodeposited coating, a partial chimping primer or stone guard coating, an intermediate coating, and a top coating. . In addition, various plastic parts are
Separately from painting the car body, a special primer is applied for each type of plastic material, and then a top coat of paint made of polyurethane resin, amino alkyd resin, or amino acrylic resin is applied. In the case of integral painting, a special primer that has adhesive properties is applied to polyamide resin, polybutylene terephthalate resin, polyurethane resin, polycarbonate resin, and their reinforced plastic resins, and then a fatty acid suitable for the steel plates that make up the car body is applied. An intermediate coating mainly composed of modified polyester resin, oil-free polyester resin, epoxy modified polyester resin, melamine resin, etc. is applied. After the intermediate coating is applied, baking is performed at 130 to 150°C for 15 to 40 minutes, and then amino alkyd is applied. resin and/
Alternatively, a top coat containing aminoacrylic resin as a main component is applied, and after application, baking is performed at 130 to 150°C for 15 to 40 minutes to form a coating film.
（発明が解決しようとする問題点）
しかしながら、このような従来の塗装方法によると鋼板
素材上とプラスチック素材上でそれぞれ異なる塗膜構成
となり、使用する塗料や塗装工程が異なることから
（１）鋼板素材塗装用とプラスチック素材塗装用と別々
の塗装設備を設置しなければならず、作業効率が悪いば
かりでなく、膨大な設備投資が必要となる。(Problems to be Solved by the Invention) However, such conventional coating methods result in different coating film compositions on the steel sheet material and the plastic material, and the paints and coating processes used are different. Separate painting equipment must be installed for painting materials and for painting plastic materials, which not only reduces work efficiency but also requires a huge investment in equipment.
（２）鋼板素材上とプラスチック素材上との色調や光沢
などの外観に差が生じ、自動車全体としての商品価値を
低下させる。(2) Differences in appearance, such as color tone and gloss, occur between the steel sheet material and the plastic material, reducing the commercial value of the automobile as a whole.
（３）鋼板素材部とプラスチック素材部での塗装塗膜の
耐久性に差を生じ、長期的な観点からの自動車の美観を
損ねる。(3) There is a difference in the durability of the paint film between the steel sheet material part and the plastic material part, which impairs the aesthetic appearance of the automobile from a long-term perspective.
（４）プラスチック素材に専用プライマーを塗装後、鋼
材素材部に取り付け、以降同時塗装する場合は、前記（
１１〜（３）の問題はないが、中塗り塗料、上塗り塗料
の選択に際し、プラスチック素材用に合わせて軟質塗膜
にすると、耐候性、ポリッシュ性、耐溶剤性および耐ｌ
η染性等が低下し、反面、鋼板素材用に合わせて硬質塗
膜にすると、プラスチック素材上での低温時に於ける耐
衝撃性が低下する等、中塗り塗料及び上塗り塗料の制約
を受ける。(4) After painting the plastic material with a special primer, attach it to the steel material part, and then apply the same coating as described above (
There are no problems with 11 to (3), but when selecting intermediate and top coats, if you choose a soft coating for plastic materials, you will have problems with weather resistance, polishability, solvent resistance, and lubricant resistance.
On the other hand, if a hard coating film is used for steel sheet materials, the impact resistance at low temperatures on plastic materials will be reduced, and there will be restrictions on intermediate coatings and top coatings.
という問題点があった。There was a problem.
（問題点を解決するための手段）
本発明者らは上記問題点を解決すべく鋭意研究の結果、
特定のポリウレタン樹脂をプライマーとして用いること
により、車体外板用および部品用として近年研究されて
いるエンジニアリングプラスチック素材、例えばポリア
ミド樹脂、ポリブチレンテレフタレート樹脂、ポリウレ
タン樹脂、ポリカーボネート樹脂、およびそれらの強化
プラスチック樹脂などの素材と密着性が良い上に、プラ
スチック素材に比べて伸び率の低いアミノアルキド樹脂
またはアミノアクリル樹脂を主成分とする中塗りおよび
／または上塗り塗料を塗り重ねることができ、かつ低温
時の耐衝撃性、一体塗装後の外観性に優れた塗膜が得ら
れることを見出した。(Means for Solving the Problems) As a result of intensive research by the present inventors to solve the above problems,
By using a specific polyurethane resin as a primer, engineering plastic materials that have been researched in recent years for use in car body exterior panels and parts, such as polyamide resin, polybutylene terephthalate resin, polyurethane resin, polycarbonate resin, and their reinforced plastic resins, etc. In addition to having good adhesion to other materials, intermediate and/or top coats mainly composed of aminoalkyd resin or aminoacrylic resin, which have a lower elongation rate than plastic materials, can be applied over and over again, and are resistant to low temperatures. It has been found that a coating film with excellent impact resistance and appearance after integral coating can be obtained.
また鋼板部に対しては電着塗膜と中塗り塗膜との間に塗
装することにより塗膜の耐チッピング性、耐スキャブ錆
性、外観性などに著しい効果があることを見出し本発明
を達成するに至った。Furthermore, for steel plate parts, it was discovered that coating between the electrodeposited coating and the intermediate coating had a significant effect on the chipping resistance, scab rust resistance, appearance, etc. of the coating, and the present invention was developed. I have achieved this goal.
即ち本発明のプライマー用樹脂組成物は、（Ａ）末端に
水酸基を有する分子ｍ １ 、５ｏｏ〜４ 、０００の
ポリテトラメチレングリコールまたはポリカプロラクト
ンエステルと
（Ｂ）ヘキサメチレンジイソシアネートまたはイソホロ
ンジイソシアネートと
（Ｃ） インホロンジアミン
との反応物で、Ｂ／Ａ ＝ １．５〜３．０モルでかつ
分子量が１０，０００〜４０，０００の範囲にある反応
物であるポリウレタン樹脂を主成分としたことを特徴と
する。That is, the resin composition for a primer of the present invention comprises (A) a polytetramethylene glycol or polycaprolactone ester having molecules m 1 , 5oo to 4,000 having a hydroxyl group at the terminal, (B) hexamethylene diisocyanate or isophorone diisocyanate, and (C ) The main component is a polyurethane resin which is a reaction product with inphorondiamine and has a B/A = 1.5 to 3.0 mol and a molecular weight in the range of 10,000 to 40,000. Features.
この発明において必須成分は上記ポリウレタン樹脂であ
り、ポリウレタン樹脂に使用されるポリオールとしては
、アジピン酸のような二塩基酸とエチレングリコール（
ＰＨ八）、１．４−フ゛タンジオール（ＰＢＡ）のよう
なジオールから成るポリエステルポリオールや、ポリプ
ロピレングリコールエーテル（ＰＰＧ）、ポリエチレン
グリコールエーテル（ＰＥＧ）などのポリエーテルポリ
オールが一般的であるが、これらのポリオールから成る
ポリウレタン樹脂のガラス転移点は、ポリテトラメチレ
ングリコール（ＰＴＧ）またはポリカプロラクトンエス
テル（ＰＣＬ）から成るポリウレタン樹脂に比べ一般的
に高いため、低温時における衝撃性に劣る。一方ポリウ
レタンに使用されるジイソシアネートとしては、トリレ
ンジイソシアネート（ＴＤＩ）や、４．４′−ジフェニ
ルメタンジイソシアネート（ＭＤＩ）が一般的であるが
、これらのジイソシアネートから成るポリウレタンも、
ヘキサメチレンジイソシアネート（ＨＭＤＩ）、イソホ
ロンジイソシアネート（Ｉｒ’ＤＩ）から成るポリウレ
タンより低温時における衝撃性の点で劣る。In this invention, the essential component is the above polyurethane resin, and the polyols used in the polyurethane resin include dibasic acids such as adipic acid and ethylene glycol (
Polyester polyols consisting of diols such as PH8) and 1,4-butanediol (PBA), and polyether polyols such as polypropylene glycol ether (PPG) and polyethylene glycol ether (PEG) are common; The glass transition point of polyurethane resins made of polyols is generally higher than that of polyurethane resins made of polytetramethylene glycol (PTG) or polycaprolactone ester (PCL), so they have poor impact resistance at low temperatures. On the other hand, tolylene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI) are commonly used as diisocyanates for polyurethanes, but polyurethanes made from these diisocyanates also
It is inferior to polyurethanes made of hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (Ir'DI) in terms of impact resistance at low temperatures.
塗料物性として低温特性と耐熱性は両立しないとされて
いるが、上記の本発明のポリオールとジイソシアネート
のある特定の範囲の組み合せに、さらに特定の鎖延長剤
を組み合せることにより、低温特性のみならずある程度
高い温度においても軟化しない樹脂が得られることを見
出した。さらにまた、これらの樹脂は、スプレー塗装さ
れるため溶剤に溶解しなければ使用できない。一般に耐
熱性のよいポリウレタン樹脂は溶剤に溶けにくいが、上
記のある特定範囲の樹脂は一般に塗料に使用されている
溶剤に可溶である。この特定の範囲とは、まず使用され
るＩ’ＴＧまたはＰＣＬの分子量がｔ 、 ｓｏｏ〜４
、０００の範囲にあることである。分子量が１ 、５
００未満のポリオールを用いた場合はウレタン基の割合
が高くなり、低温時に於ける耐衝撃性、耐湿性が劣る。It is said that low-temperature properties and heat resistance are not compatible with each other as physical properties of paints, but by combining the polyol and diisocyanate of the present invention in a certain range with a specific chain extender, it is possible to achieve only low-temperature properties. It has been found that a resin that does not soften even at a somewhat high temperature can be obtained. Furthermore, since these resins are spray-painted, they cannot be used unless they are dissolved in a solvent. In general, polyurethane resins with good heat resistance are difficult to dissolve in solvents, but resins in a certain range mentioned above are generally soluble in solvents used in paints. This specific range means that the molecular weight of I'TG or PCL used is t, soo ~ 4
, 000. Molecular weight is 1,5
If a polyol having a molecular weight of less than 0.00 is used, the proportion of urethane groups will be high, resulting in poor impact resistance and moisture resistance at low temperatures.
また分子量が４．０００を越える場合は、ポリオールの
性質が著しく表われるため、常温で粘着がある弱い樹脂
となり、塗膜の外観が著しく劣る。さらにこの範囲にあ
るポリオールを用いた場合でも、ＴＤＩやＭＤＩのよう
な芳香環を持ったイソシアネートと組み合せると、低温
時に於ける耐衝撃性が劣るだけでなく、一般的な塗料用
溶剤にも溶けに（くなる。ＩＩＭＤＩまたはＩＰＤＩと
上記の範囲のポリオールの組み合せでは、低温時に於け
る耐衝撃性が非常に優れた物となる。さらにＮＧＯ１０
１１＝１．５〜３．０モルの範囲にすることにより高温
特性と溶解性のバランスがとれるようになってくるが、
鎖延長剤としてイソホロンジアミン（ＩＰＤＡ）を用い
ることにより、より優れたものとなる。If the molecular weight exceeds 4.000, the properties of the polyol will be significantly exhibited, resulting in a weak resin that is sticky at room temperature, and the appearance of the coating film will be significantly inferior. Furthermore, even when polyols within this range are used, if they are combined with isocyanates with aromatic rings such as TDI and MDI, they not only have poor impact resistance at low temperatures, but also are not compatible with common paint solvents. The combination of IIMDI or IPDI and a polyol in the above range provides a product with extremely excellent impact resistance at low temperatures.Furthermore, NGO10
By setting 11=1.5 to 3.0 moles, a balance between high temperature properties and solubility can be achieved,
The use of isophorone diamine (IPDA) as a chain extender makes it even better.
なお、Ａ成分である末端に水酸基を有する分子Ｉｆ 、
５００〜４，０００のポリテトラメチレングリコール
またはポリカプロラクトンエステルとＢ成分であるヘキ
サメチレンジイソシアネートまたはイソホロンジイソシ
アネートとのＮＧＯｌｏｌｌのモル比が１．５〜３．０
および反応物の分子量が１０，０００〜４０．０００の
範囲にあることを規定することにより、イソホロンジア
ミンの使用量は自動的に規定される。ＮＣ０１０Ｈのモ
ル比が１．５モル未満の場合、常温でも粘着のある弱い
塗膜となるために、低温時に於ける耐衝撃性、外観、耐
湿性が劣り、３．０モルを越えると溶剤への溶解性が極
端に低下すると共に、低温時に於ける耐衝撃性が劣る。In addition, the molecule If having a hydroxyl group at the terminal, which is component A,
The molar ratio of NGOloll of polytetramethylene glycol or polycaprolactone ester of 500 to 4,000 and hexamethylene diisocyanate or isophorone diisocyanate as component B is 1.5 to 3.0.
By specifying that the molecular weight of the reactant is in the range of 10,000 to 40,000, the amount of isophorone diamine used is automatically specified. If the molar ratio of NC010H is less than 1.5 mol, the film will be sticky and weak even at room temperature, resulting in poor impact resistance, appearance, and moisture resistance at low temperatures, and if it exceeds 3.0 mol, it will become a solvent. The solubility of the material is extremely reduced, and the impact resistance at low temperatures is poor.
ポリウレタン用の鎖延長剤としては一般的にエチレング
リコールや１．４−ブタンジオールが用いられるが、本
発明の用途分野では軟化点が低くなりすぎると溶解性に
も問題が出てくる。しかし脂環を持ったＩＰＤＡを用い
ると、ＮＧＯ基との反応により生成する尿素基の凝集力
により軟化点が高くなるとともに、脂環の影響で溶剤へ
の溶解性も向上することが見出された。このような組み
合せにより得られた樹脂は、トルエン、酢酸エチル、ア
セトン、メチルエチルケトン、イソプロピルアルコール
などの溶剤に溶解して使用されるが、樹脂の分子量が１
０．０００未満であると強度が極端に低くなるし、４０
，０００を越えるとスプレー塗装ができにくい溶液とな
ってしまう。性能と作業性の面から１０．０００〜４０
．０００の分子量が好ましい。Ethylene glycol and 1,4-butanediol are generally used as chain extenders for polyurethane, but in the field of application of the present invention, if the softening point becomes too low, problems will arise in solubility. However, it has been found that when IPDA with an alicyclic ring is used, the softening point becomes higher due to the cohesive force of the urea group generated by the reaction with the NGO group, and the solubility in solvents also improves due to the influence of the alicyclic group. Ta. The resin obtained by such a combination is used by dissolving it in a solvent such as toluene, ethyl acetate, acetone, methyl ethyl ketone, or isopropyl alcohol.
If it is less than 0.000, the strength will be extremely low;
,000, the solution becomes difficult to spray paint. 10,000 to 40 in terms of performance and workability
．． A molecular weight of 000 is preferred.
本発明のプライマー用樹脂組成物はつぎのようにして製
造される。The resin composition for a primer of the present invention is produced as follows.
攪拌機付きのフラスコに、分子量 １ 、５００〜４，
０００のポリテトラメチレングリコールまたはポリカプ
ロラクトンエステルとヘキサメチレンジイソシアネート
またはイソホロンジイソシアネートのＮＣ０１０！１の
モル比が１．５〜３．０の範囲に入る量を仕込み、トル
エン、酢酸エチル、アセトン、メチルエチルケトンなど
の溶剤を加えて溶解した後、窒素ガス気流中、７０〜９
０℃で２〜６時間反応させる。Molecular weight 1,500-4, in a flask equipped with a stirrer.
000 polytetramethylene glycol or polycaprolactone ester and hexamethylene diisocyanate or isophorone diisocyanate in an amount in which the molar ratio of NC010!1 falls within the range of 1.5 to 3.0, and toluene, ethyl acetate, acetone, methyl ethyl ketone, etc. After adding and dissolving the solvent, in a nitrogen gas stream, 70 to 9
React at 0°C for 2-6 hours.
つぎに、イソホロンジアミンとイソプロピルアルコール
やｎブチルアルコールなどの混合物を添加して７０〜９
０℃で１〜６時間反応させて分子量が１０．０００〜４
０．０００のプライマー用樹脂組成物が得られる。Next, a mixture of isophorone diamine and isopropyl alcohol or n-butyl alcohol is added to give a 70-90%
React at 0℃ for 1 to 6 hours to obtain a molecular weight of 10.000 to 4.
A primer resin composition of 0.000 is obtained.
このようにして得られた樹脂溶液を塗装する場合、ポリ
ウレタン塗料に用いられる通常のポリイソシアネートを
硬化剤として、例えば、コロネート上１コロネート１１
Ｌ、コロネー１−［ＥＩ＋（商品名：いづれも日本ポリ
ウレタン工業■製）などを用いてもよい。塗装された塗
膜には、乾燥後上塗りが施される。焼付型−漆塗料とし
てはメラミン硬化型やブロックイソシアネート硬化型が
あるが、いづれも通常１２０℃以上で焼付けられる。When coating the resin solution obtained in this way, use a normal polyisocyanate used in polyurethane paint as a hardening agent, for example, 1 Coronate 1 Coronate 11
L, Coronet 1-[EI+ (trade name: all manufactured by Nippon Polyurethane Industries, Ltd.), etc. may also be used. After drying, a top coat is applied to the painted film. Baking-type lacquer paints include melamine-curing type and block isocyanate-curing type, both of which are usually baked at 120°C or higher.
本発明のプライマー用樹脂組成物を用いて、自動車車体
用鋼板と同一塗装系で塗装された各種プラスチック素材
は、１２０℃以上で焼付後も外観性に優れ、また−３０
°Ｃ以下での耐低温衝撃性にも優れた性能を示す。また
鋼板部においては、電着塗膜と中塗り塗膜との間に塗装
することにより、エネルギー吸収層あるいは応力緩和層
として働くため、耐チッピング性の向上、耐スキャブ性
、耐糸錆性の向上が認められる。その他の成分としては
、プラスチック素材上で中塗りおよび／または上塗り塗
料を静電塗装することを可能にするため導電材を加える
ことができる。導電材としては導電性顔料が用いられる
が、特に導電性カーボンが好ましい。導電性カーボンは
公知のものとして市販されているものを使用することが
でき、例えばキャボット社製パルカンＸＣ−７２（商品
名）、コロンビアカーボン社製コンダクテックス９７５
（商品名）などがある。プライマーの固形分中に含まれ
るポリウレタン樹脂の比率は３０〜９７重景％、好まし
くは４０〜９５重量％である。３０重量％未満の場合は
、耐衝撃性が劣り、９７重量％を越える場合は、耐衝撃
性の点では問題はないが、上塗りの静電塗装作業性およ
びプライマーの指触乾燥性が劣る。また固型分中に含ま
れる導電性カーボンの比率は３〜３０重量％、好ましく
は５〜２０重呈％である。３重量％未溝の場合はプライ
マーの導電性が小さく、上塗りの静電塗装性が劣り、さ
らにプライマーの指触乾燥性が遅くなり、ごみの付着が
多くなって美観を損ね、一方３０重量％を越える場合は
、プライマー表面の凹凸が著しくなり、上塗り外観性（
平滑性）が劣る。本発明における前記プライマーに用い
る樹脂としては本発明のウレタン樹脂の他に、エポキシ
樹脂、アルキド樹脂、アクリル樹脂、本発明以外のウレ
タン樹脂、架橋剤としてブロックイソシアネート樹脂、
メラミン樹脂などを添加してもよい。また顔料としては
導電性カーボンの他、通常のカーボンブラック、二酸化
チタン、亜鉛華、タルク、カオリンなどの着色顔料や体
質顔料を使用することができる。さらに添加剤として、
シリコン系、非シリコン系添加剤、紫外線吸収剤、酸化
防止剤、光安定剤、帯電防止剤、アクリル系表面調整剤
、アマイド系ワックスなどを用いることができる。本発
明のプライマー用樹脂組成物は、顔料をウレタン樹脂に
公知の分散方法によって分散させて製造することができ
る。すなわち導電材や他の顔料とウレタン樹脂を混合し
ボールミルやロールミルで分散せしめ、その後適宜、溶
剤、添加剤、必要に応じて他の樹脂を加え、均一に攪拌
することにより、プライマー用樹脂組成物が得られる。Various plastic materials coated with the same coating system as steel plates for automobile bodies using the resin composition for primers of the present invention have excellent appearance even after baking at temperatures above 120°C, and -30°C
It also exhibits excellent low-temperature impact resistance at temperatures below °C. In addition, on steel plate parts, by coating between the electrodeposition coating film and the intermediate coating film, it acts as an energy absorption layer or stress relaxation layer, which improves chipping resistance, scab resistance, and thread rust resistance. Improvement is recognized. Other components may include conductive materials to enable electrostatic application of intermediate and/or top coats on plastic materials. As the conductive material, conductive pigments are used, and conductive carbon is particularly preferred. As the conductive carbon, commercially known ones can be used, such as Palcan XC-72 (trade name) manufactured by Cabot Corporation and Conductex 975 manufactured by Columbia Carbon Corporation.
(product name) etc. The proportion of polyurethane resin contained in the solid content of the primer is 30 to 97% by weight, preferably 40 to 95% by weight. If it is less than 30% by weight, the impact resistance will be poor, and if it exceeds 97% by weight, there will be no problem in terms of impact resistance, but the electrostatic coating workability of the top coat and the dryness to the touch of the primer will be poor. The proportion of conductive carbon contained in the solid content is 3 to 30% by weight, preferably 5 to 20% by weight. If 3% by weight is ungrooved, the conductivity of the primer will be low, the electrostatic coating properties of the top coat will be poor, and the dryness of the primer will be slow to the touch, and more dust will adhere to it, spoiling the aesthetics, while at 30% by weight If it exceeds this, the unevenness of the primer surface will become significant and the topcoat appearance
smoothness) is poor. In addition to the urethane resin of the present invention, resins used in the primer of the present invention include epoxy resins, alkyd resins, acrylic resins, urethane resins other than the present invention, and block isocyanate resins as crosslinking agents.
Melamine resin or the like may also be added. As the pigment, in addition to conductive carbon, ordinary coloring pigments and extender pigments such as carbon black, titanium dioxide, zinc white, talc, and kaolin can be used. Furthermore, as an additive,
Silicone-based and non-silicon-based additives, ultraviolet absorbers, antioxidants, light stabilizers, antistatic agents, acrylic surface conditioners, amide waxes, and the like can be used. The resin composition for a primer of the present invention can be produced by dispersing a pigment in a urethane resin by a known dispersion method. That is, a resin composition for a primer is prepared by mixing a conductive material and other pigments with a urethane resin and dispersing the mixture using a ball mill or roll mill, then adding appropriate solvents, additives, and other resins as necessary, and stirring uniformly. is obtained.
本発明においてプライマー膜厚は３〜３０μ、好ましく
は５〜１５μであり、３μ未満では連続膜にならず、ま
た３０μを越える場合は静電作業性上は問題はないが、
コスト面で不利益になる。In the present invention, the primer film thickness is 3 to 30μ, preferably 5 to 15μ; if it is less than 3μ, it will not form a continuous film, and if it exceeds 30μ, there will be no problem in terms of electrostatic workability.
This will be disadvantageous in terms of cost.
（発明の効果）
本発明のプライマー樹脂組成物は、種々のエンジニアリ
ングプラスチック素材への適用ができ、かつ低温時の耐
衝撃性および外観、耐湿性が向上し、かつ車体用の中塗
りおよび／または上塗り塗料を塗装することができるた
め、車体と同一ラインで一体塗装することが可能となり
、塗装工程が簡略化して塗装費を節減できるとともに、
鋼板部においては耐チッピング性、耐スキャブ性、耐糸
錆性等が向上し、かつ仕上り外観性の優れた塗膜が得ら
れるなどの効果がある。(Effects of the Invention) The primer resin composition of the present invention can be applied to various engineering plastic materials, has improved impact resistance and appearance at low temperatures, and moisture resistance, and can be used as an intermediate coating for car bodies and/or Since it is possible to apply a top coat of paint, it is possible to paint the car body in one piece on the same line, which simplifies the painting process and reduces painting costs.
In the steel plate part, chipping resistance, scab resistance, string rust resistance, etc. are improved, and a coating film with excellent finished appearance can be obtained.
（実施例）
次に本発明の実施例および比較例をあげて、本発明をさ
らに詳細に説明する。例中、部は重量部、％は重量％を
示す。(Example) Next, the present invention will be explained in further detail by giving examples and comparative examples of the present invention. In the examples, parts indicate parts by weight, and % indicates weight %.
実施１１〜６．比六例１〜９
〔プライマー用樹脂組成物の製造〕 −合成例１
第１表に示す配合組成物にもとづき分子量１，５００の
ＰＣＬ （ＰＣＬ−１、５００ダイセル化学工業０１製
商品名）１．５００ ｇ（１モル）とＩＰＤＩ ６６６
ｇ （３モル）およびトルエン３，５４０ｇを１０℃
の四ツ目フラスコに仕込んで溶解し、窒素ガス気流中８
０℃で３時間反応させた。つぎにＩＰＯＡ ３６０ｇ
（２，１２モル）とイソプロピルアルコール２，３６０
ｇの混合物を添加して８０°Ｃで１時間反応させた。数
平均分子ｆｆ１２０．ｏｏｏのプライマー用樹脂組成物
が得られた。Implementation 11-6. Comparison Examples 1 to 9 [Manufacture of resin composition for primer] - Synthesis Example 1 Based on the blended composition shown in Table 1, PCL with a molecular weight of 1,500 (PCL-1, 500 product name manufactured by Daicel Chemical Industries 01) 1 .500 g (1 mole) and IPDI 666
g (3 mol) and 3,540 g of toluene at 10°C.
Pour into a four-eye flask, dissolve, and evaporate in a nitrogen gas stream.
The reaction was carried out at 0°C for 3 hours. Next, 360g of IPOA
(2,12 mol) and isopropyl alcohol 2,360
g of the mixture was added and reacted at 80°C for 1 hour. Number average molecule ff120. A resin composition for a primer of ooo was obtained.
合成例９
第１表に示す配合組成物にもとづき分子量２，０００の
ＰＣＬ （ＰＣＬ−２，０００ダイセル化学工業［＠製
商品名）２．０００ ｇ（１モル）、エチレングリコー
ル６８ ｇ （１，０９モル）およびメチルエチルケト
ン５，８６０ｇを１０７！の四ツ目フラスコに仕込んで
溶解した７ｉ１ＰＤ１４４４ｇ（２モル）を加え、窒素
ガス気流中８０℃で５時間反応させた。数平均分子ｔｔ
３０．ｏｏＯのプライマー用樹脂組成物が得られた。Synthesis Example 9 Based on the blended composition shown in Table 1, 2.000 g (1 mol) of PCL (PCL-2,000 trade name manufactured by Daicel Chemical Industries [@]) with a molecular weight of 2,000, 68 g (1 mol) of ethylene glycol, 09 mol) and 5,860 g of methyl ethyl ketone to 107! 1444 g (2 moles) of 7i1PD dissolved in a four-eye flask was added thereto, and the mixture was reacted at 80° C. for 5 hours in a nitrogen gas stream. number average molecule tt
30. A resin composition for primer of ooO was obtained.
合成例２〜８及び合成例１０〜１５
第１表に示す配合組成物にもとづき、合成例１と同様に
して合成を行った。Synthesis Examples 2 to 8 and Synthesis Examples 10 to 15 Synthesis was carried out in the same manner as in Synthesis Example 1 based on the blended compositions shown in Table 1.
第１表に示す配合組成物にもとづき、合成した前記プラ
イマー用樹脂組成物と顔料を第２表の配合にもとづき、
それぞれディシルバーで十分混練し、次いでペイントシ
ェーカーで１時間混練した。Based on the compounded composition shown in Table 1, the resin composition for primer synthesized and the pigment were combined based on the compounded composition shown in Table 2,
Each mixture was thoroughly kneaded using a disilver, and then kneaded for 1 hour using a paint shaker.
混練後、トルエン／イソプロピルアルコールの等重量混
合溶剤を添加し、スプレー粘度をフォードカップ＃４で
１２秒（２０℃）とし、プライマーを製造した。After kneading, an equal weight mixed solvent of toluene/isopropyl alcohol was added and the spray viscosity was adjusted to 12 seconds (20° C.) using a #4 Ford cup to produce a primer.
第２表
プライマー用樹脂組成物（固型分３０％） ９６．１
導電製カーボン゛ ３．９＊コロ
ンビア力−ボン社製：商品名コンダクテソクス９７５
合成されたプライマー用樹脂組成物を使用して製造され
たプライマーの実施例１〜６及び比較例１〜９を第１表
に示す。Table 2 Resin composition for primer (solid content 30%) 96.1
Conductive Carbon 3.9 * Manufactured by Columbia Power-Bon Co., Ltd.: Trade name Conductexox 975 Examples 1 to 6 and Comparative Examples 1 to 9 of primers manufactured using the synthesized primer resin composition were Shown in the table.
試験例
プライマーとして実施例１〜６、比較例１〜９の組成物
を用い、各組成物を次に示すように各試験板に塗装し、
中塗り塗料として車体用のエポキシ変性ポリエステル樹
脂系塗料（日本油脂（４菊製、商品名エビコＮｕ １
、５００シーラー）、上塗り塗料として車体用のアミノ
アルキド樹脂系塗料（日本油脂側製、商品名メラミ１ｌ
ｈｌ赤）を用い、下記の如く試験用塗装板を作成した。Using the compositions of Examples 1 to 6 and Comparative Examples 1 to 9 as test example primers, each composition was applied to each test board as shown below,
Epoxy-modified polyester resin paint for car bodies as an intermediate coating (Nippon Oil Co., Ltd. (manufactured by 4 Kiku, product name: Ebico Nu 1)
, 500 sealer), amino alkyd resin paint for car bodies as a top coat (manufactured by NOF, trade name Melami 1l)
A test coated board was prepared using HL Red) as described below.
１、プラスチック素材の場合
下記プラスチック素材を１．１．１−トリクロルエタン
の蒸気（７４℃）で６０秒間洗浄した後、実施例１〜６
、比較例１〜９の各プライマーを空気霧化塗装し、次い
で５分間放置した後、中塗り塗料を静電空気霧化塗装し
、１４０℃で３０分間焼き付は乾燥を行い、さらに上塗
り塗料を静電空気霧化塗装し、１４０℃で３０分間焼き
付は乾燥した。得られた試験用塗装板のプライマー乾燥
塗膜厚は５〜８μ、中塗り乾燥塗膜厚は２８〜３０μ、
上塗り乾燥塗膜厚は３８〜４０μであった。1. In the case of plastic materials After washing the following plastic materials with 1.1.1-trichloroethane vapor (74°C) for 60 seconds, Examples 1 to 6
, each primer of Comparative Examples 1 to 9 was applied by air atomization, and then left for 5 minutes, an intermediate coating was applied by electrostatic air atomization, baked and dried at 140°C for 30 minutes, and then the top coating was applied. was applied by electrostatic air atomization and baked at 140°C for 30 minutes to dry. The dry primer film thickness of the obtained test coated board was 5 to 8μ, the intermediate coat dry film thickness was 28 to 30μ,
The dry topcoat film thickness was 38 to 40 microns.
２、鋼板の場合
自動車車体用冷間圧延鋼板にボンデライｌ−６３００４
（日本パー力うイジング■製、商品名）によりリン酸亜
鉛処理被膜を形成し、カチオン電着塗料のアクアｌ１ｈ
４１００ （日本油脂（４喝製、商品名）を塗装し、１
７５℃で２０分間焼き付は乾燥した。得られた電着塗膜
の乾燥塗膜厚は１５μであった。次いで前記プラスチッ
ク素材と同様の塗装条件により、プライマー、中塗り、
上塗り塗料を塗装し、得られた試験用塗装板のプライマ
ー乾燥膜厚は５〜８μ、中学り乾燥膜厚は２８〜３０μ
、上塗り乾燥膜厚は３８〜４０μであった。2. In the case of steel plates, Bonderai l-63004 is used for cold rolled steel plates for automobile bodies.
(manufactured by Nippon Paru Ising ■, trade name) to form a zinc phosphate treatment film, and use the cationic electrodeposition paint Aqua l1h.
4100 (made by Nippon Oil & Fats Co., Ltd., product name), 1
The bake was dried at 75°C for 20 minutes. The dry film thickness of the obtained electrodeposited film was 15 μm. Next, under the same coating conditions as for the plastic material, primer, intermediate coat,
The primer dry film thickness of the test coated board obtained by applying the top coat paint is 5 to 8 μm, and the dry film thickness of junior high school paint is 28 to 30 μm.
The topcoat dry film thickness was 38 to 40μ.
此膚■江刊
実施例１〜６、比較例１〜９と同様にして自動車車体用
冷間圧延鋼板にリン酸亜鉛処理被膜を形成し、電着塗膜
を形成した後、本発明のプライマーを塗装しないで、中
塗り塗膜及び上塗り塗膜を形成した。得られた試験用塗
装板の中塗り乾燥塗膜は２８〜３０μ、上塗り乾燥塗膜
は３８〜４０μであった。In the same manner as in Examples 1 to 6 and Comparative Examples 1 to 9, a zinc phosphate treatment film was formed on a cold rolled steel plate for an automobile body, and an electrodeposition coating film was formed, and then the primer of the present invention was applied. An intermediate coat film and a top coat film were formed without painting. The dry intermediate coating film of the obtained test coated board was 28 to 30 μm, and the dry top coat film was 38 to 40 μm.
上記の工程で得られた試験用塗装板につき、次の試験を
行い、得られた結果を第３〜８表に示す。The following tests were conducted on the test coated plates obtained in the above steps, and the results are shown in Tables 3 to 8.
ａ）耐低温衝撃性
ｂ）塗膜性能
イ）塗膜外観性
Ｏ）ゴバン目付着性
ハ）耐湿性
二）耐熱性
ネ）耐ガソリン性
へ）耐チッピング性
ト）耐スキャプ錆性
チ）耐糸錆性
ただしへ）〜チ）は鋼板のみ実施
なお前記プラスチック素材としては次のものを使用した
。a) Low-temperature impact resistance b) Coating film performance a) Coating film appearance O) Goblin adhesion c) Moisture resistance d) Heat resistance d) Gasoline resistance) Chipping resistance d) Scapping rust resistance d) Resistance Thread rust resistance However, only steel plates were used for tests (I) to (I)).The following plastic materials were used as the plastic materials.
プラスチック素材
Ａ）ポリアミド（ＰＡ）樹脂素材
６ナイロンあるいは６．６ナイロンをベースにガラス繊
維、タルクなどの無機質を単独あるいは複合して５〜４
０％充填して剛性を向上させ、さらに耐衝撃性向上のた
めにエラストマを５〜２０％ブレンドしたもの（商品名
１０１３ＲＷ−１宇部興産■）。Plastic material A) Polyamide (PA) Resin material Based on 6 nylon or 6.6 nylon, inorganic materials such as glass fiber and talc are used alone or in combination 5 to 4
Filled with 0% to improve rigidity, and further blended with 5 to 20% of elastomer to improve impact resistance (trade name: 1013RW-1 Ube Industries ■).
Ｂ）ポリブチレンテレフタレート（ＰＢＴ）樹脂素材耐
衝撃性向上の手段として、ポリブタジェン、エチレンプ
ロピレンゴム（ＥＰＲ）などのエラストマを５〜２０％
ブレンドした変性ＰＢＴ樹脂（商品名５２０１ Ｘ １
１ 東し■） 。B) Polybutylene terephthalate (PBT) resin material As a means of improving impact resistance, 5 to 20% of elastomer such as polybutadiene or ethylene propylene rubber (EPR) is added.
Blended modified PBT resin (product name 5201
1 East ■).
Ｃ）強化プラスチック（ＳＭＣ）樹脂素材ポリエステル
系樹脂にガラス繊維、炭酸カルシウム、タルクなどを充
填して強化したもので、加熱した成形型により形成した
もの（商品名 Ｎ１２武田薬品Ｇ１１））。C) Reinforced plastic (SMC) Resin material Polyester resin filled with glass fiber, calcium carbonate, talc, etc. to strengthen it, and formed using a heated mold (product name N12 Takeda Pharmaceutical G11)).
Ｄ）ポリウレタン（ＰＵ）樹脂素材
イソシアネートとポリオールの反応生成物で、ウレタン
結合を持っていることからこのように呼ばれている （
商品名 Ｃ１０５６／ＦＡ７２０日本ポリウレタン（Ｉ
荀）。D) Polyurethane (PU) A reaction product of resin material isocyanate and polyol, so called because it has urethane bonds (
Product name C1056/FA720 Japan Polyurethane (I
Xun).
Ｅ）ポリカーボネー） （ＰＣ）樹脂素材ｐｃ樹脂をベ
ースに耐熱性、耐薬品性を改良するためにＰＯＴ樹脂な
どを５〜４０％ブレンドして変性した変性ＰＣ樹脂（商
品名 ニーピロンＭＢ−２２０１三菱瓦斯化学＠）。E) Polycarbonate) (PC) Resin material Modified PC resin made by blending 5 to 40% of POT resin etc. to improve heat resistance and chemical resistance based on resin material (Product name: Kneepilon MB-2201 Mitsubishi) Gas Chemistry @).
■璽１火
＾）耐低温衝撃性
ハイレートインパクト試験（旧ｇｈ Ｒａｔｅ Ｉｍｐ
ａｃｔＴｅｓ ｔ）米国レオメトリック社製ＲＩＴ試験
機を用い、撃心が試験用塗装板を打ち抜いた時の衝撃エ
ネルギー値を測定する。■Seal 1 fire ^) Low temperature impact resistance high rate impact test (formerly GH Rate Imp
actTest) Using a RIT testing machine manufactured by Rheometric, USA, the impact energy value when the center of impact punches through the test painted plate is measured.
当該試験条件は、堅忍先端径１．６ｃｍ（５／８インチ
）、ホルダー５．１ｃａ＋（２インチ）、衝撃速度１１
．１ｍ／ｓｅｃで一４０℃での降伏エネルギー値（ジュ
ール）を算出する。The test conditions were: tenacity tip diameter 1.6 cm (5/8 inch), holder 5.1 ca+ (2 inch), and impact speed 11.
．． Calculate the yield energy value (joule) at -40°C at 1 m/sec.
数値の大きい方が耐低温衝撃性に優れている。The larger the number, the better the low-temperature impact resistance.
Ｂ〕塗膜性能 次の試験項目につき、試験、評価を行う。B] Paint film performance The following test items will be tested and evaluated.
ａ）塗膜外観 ＪＩＳ Ｋ−５４００（６−１）評価
◎：外観異常がなく特に優良なもの。a) Paint film appearance JIS K-5400 (6-1) evaluation
◎: Particularly excellent with no abnormalities in appearance.
○：外観異常がなく良好なもの。○: Good appearance with no abnormalities.
Δ：チジミ、吸い込みなど異常のあるもの。Δ: Items with abnormalities such as tingling or suction.
×：チジミ、吸い込みなどが特にはげしいもの。×: Particularly severe staining and suction.
ｂ）密着性 ＪＩＳ Ｋ−５４００（６−１５）評価
セロハンテープはく離後の残存数で表示１００／１００
＝残存数／カット数
Ｃ）耐湿性
温度、湿度ともに調整可能な密閉箱を使用し、試験片を
温度５０±ｌ ”Ｃ１相対湿度９８％以上に調整した密
閉箱に水平におき、２４時間ごとにふくれの発生および
その変化の状態を調べ２４０時間まで行う。b) Adhesion JIS K-5400 (6-15) evaluation
Displayed as number remaining after cellophane tape is removed 100/100
=Remaining number/Cut number C) Moisture resistance Use a sealed box where both temperature and humidity can be adjusted, and place the test piece horizontally in the sealed box adjusted to a temperature of 50 ± 1 C1 relative humidity of 98% or more, and test every 24 hours. The occurrence of blisters and their changes are examined for up to 240 hours.
評価 ◎：ふくれの発生なし。Evaluation ◎: No blistering occurred.
○：小ふくれ発生するも２４時間後に消滅する。○: Small blisters occur, but disappear after 24 hours.
八：０．５ｍｍ程度のふくれ発生。8: Blistering of about 0.5 mm occurred.
Ｘ ： ０．５ｍｔｍ以上のふくれ発生。X: Blistering of 0.5 mtm or more occurred.
ｄ）耐熱性
試験片を９０℃の恒温槽に５００時間設置し、２４時間
室温に放置した後、塗膜外観および変色、つや引けなど
、熱による塗膜表面の変化を調べる。d) Heat resistance The test piece was placed in a constant temperature bath at 90° C. for 500 hours, and after being left at room temperature for 24 hours, the appearance of the coating film and changes in the coating surface caused by heat, such as discoloration and gloss shrinkage, were examined.
評価 ◎：基準板に比べ全く外観差なし。Evaluation: ◎: No difference in appearance compared to the reference plate.
○：基準板に比べほとんど外観差なし。○: There is almost no difference in appearance compared to the reference plate.
△：基準板に比べ変色、つや引けの有るもの。△: Discoloration and loss of gloss compared to the reference plate.
×：基準板に比べ外観差著しいもの。×: Significant difference in appearance compared to the reference plate.
ｅ）耐ガソリン性
試験片の表面にガソリンを約０．３〜０．５ｍ１滴下し
、試験室に４時間放置した後、布でふきとり、ただちに
塗膜について、つや引け、しみ、変色、軟化、はがれお
よびきれつの有無について調べる。e) Drop about 0.3 to 0.5 ml of gasoline onto the surface of the gasoline resistance test piece, leave it in the test room for 4 hours, wipe it off with a cloth, and immediately check for gloss, stains, discoloration, softening, etc. Inspect for peeling and cracking.
評価 ◎：全く異常なし。Evaluation ◎: No abnormality at all.
○：はとんど異常なし。○: Almost no abnormality.
△：しみ跡がわずかに残る。Δ: Slight stain marks remain.
×ニジみ跡、軟化など異常が認められる。× Abnormalities such as scratches and softening are observed.
ｆ）耐チッピング性
グラベロメータＳＡＥ Ｊ４００の規定に準拠したもの
を用い、シヨ・７ト材６号砕石（ＪＩＳ＾５００１−７
７に規定するもの） ２５０ｇ、エアー圧４．０ｋｇ／
ｃｍ”の条件で試験片に９０度の角度で当たるようにセ
ットし、吹き付ける。吐出後、試験片を取り外し、セロ
ハンテープはく離をして塗面のはく離状態、きすの程度
を調べる。f) Chipping resistance Gravelometer using a gravelometer that complies with SAE J400 regulations and using No. 6 crushed stone (JIS^5001-7).
7) 250g, air pressure 4.0kg/
cm", set it so that it hits the test piece at a 90 degree angle, and spray it. After dispensing, remove the test piece, peel off the cellophane tape, and check the peeling state of the painted surface and the degree of scratching.
評価 ◎：はく離の径が０ 、５ｍｍ未満○：はく離の
径が０．５〜１ 、０ｍｍΔ：はく離の径が１．０〜１
．５ｎ＋ｍ×：はく離の径が１．５ｍｍ以上
ｇ）耐スキャブ錆性
ｆ）の方法で得られた試験片につき、複合腐食試験方法
の方法により所定のサイクルまで連続して試験を行い、
スキャブ錆の発生を調べる。サイクルは塩水噴霧２時間
−乾燥（６０℃）２時間−湿潤（５０℃、９５％Ｒ１１
以上）４時間を１サイクルトし６０サイクル実施。Evaluation ◎: Diameter of flaking is 0, less than 5 mm ○: Diameter of flaking is 0.5-1, 0 mm Δ: Diameter of flaking is 1.0-1
．． 5n+m×: The diameter of the flaking is 1.5 mm or more g) Scab rust resistance f) The test piece obtained by the method of f) is continuously tested up to a predetermined cycle by the method of the composite corrosion test method,
Inspect the occurrence of scab rust. The cycle was 2 hours salt spray - 2 hours dry (60°C) - 2 hours wet (50°C, 95% R11)
Above) One cycle of 4 hours was performed for 60 cycles.
評価 ◎ニスキャブ錆発生全くなし
Ｏニスキャブ錆径０ 、５ｍｍ以下
△ニスキャブ錆径０．５〜１．Ｏｍｍ
×ｍｍ×ニスキャブ、０ｍｍ以上
ｈ）耐糸錆性
ｆ）の方法で得られた試験片につき、塩水噴霧試験を２
４時間実施した後、温度、湿度ともに調整可能な密閉箱
を使用し、試験片を温度４０±１’ｃ、相対湿度８０〜
８５％ＲＨに調整して、密閉箱に水平に４８０時間置き
、糸錆の発生状態を調べる。Evaluation: ◎No varnish cab rust at all; 0. Varnish cab rust diameter: 0, 5 mm or less; △Varnish cab rust diameter: 0.5-1. Omm × mm × varnish cab, 0 mm or more h) Thread rust resistance f) The test piece obtained by method 2 was subjected to a salt spray test.
After 4 hours of testing, the test piece was placed at a temperature of 40 ± 1'C and a relative humidity of 80~80°C using a sealed box where both temperature and humidity can be adjusted.
Adjust the RH to 85%, place it horizontally in a closed box for 480 hours, and check for thread rust.
評価 ◎：糸錆の発生全くなし
Ｑ：糸錆の発生なく、０ 、５ｍｍ以下の点ふくれの状
態
Δ：糸錆の発生１ｍｍ以下
×：糸錆の発生１ｍｍ以上
第３表から第８表までの実施例から明らかなように、本
発明のプライマー用樹脂組成物は、全てのプラスチック
素材に対しては、耐低温衝撃性、傅膜の外観、耐湿性に
優れており、鋼板素材に対しては、外観、耐湿性、耐チ
ッピング性、耐スキャプ性、耐糸錆性に優れているため
、本発明のプライマー用樹脂組成物を全てのプラスチッ
ク素材及び鋼板素材に塗装することにより、現用の中塗
り、または上塗り塗料を同時に塗装することが可能であ
る。Evaluation ◎: No occurrence of thread rust Q: No occurrence of thread rust, point bulges of 0.5 mm or less Δ: Occurrence of thread rust 1 mm or less ×: Occurrence of thread rust 1 mm or more Tables 3 to 8 As is clear from the examples, the primer resin composition of the present invention has excellent low-temperature impact resistance, film appearance, and moisture resistance for all plastic materials, and is excellent for steel sheet materials. Because it has excellent appearance, moisture resistance, chipping resistance, scabbing resistance, and thread rust resistance, by coating all plastic materials and steel sheet materials with the resin composition for primer of the present invention, it can be used in modern applications. It is possible to apply a coat or a top coat at the same time.
これに対して、比較例１は、ポリオールの分子量が１５
００未満であり、全てのプラスチック素材に対する耐低
温衝撃性、外観、耐湿性が劣る。On the other hand, in Comparative Example 1, the molecular weight of the polyol was 15
00, and the low-temperature impact resistance, appearance, and moisture resistance of all plastic materials are poor.
比較例２は、反応物の分子量が４００００を越える場合
であり、全てのプラスチック素材及び鋼板素材に対する
外観が著しく劣る。Comparative Example 2 is a case where the molecular weight of the reactant exceeds 40,000, and the appearance is significantly inferior to all plastic materials and steel sheet materials.
比較例３は、鎖延長剤としてエチレングリコールを使用
した場合であり、全てのプラスチック素材に対する耐低
温衝撃性、外観、耐湿性が劣り、鋼板素材に対する外観
、耐湿性、耐チッピング性、耐スキャプ性、耐糸錆性が
劣る。Comparative Example 3 is a case where ethylene glycol is used as a chain extender, and the low-temperature impact resistance, appearance, and moisture resistance are inferior to all plastic materials, and the appearance, moisture resistance, chipping resistance, and scaping resistance to steel sheet materials are poor. , poor thread rust resistance.
比較例４は、反応物の分子量が１０．０００未満の場合
であり、全てのプラスチック素材及び鋼板に対する外観
が著しく劣る。Comparative Example 4 is a case where the molecular weight of the reactant is less than 10.000, and the appearance is significantly inferior to all plastic materials and steel plates.
比較例５は、イソシアネート／ポリオールのモル比が１
．５モル未膚の場合であり、全てのプラスチック素材に
対する耐低温衝撃性、外観、耐湿性が劣り、鋼板素材に
対する外観、耐湿性が劣る。Comparative Example 5 has an isocyanate/polyol molar ratio of 1.
．． In this case, the low temperature impact resistance, appearance, and moisture resistance are inferior to all plastic materials, and the appearance and moisture resistance are inferior to steel sheet materials.
比較例６は、イソシアネート／ポリオールのモル比が３
．０モルを越える場合であり、全てのプラスチック素材
に対する耐低温衝撃性が劣る。Comparative Example 6 has an isocyanate/polyol molar ratio of 3.
．． If the amount exceeds 0 mol, the low-temperature impact resistance of all plastic materials is poor.
比較例７は、イソシアネートとしてＭＤＩを使用した場
合であり、全てのプラスチック素材に対する耐低温衝撃
性、外観が劣り、鋼板素材に対する外観が劣る。Comparative Example 7 is a case where MDI is used as the isocyanate, and the low-temperature impact resistance and appearance are inferior to all plastic materials, and the appearance is inferior to steel sheet materials.
比較例８は、イソシアネートとしてＴＤＩを使用した場
合であり、全てのプラスチック素材に対する耐低温衝撃
性が劣る。Comparative Example 8 uses TDI as the isocyanate, and has poor low-temperature impact resistance for all plastic materials.
比較例９は、ポリオールとして１．４−ブタンジオール
とアジピン酸とのポリエステルポリオールを使用した場
合であり、全てのプラスチック素材に対する耐低温衝撃
性、外観が劣り、鋼板素材に対する外観、耐チッピング
性、耐スキャプ性、耐糸錆性が劣る。Comparative Example 9 is a case where a polyester polyol of 1,4-butanediol and adipic acid is used as the polyol, and the low-temperature impact resistance and appearance are inferior to all plastic materials, and the appearance and chipping resistance to steel sheet materials are poor. Scapping resistance and thread rust resistance are poor.
比較例１０は、鋼板素材を電着塗装後本発明のプライマ
ーを塗装しないで、実施例と同様の中塗り及び上塗り塗
装した場合であり（現行の鋼板用塗装ラインと同じ塗装
システム）、外観、耐チッピング性、耐スキャプ性、耐
糸錆性が劣る。Comparative Example 10 is a case where the steel sheet material was electrodeposition coated and then the primer of the present invention was not applied, but the same intermediate and top coats were applied as in the example (same coating system as the current steel sheet painting line). Poor chipping resistance, scabbing resistance, and thread rust resistance.
Claims (1)
，０００のポリテトラメチレングリコールまたはポリカ
プロラクトンエステルと （Ｂ）ヘキサメチレンジイソシアネートまたはイソホロ
ンジイソシアネートと （Ｃ）イソホロンジアミン との反応物で、Ｂ／Ａ＝１．５〜３．０モルで、かつ分
子量が１０，０００〜４０，０００の範囲にある反応物
を主成分としたことを特徴とするプライマー用樹脂組成
物。[Claims] 1. (A) having a hydroxyl group at the terminal and having a molecular weight of 1,500 to 4;
,000 polytetramethylene glycol or polycaprolactone ester, (B) hexamethylene diisocyanate or isophorone diisocyanate, and (C) isophorone diamine, with B/A = 1.5 to 3.0 mol and a molecular weight of A resin composition for a primer, characterized in that the main component thereof is a reactant having a molecular weight of 10,000 to 40,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115386A JPS62169864A (en) | 1986-01-23 | 1986-01-23 | Primer resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115386A JPS62169864A (en) | 1986-01-23 | 1986-01-23 | Primer resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62169864A true JPS62169864A (en) | 1987-07-27 |
| JPH029063B2 JPH029063B2 (en) | 1990-02-28 |
Family
ID=11770071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1115386A Granted JPS62169864A (en) | 1986-01-23 | 1986-01-23 | Primer resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62169864A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929667A (en) * | 1988-02-01 | 1990-05-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Urethane prepolymer composition and a polyurethane coating composition system |
| WO2000039184A1 (en) * | 1998-12-24 | 2000-07-06 | Ppg Industries Ohio, Inc. | Coating composition |
-
1986
- 1986-01-23 JP JP1115386A patent/JPS62169864A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929667A (en) * | 1988-02-01 | 1990-05-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Urethane prepolymer composition and a polyurethane coating composition system |
| WO2000039184A1 (en) * | 1998-12-24 | 2000-07-06 | Ppg Industries Ohio, Inc. | Coating composition |
| US6482474B1 (en) | 1998-12-24 | 2002-11-19 | Ppg Industries Ohio, Inc. | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH029063B2 (en) | 1990-02-28 |
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