JPS63107784A - Coating method of reactive injection moldings - Google Patents
Coating method of reactive injection moldingsInfo
- Publication number
- JPS63107784A JPS63107784A JP25242886A JP25242886A JPS63107784A JP S63107784 A JPS63107784 A JP S63107784A JP 25242886 A JP25242886 A JP 25242886A JP 25242886 A JP25242886 A JP 25242886A JP S63107784 A JPS63107784 A JP S63107784A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- cured
- paint
- coating
- urethane
- 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
- 238000000576 coating method Methods 0.000 title claims description 37
- 238000001746 injection moulding Methods 0.000 title abstract 2
- 239000003973 paint Substances 0.000 claims abstract description 32
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 5
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 5
- 239000012948 isocyanate Substances 0.000 claims abstract 2
- 150000002513 isocyanates Chemical class 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000001723 curing Methods 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 abstract description 3
- 238000013007 heat curing Methods 0.000 abstract description 2
- -1 acrylic polyols Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 210000003127 knee Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical class O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ICMJHPBQTVWCNT-UHFFFAOYSA-N 1-(dibutylamino)propan-2-ol Chemical compound CCCCN(CC(C)O)CCCC ICMJHPBQTVWCNT-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- FMFWSIARXFCACS-UHFFFAOYSA-N 2-[bis(2-ethylhexyl)amino]ethanol Chemical compound CCCCC(CC)CN(CCO)CC(CC)CCCC FMFWSIARXFCACS-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 101100353042 Mycobacterium bovis (strain BCG / Pasteur 1173P2) lnt gene Proteins 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 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
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KVFIJIWMDBAGDP-UHFFFAOYSA-N ethylpyrazine Chemical compound CCC1=CN=CC=N1 KVFIJIWMDBAGDP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical class COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 101150028022 ppm1 gene Proteins 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は反応性射出成形品の塗装方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for coating reactive injection molded articles.
反応性射出成形品とは、熱硬化性樹脂を成形用金型内部
において硬化および成形を同時に行なうことにより得ら
れる樹脂成形品であり、例えばポリオールおよびポリイ
ソシア卑−トを原料として成形したウレタンＲＩＭ （
ＲｅａｃｔｉｏｎＩｎｊｅｃｔｉｏｎ Ｍｏｕｌｄｉｎ
ｇ）が実用に供されており、その優れた強度、可撓性、
並びに成形時の形状設計が自由である等の点から、主と
して自動車部品の分野で有用である。A reactive injection molded product is a resin molded product obtained by simultaneously curing and molding a thermosetting resin inside a mold. For example, a urethane RIM (
Reaction Injection Moldin
g) is in practical use, and its excellent strength, flexibility,
In addition, it is useful mainly in the field of automobile parts because it allows freedom in shape design during molding.
ウレタンＲＩＭは原則的には内部が発泡し、表面は平滑
になっている成形品であるが、成形条件等により、その
表面も部分的に多孔質になっている場合がしばしば見受
けられる。特に成形直後にはその多孔質が多いことが通
常である。In principle, urethane RIM is a molded product with a foamed interior and a smooth surface, but depending on the molding conditions, the surface often becomes partially porous. Particularly immediately after molding, it is normal that the material is highly porous.
かかる成形品の塗装においてはその微細孔を防ぐため急
速硬化が可能であって、成形品の可撓性に追随できる可
撓性を有する塗膜を形成しつる塗料並びに塗装法が要求
される。In coating such molded products, there is a need for paints and coating methods that can be rapidly cured to prevent micropores and form a coating film with flexibility that can follow the flexibility of the molded product.
従来ウレタンＲＩＭへの塗装は（１）ウレタンＲＩＭ成
形後ボストキュアを行ない表面の微細孔を更に小さくし
た後、常温に近い温度で２液型ポリウレタン樹脂塗料を
塗装する方法、あるいは触媒等を加えた低温硬化型のポ
リウレタン樹脂塗料を塗装する方法、（２）ウレタンＲ
ＩＭ成形後数日間放置し、表面が平滑になった後低温型
ポリウレタン樹脂塗料を塗装する方法などが知られてい
る。また（３）ウレタンＲＩＨの塗料および塗装法とし
【、特開昭５８−７８７３７号が知られている。Conventional methods for painting urethane RIM include (1) After forming the urethane RIM, perform a boss cure to further reduce the micropores on the surface, and then apply a two-component polyurethane resin paint at a temperature close to room temperature, or a low-temperature method using a catalyst, etc. Method of applying hardening polyurethane resin paint, (2) Urethane R
A known method is to leave it for several days after IM molding, and then apply a low-temperature polyurethane resin paint after the surface becomes smooth. Furthermore, (3) urethane RIH paint and coating method is known in Japanese Patent Application Laid-open No. 78737/1983.
しかしながら上述した（１）および（２）の塗装法は乾
燥に長時間を要したり、低温タイプポリウレタン樹脂塗
料では可使時間が短く、現場での取扱いが繁雑もしくは
困離であったり、更に作業工程に大きなロスがでる欠点
を有しており、得られた塗膜もウレタンＲＩＭの可撓性
に十分に適した性質を有していなかった。However, the coating methods (1) and (2) described above require a long time to dry, low-temperature type polyurethane resin paint has a short pot life, and handling on site is complicated or difficult. It had the disadvantage of causing a large loss in the process, and the resulting coating film did not have properties sufficiently suited to the flexibility of urethane RIM.
また、上記（３）の特開昭５８−７８７３７号にはウレ
タンＲＩＭの塗装に用いる塗料が記載されているが、ウ
レタンＲＩＭのピンホールの抑制の効果は記載されてお
らず明らかに本発明と目的を異にするものである。In addition, although JP-A-58-78737 mentioned above (3) describes a paint used for coating urethane RIM, it does not describe the effect of suppressing pinholes in urethane RIM, and it is clearly not related to the present invention. They have different purposes.
更に本出願人らが先に出願した特開昭６０−３１５３３
号は硬質成形品の塗装を主たる目的としており、この方
法のみではウレタンＲＩＭすどの軟質成形品には十分に
は適していない。Furthermore, Japanese Patent Application Laid-Open No. 60-31533, which was previously filed by the present applicants,
The main purpose of this method is to coat hard molded products, and this method alone is not fully suitable for soft molded products such as urethane RIM doors.
従って本発明の目的は、反応性射出成形品、例えばウレ
タンＲＩＭの塗装に関し、ウレタンＲＩＭの表面欠陥に
起因する塗膜外観の不良をなくし、低温短時間で硬化で
き、可撓性のある塗膜を形成しうるウレタンＲＩＭへの
塗装方法を提供することにある。Therefore, an object of the present invention is to eliminate defects in the appearance of the coating film caused by surface defects of the urethane RIM, and to provide a flexible coating film that can be cured at low temperatures and in a short time, with respect to the coating of reactive injection molded products such as urethane RIM. An object of the present invention is to provide a method for coating a urethane RIM that can form a urethane RIM.
本発明は、反応性射出成形品をポリウレタン樹脂下塗り
塗料で塗装し、次いで気相状態にあるアミン雰囲気中で
塗膜を硬化させた後、更に熱硬化性樹脂塗料またはポリ
ウレタン樹脂塗料を塗装し、硬化させる反応性射出成形
品の塗装方法であり、上記アミン雰囲気中で硬化させる
下：蓬りポリウレタン樹脂塗料は（ａ） Ｔｇ： −４
０〜３０℃、水酸基価：２０〜１６０１数平均分子［：
１０００〜１００００からなるポリオールと（ｂ）ポリ
イソシアネートとを含み、（ｃ）ＯＨ当量対イソシフ４
−ト当世の比が０．５：１〜２：１である塗料を使用す
る方法である。The present invention involves coating a reactive injection molded article with a polyurethane resin undercoat, then curing the coating film in an amine atmosphere in a gaseous state, and then further coating with a thermosetting resin paint or a polyurethane resin paint, This is a coating method for reactive injection molded products that is cured, and the bottom polyurethane resin paint that is cured in the above amine atmosphere is (a) Tg: -4
0-30℃, hydroxyl value: 20-1601 number average molecule [:
1000 to 10000 and (b) polyisocyanate, (c) OH equivalent to isosif
- This method uses a paint with a current ratio of 0.5:1 to 2:1.
本発明において用いられる反応性射出成形品は前記した
如きものであり、ウレタンＲＩＭ 、繊維強化ウレタン
ＲＩＭなどが挙げられる。The reactive injection molded product used in the present invention is as described above, and includes urethane RIM, fiber-reinforced urethane RIM, and the like.
また気相状態のアミン雰囲気中で硬化させるポリウレタ
ン樹脂下塗り塗料のポリオールとしては、アクリルポリ
オール、ポリエステルポリオール、アルキッドポリオー
ル、ポリオレフィンポリオールなどのポリオールが用い
られるが、特にアクリルポリオールおよびポリオレフィ
ンポリオールが適しており、この中でもＴｇ ニー４０
℃〜３０℃、水酸基価：２０〜１６０、数平均分子ｉ：
１０００〜１００００のポリオールが適している。特に
Ｔ９ニー２０〜２０℃、水酸基価：４０〜１４５、数平
均分子ｆｆｉ：１５００〜６０００のポリオレフィンポ
リオールおよびアクリルポリオールが望ましい。In addition, polyols such as acrylic polyols, polyester polyols, alkyd polyols, and polyolefin polyols are used as polyols for polyurethane resin undercoating paints that are cured in a gaseous amine atmosphere, but acrylic polyols and polyolefin polyols are particularly suitable. Among these, Tg knee 40
°C to 30 °C, hydroxyl value: 20 to 160, number average molecule i:
Polyols from 1000 to 10000 are suitable. Particularly desirable are polyolefin polyols and acrylic polyols having a T9 knee of 20 to 20°C, a hydroxyl value of 40 to 145, and a number average molecular ffi of 1500 to 6000.
Ｔｇが３０℃より高いと可撓性が不足し１また一４０℃
より低いと表面硬度が不足し、水酸基価が１６０より高
いと可撓性が不足し、また２０より低いと耐湿性、耐温
水性等の化学的性能が劣るようになり、数平均分子量が
１００００より大であると塗膜外観が不良となり、１０
００より小さいと耐湿性、耐温水性等の化学的性能が劣
るようになる。If Tg is higher than 30℃, flexibility will be insufficient and the temperature will rise to 40℃.
If the hydroxyl value is lower, the surface hardness will be insufficient, if the hydroxyl value is higher than 160, the flexibility will be insufficient, and if it is lower than 20, the chemical performance such as moisture resistance and hot water resistance will be inferior, and the number average molecular weight will be 10,000. If it is larger, the appearance of the paint film will be poor, and 10
If it is less than 00, chemical properties such as moisture resistance and hot water resistance will be inferior.
本発明で上記ポリウレタン樹脂下塗り塗料に使用するの
に適したポリイソシアネートは、トルイレンジイソシア
＋ −） （ＴＤＩ） 、ジフェニルメタンジイソレア
ネー） （ＭＤＩ） 、メチレンジイソシア卑−ト、キ
シリレンジイソシアネート（ＸＤＩ）、ヘキサメチレン
ジイソシ７ネー）（ＨＭＤＩ）、イソホロンジイソシア
ネート（ＩＰＤＩ）、）リフェニルメタントリイソシア
ネート、フェニレンジイソシアネート、リシンジイソシ
ア卑−ト、および上記のメチロール付加物または３〜５
全体など、更にはこれらの混合物である。Polyisocyanates suitable for use in the polyurethane resin undercoat in the present invention include toluylene diisocyanate (TDI), diphenylmethane diisoleane (MDI), methylene diisocyanate, and xylylene diisocyanate (XDI). ), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), ) liphenylmethane triisocyanate, phenylene diisocyanate, lysine diisocyanate, and methylol adducts of the above or 3 to 5
These include the whole, or even a mixture of these.
上述したポリオールとポリイソシアネートとは、そのＯ
Ｈ当量対インシアネート当量の比が０．５：１〜２：１
となるように使用する。ＯＨ当量が０．５より小さくな
ると付着性の低下、可撓性の低下が生じまた２より大き
くなると耐水性、耐温水性の低下および架橋密度が小さ
くなることによりピンホール抑制効果が小さくなる。The polyols and polyisocyanates mentioned above are
The ratio of H equivalent to incyanate equivalent is 0.5:1 to 2:1
Use it as follows. When the OH equivalent is less than 0.5, adhesion and flexibility are lowered, and when it is greater than 2, water resistance and hot water resistance are lowered, and crosslinking density is lowered, resulting in a smaller pinhole suppressing effect.
本発明においては上述のポリウレタン樹脂下塗り塗料を
塗装後これを気相状態にあるアミン雰囲気中で硬化させ
るのであるがこの時使用し得るアミンとしては第３アミ
ンが好ましく、例えばトリメチルアミン、トリエチルア
ミン、トリプロピルアミン、トリブチルアミン、トリア
ミルアミンなどの脂肪族第３アミン、ジメチルアニリン
、ジエチルアニリン、トリベンジルアミンなどの芳香族
アミン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン
あるいはトリエタノールアミン、メチルジェタノールア
ミン、ジメチルエタノールアミン、ジエチルエタノール
アミン、ジブチルエタノールアミン、ジ（２−エチルヘ
キシル）エタノールアミン、エチルジェタノールアミン
、トリイソプロパツールアミン、ジブチルイソプロパノ
ールアミンなどのフルカノールアミンが使用でき中でも
ジメチルエタノールアミンが好ましい。In the present invention, after the above-mentioned polyurethane resin undercoat is applied, it is cured in an amine atmosphere in a gas phase.The amine that can be used at this time is preferably a tertiary amine, such as trimethylamine, triethylamine, tripropyl. amines, aliphatic tertiary amines such as tributylamine and triamylamine, aromatic amines such as dimethylaniline, diethylaniline and tribenzylamine, N-methylmorpholine, N-ethylmorpholine or triethanolamine, methyljetanolamine, Flukanolamines such as dimethylethanolamine, diethylethanolamine, dibutylethanolamine, di(2-ethylhexyl)ethanolamine, ethyljetanolamine, triisopropanolamine, and dibutylisopropanolamine can be used, and dimethylethanolamine is preferred.
上記アミン類による雰囲気としては気相中のアミン濃度
が約１０〜３０００ ｐｐｍ１好ましくは３００〜１２
００ ｐｐｍが適している。温度は０〜８０℃、好まし
くは２０〜４０℃が適している。アミン雰囲気中での硬
化時間は樹脂組成、形成する膜厚、第３アミンの種類、
温度および濃度などによって異なるが一般的には１〜１
０分間、好ましくは２〜４分間である。なお、アミン気
相中での処理後必要であれば更に１０３℃以下の温度で
３〜１５分間加熱処理してもよい。The atmosphere with the above amines has an amine concentration in the gas phase of about 10 to 3000 ppm1, preferably 300 to 12
00 ppm is suitable. A suitable temperature is 0 to 80°C, preferably 20 to 40°C. The curing time in an amine atmosphere depends on the resin composition, the thickness of the film formed, the type of tertiary amine,
Generally 1 to 1, although it varies depending on temperature and concentration etc.
0 minutes, preferably 2 to 4 minutes. Note that, if necessary, after the treatment in the amine gas phase, a heat treatment may be performed at a temperature of 103° C. or lower for 3 to 15 minutes.
本発明で用いられる上塗り塗料である熱硬化性樹脂塗料
あるいはウレタン樹脂塗料にはウレタン樹脂塗料として
市販されている低温型のアルキッドメラミン樹脂塗料、
アクリルメラミン樹脂塗料、更には１液型または２液型
ウレタン樹脂塗料が使用できる。The thermosetting resin paint or urethane resin paint that is the top coat used in the present invention includes a low-temperature alkyd melamine resin paint commercially available as a urethane resin paint,
Acrylic melamine resin paints and furthermore one-component or two-component urethane resin paints can be used.
これら上塗り塗料の塗装後の加熱硬化条件は一般的には
８０〜１４０℃、２０〜６０分である。The heat curing conditions for these top coatings after application are generally 80 to 140°C and 20 to 60 minutes.
本発明に用いられるアミン気相中で硬化させるポリウレ
タン樹脂下塗り塗料および上塗り塗料には公知の種々の
添加剤、着色顔料、体質顔料などの顔料類、界面活性剤
、消泡剤、レベリング剤、色分れ防止剤など更にエステ
ル、ケトン、脂肪族または芳香族の炭化水素系溶剤など
を含有できる。The polyurethane resin undercoat and topcoat that are cured in the amine gas phase used in the present invention contain various known additives, pigments such as coloring pigments and extender pigments, surfactants, antifoaming agents, leveling agents, and colors. In addition to anti-separation agents, esters, ketones, aliphatic or aromatic hydrocarbon solvents, etc. can be contained.
本発明方法により、ポリウレタン樹脂下塗り塗料で塗装
し、次いでアミン雰囲気中で塗膜を硬化させると、この
時形成される塗膜はアミン雰囲気中で完全に硬化しない
状態であっても、その後高温にさらしても何ら発泡など
の異状を生じないことが判明した。By the method of the present invention, when a polyurethane resin undercoat is applied and the coating film is then cured in an amine atmosphere, the coating film formed at this time may not be completely cured in the amine atmosphere, but it will be exposed to high temperatures afterwards. It was found that no abnormalities such as foaming occurred when exposed.
また本発明に用いるアミン雰囲気中で硬化させるポリウ
レタン樹脂下塗り塗料を塗装する方法はエアースプレー
、エアレススプレー、ＯＮ塗装など公知の塗装法が適用
される。Further, as a method for applying the polyurethane resin undercoat paint that is cured in an amine atmosphere used in the present invention, known painting methods such as air spray, airless spray, and ON coating are applied.
また本発明方法による上塗り塗料による塗装方法は、公
知の任意の方法が使用でき、例えばエアースプレー、エ
アレススプレー、静電塗装等を使用できる。Further, as the coating method using the top coat according to the method of the present invention, any known method can be used, for example, air spray, airless spray, electrostatic coating, etc. can be used.
本発明の方法は室温で短時間硬化させることが可能であ
るためウレタンＲＩＭの多孔質性によって生ずる塗膜の
発泡を抑制できると共にウレタンＲＩＭのもつ可撓性に
追随できる性能を有する塗膜を形成できる。更に本発明
の方法はこれらの特長の他に、室温で硬化できるため、
二不ルギー面より経済的節約が得られること、長時間の
可使時間を保持できることの利点を有する。Since the method of the present invention can be cured at room temperature for a short time, it is possible to suppress foaming of the coating film caused by the porosity of urethane RIM, and to form a coating film that has performance that can follow the flexibility of urethane RIM. can. Furthermore, in addition to these features, the method of the present invention can be cured at room temperature;
It has the advantages of economical savings and long pot life.
以下に実施例を挙げて本発明を説明する。実施例中部は
他に特記せぬ限り重量部である。The present invention will be explained below with reference to Examples. Parts in the examples are parts by weight unless otherwise specified.
実施例 １
（１）ポリオールの調製：
単量体としてメタクリル酸メチ／Ｉ／３５．０部、アク
リル酸ブチル３６．０部、アクリル酸エチル１３．９部
および２−ヒドロキシエチルメタクリレート１５．１部
（単量体計１００部）を用い、溶媒として午シロール６
６部、重合開始剤としてアゾビスイソブチロニトリル３
．４部を用いて通常の方法で重合を行ない、アクリルポ
リオールを得た。この溶液の固形分は６５重量％であっ
た。Example 1 (1) Preparation of polyol: As monomers, methacrylate/I/35.0 parts, butyl acrylate 36.0 parts, ethyl acrylate 13.9 parts, and 2-hydroxyethyl methacrylate 15.1 parts (total of 100 parts of monomer) was used as a solvent.
6 parts, 3 parts of azobisisobutyronitrile as a polymerization initiator
．． Polymerization was carried out using 4 parts in a conventional manner to obtain an acrylic polyol. The solids content of this solution was 65% by weight.
得られたアクリルポリオールの特数は、 ＴにＩ：５℃
、水酸基価：６５、数平均分子量： ４５００であった
。The characteristics of the obtained acrylic polyol are: T to I: 5℃
, hydroxyl value: 65, and number average molecular weight: 4,500.
（２）ポリウレタン樹脂塗料の調製：
上記（１）で作ったアクリルポリオール溶液１００部に
酸化チタン粉末（石頭産業社製、商品名タイベークＣＲ
−９０） ３０部、体質顔料（林化成社製、商品名ダイ
ヤクレー）１５部、セロソルブアセテート２０部および
中シロール１０部からなる基材と、硬化剤としてのトリ
レンジイソシアネート（住友バイエルウレタン社製、商
品名スミジュールＬ−７５）２４部からなる２液型ポリ
ウレタン摺脂塗料を調製した。ＯＨ／Ｎ ＣＯ比は１／
１であった。(2) Preparation of polyurethane resin paint: Add 100 parts of the acrylic polyol solution prepared in (1) above to titanium oxide powder (manufactured by Ishito Sangyo Co., Ltd., product name: TYBAKE CR).
-90), a base material consisting of 30 parts of extender pigment (manufactured by Hayashi Kasei Co., Ltd., trade name Diaclay), 20 parts of cellosolve acetate and 10 parts of medium silole, and tolylene diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd.) as a hardening agent. A two-component polyurethane resin paint was prepared containing 24 parts of Sumidur L-75 (trade name). OH/N CO ratio is 1/
It was 1.
（３）塗装
ウレタンＲＩＭを常法にて脱脂した後、上記（２）で調
整した塗料を膜厚２５μになるようにスプレー塗装し１
室温で２分間セツティングした後、ジメチルエタノール
アミン６００ ｐｐｍの雰囲気中で、雰囲気風速１．２
ｍ／秒で２０℃の温度で２分間放ｆｉｌた。その後３０
℃で１０分間乾燥後ウレタン樹脂塗料（神東塗料社製、
商品名ボリン／％ＩＲ５）で膜厚３０μになるようにス
プレー塗装し、１００℃で３０分間加熱した。得られた
塗膜の試験結果を表２に示す。表２の結果からピンホー
ルのない、可撓性、付着性のすぐれた塗膜が得られたこ
とが判る。(3) After degreasing the painted urethane RIM using a conventional method, spray paint the paint prepared in (2) above to a film thickness of 25 μm.
After setting for 2 minutes at room temperature, the air flow rate was 1.2 in an atmosphere containing 600 ppm of dimethylethanolamine.
m/s at a temperature of 20° C. for 2 minutes. After that 30
After drying at ℃ for 10 minutes, apply urethane resin paint (manufactured by Shinto Paint Co., Ltd.,
The film was spray-coated with Boline (trade name: %IR5) to a film thickness of 30 μm, and heated at 100° C. for 30 minutes. Table 2 shows the test results of the obtained coating film. From the results in Table 2, it can be seen that a coating film with no pinholes and excellent flexibility and adhesion was obtained.
比較例 １
実施例１で用いたポリウレタン樹脂塗料を実施例１と同
様に塗装した後、アミン雰囲気処理なせずに１００℃で
３０分間乾燥後、実施例１と同様に上塗り塗装した。形
成された塗膜は表２に示すように多くのピンホールが見
られた。Comparative Example 1 The polyurethane resin paint used in Example 1 was applied in the same manner as in Example 1, and after drying at 100° C. for 30 minutes without amine atmosphere treatment, a top coat was applied in the same manner as in Example 1. As shown in Table 2, many pinholes were observed in the formed coating film.
実施例 ２〜４
下表１に示す単量体および硬化剤および溶剤を用いてポ
リオールを実施例１と同様にして調製した（なお表１中
に実施例１の場合も併記した）。数値は重量部である。Examples 2 to 4 Polyols were prepared in the same manner as in Example 1 using the monomers, curing agents, and solvents shown in Table 1 below (the case of Example 1 is also listed in Table 1). Values are parts by weight.
表 １
上記各実施例で使用したポリオールの特数およびそれを
用いてウレタンＲＩＭを実施例１と同様に塗装して得ら
れた塗膜の試験結果を表２（こ示す。Table 1 The characteristics of the polyols used in each of the above examples and the test results of the coating film obtained by coating urethane RIM using the same in the same manner as in Example 1 are shown in Table 2.
得られた塗膜は何れもピンホールのない。可撓性のすぐ
れた塗膜であった。All of the resulting coatings are free of pinholes. The coating film had excellent flexibility.
比較例 ２〜７
表２に示す如き特数を有するポリオールを使用し、表２
に示すＯＨ１ＮＣＯ比で使用して実施例１と同様にウレ
タンＲＩＭを塗装した結果を表２に示す。形成された塗
膜は表２に示す如く塗膜に多くのピンホールが見られる
か、可撓性がないか、欠陥のある塗膜であった。Comparative Examples 2 to 7 Using polyols having special properties as shown in Table 2,
Table 2 shows the results of coating urethane RIM in the same manner as in Example 1 using the OH1NCO ratio shown in Table 2. As shown in Table 2, the formed coating film had many pinholes, lacked flexibility, or had defects.
（１）水酸基価は無水酢酸でアセチル化し、遊離酢酸を
苛性カリで定量し、樹脂１９中に含まれる水酸基と当量
の苛性カリのダ数で示す。(1) The hydroxyl value is determined by acetylating with acetic anhydride, quantifying free acetic acid with caustic potassium, and indicating the number of caustic potassium equivalent to the hydroxyl group contained in the resin 19.
（２）付着性はゴパン目試験法（ＪＩＳ −Ｋ −５４
００）に従い、１罪間隔でのゴバン目１００についての
残数で示す。(2) Adhesion was determined using the Gopan eye test method (JIS-K-54
00), it is shown as the remaining number for 100 gobans at one sin interval.
（３）−２０℃屈曲性は試験片を一２０℃に保ち７０１
の１８０°折り曲げ性である。(3) -20°C flexibility is determined by keeping the test piece at -20°C.
180° bendability.
（４）耐温水性は４０℃で２４時間水に浸漬後のゴバン
目試験の結果を示す。(4) Hot water resistance shows the results of a cross-cut test after being immersed in water at 40°C for 24 hours.
（５）可使時間は３０℃でフォードカップ＃４を用い粘
度が初期より３秒を越えない時間で示す。(5) Pot life is expressed as the time when the viscosity does not exceed 3 seconds from the initial temperature using a #4 Ford cup at 30°C.
表中のＯ２△、×は次の定義による。O2Δ and × in the table are defined as follows.
本発明方法によれば、反応性射出成形品の塗装に当り、
ポリウレタン下塗り塗膜を迅速硬化で形成でき、そのた
め反応性射出成形品のピンホール等の塗膜欠陥を防止で
き、更に反応性射出成形品の可撓性に追随できる可撓性
のある塗膜が得られる。According to the method of the present invention, when painting a reactive injection molded product,
A polyurethane undercoat film can be formed with rapid curing, which prevents film defects such as pinholes on reactive injection molded products, and also provides a flexible coating that can match the flexibility of reactive injection molded products. can get.
特許出願人 トヨタ自動車株式会社 同 神東塗料株式会社Patent applicant: Toyota Motor Corporation Same Shinto Paint Co., Ltd.
Claims (1)
塗装し、次いで気相状態にあるアミン雰囲気中で塗膜を
硬化させた後、更に上塗り塗料として熱硬化性樹脂塗料
またはポリウレタン樹脂塗料を塗装し硬化させることか
らなる塗装方法であつて、上記下塗りポリウレタン樹脂
塗料が（ａ）Ｔｇ：−４０℃〜３０℃、水酸基価：２０
〜１６０）数平均分子量：１０００〜１００００である
ポリオールと、（ｂ）ポリイソシアネートとを含み、（
ｃ）ＯＨ当量対イソシアネート当量の比が０．５：１〜
２：１であることを特徴とする反応性射出成形品の塗装
方法。1. The reactive injection molded product is coated with a polyurethane resin undercoat, and then the coating is cured in an amine atmosphere in a gas phase, and then a thermosetting resin paint or polyurethane resin paint is applied as a topcoat. A coating method comprising curing, wherein the undercoat polyurethane resin paint is (a) Tg: -40°C to 30°C, hydroxyl value: 20
~160) Number average molecular weight: a polyol having a number average molecular weight of 1000 to 10000, and (b) a polyisocyanate, (
c) The ratio of OH equivalents to isocyanate equivalents is from 0.5:1
A method for coating reactive injection molded products characterized by a ratio of 2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25242886A JPS63107784A (en) | 1986-10-23 | 1986-10-23 | Coating method of reactive injection moldings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25242886A JPS63107784A (en) | 1986-10-23 | 1986-10-23 | Coating method of reactive injection moldings |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63107784A true JPS63107784A (en) | 1988-05-12 |
| JPH032025B2 JPH032025B2 (en) | 1991-01-14 |
Family
ID=17237224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25242886A Granted JPS63107784A (en) | 1986-10-23 | 1986-10-23 | Coating method of reactive injection moldings |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63107784A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02187171A (en) * | 1989-01-13 | 1990-07-23 | Shinto Paint Co Ltd | Method for painting reactive injection molded product |
| JPH10130577A (en) * | 1996-10-24 | 1998-05-19 | Shinto Paint Co Ltd | Undercoating material composition for dicyclopentadiene rim molding product |
| WO2003027195A1 (en) * | 2001-09-27 | 2003-04-03 | Nexsol Technologies, Inc. | Coating method by phase equilibrium |
-
1986
- 1986-10-23 JP JP25242886A patent/JPS63107784A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02187171A (en) * | 1989-01-13 | 1990-07-23 | Shinto Paint Co Ltd | Method for painting reactive injection molded product |
| JPH10130577A (en) * | 1996-10-24 | 1998-05-19 | Shinto Paint Co Ltd | Undercoating material composition for dicyclopentadiene rim molding product |
| WO2003027195A1 (en) * | 2001-09-27 | 2003-04-03 | Nexsol Technologies, Inc. | Coating method by phase equilibrium |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH032025B2 (en) | 1991-01-14 |
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