JPH0331361A - Heat-resistant resin composition and metal plate coated with heat-resistant resin - Google Patents
Heat-resistant resin composition and metal plate coated with heat-resistant resinInfo
- Publication number
- JPH0331361A JPH0331361A JP16724089A JP16724089A JPH0331361A JP H0331361 A JPH0331361 A JP H0331361A JP 16724089 A JP16724089 A JP 16724089A JP 16724089 A JP16724089 A JP 16724089A JP H0331361 A JPH0331361 A JP H0331361A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resistant resin
- metal plate
- resin composition
- aromatic
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229920006015 heat resistant resin Polymers 0.000 title claims description 28
- 239000011342 resin composition Substances 0.000 title claims description 20
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 23
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 23
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 13
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 6
- 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 abstract description 2
- 238000005452 bending Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 butanetricarboxylic anhydride Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性樹脂組成物および耐熱性樹脂塗装金属板
に関し、さらに詳しくは各種金属板の保護コートに好適
な加工性に優れた耐熱性樹脂組成物およびこれを用いた
耐熱性樹脂塗装金属板に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-resistant resin composition and a heat-resistant resin-coated metal plate, and more specifically to a heat-resistant resin composition with excellent processability suitable for protective coating of various metal plates. This invention relates to a resin composition and a heat-resistant resin-coated metal plate using the same.
ポリアミドイミド樹脂は、耐熱性、耐薬品性、耐溶剤性
が優れているため、特にエナメル線用フェス、耐熱塗料
などに広く使用されている。しかし、ポリアミドイミド
樹脂は、ポリエーテルスルホン、変性シリコーン樹脂な
どに比べて曲げ性に劣るため、この樹脂を塗布焼き付け
して得られる金属板は加工性に劣るという問題があった
。Polyamide-imide resin has excellent heat resistance, chemical resistance, and solvent resistance, so it is widely used, especially in festivals for enameled wires, heat-resistant paints, and the like. However, since polyamide-imide resin has poor bendability compared to polyether sulfone, modified silicone resin, etc., there is a problem in that a metal plate obtained by coating and baking this resin has poor workability.
本発明の目的は、前記従来技術の問題点を解決し、曲げ
性に優れ、塗布焼き付けして得られる金属板の加工性に
優れたポリアミドイミド樹脂組成物およびこれを用いた
耐熱性樹脂塗装金属板を提供することにある。The object of the present invention is to solve the problems of the prior art and to provide a polyamide-imide resin composition that has excellent bendability and workability into metal plates obtained by coating and baking, and a heat-resistant resin-coated metal using the same. The purpose is to provide a board.
本発明は、塩基性極性溶媒の存在下で芳香族ジイソシア
ネートと芳香族三塩基酸無水物を反応させて得られるポ
リアミドイミド樹脂と、一般式Ｉ（式中、ｎは整数）で
表される構造を主成分とするフェノキシ樹脂とを含む耐
熱性樹脂組成物およびこの耐熱性樹脂組成物を金属板に
塗布焼き付けして得られる耐熱性樹脂塗装金属板に関す
る。The present invention relates to a polyamide-imide resin obtained by reacting an aromatic diisocyanate and an aromatic tribasic acid anhydride in the presence of a basic polar solvent, and a structure represented by the general formula I (where n is an integer). The present invention relates to a heat-resistant resin composition containing a phenoxy resin whose main component is a phenoxy resin, and a heat-resistant resin-coated metal plate obtained by coating and baking this heat-resistant resin composition on a metal plate.
本発明に用いられる芳香族ジイソシアネートとしては、
４．４′−ジフェニルメタンジイソシアネート、トリレ
ンジイソシアネート、４．４′ジフエニルエーテルジイ
ソシアネート、キシリレンジイソシアネート、３，３′
−ジフェニルメタンジイソシアネートなどがあげられる
。これらの芳香族ジイソシアネートの他、トリレンジイ
ソシアネート、４．４′−ジフェニルメタンジイソシア
ネートの三量体などのポリイソシアネート、ヘキサメチ
レンジイソシアネートなどの非芳香族ジイソシアネート
を一部併用することができる。その使用量は、芳香族ジ
イソシアネートに対して３０重量％以下とすることが好
ましい。As the aromatic diisocyanate used in the present invention,
4.4'-diphenylmethane diisocyanate, tolylene diisocyanate, 4.4' diphenyl ether diisocyanate, xylylene diisocyanate, 3,3'
-Diphenylmethane diisocyanate and the like. In addition to these aromatic diisocyanates, polyisocyanates such as tolylene diisocyanate and trimer of 4,4'-diphenylmethane diisocyanate, and non-aromatic diisocyanates such as hexamethylene diisocyanate can be partially used in combination. The amount used is preferably 30% by weight or less based on the aromatic diisocyanate.
本発明で用いられる芳香族三塩基酸無水物としては、ト
リメリット酸無水物があげられる。この芳香族三塩基酸
無水物の他、酸成分としてブタントリカルボン酸無水物
などの脂肪酸三塩基酸無水物、テレフタル酸、イソフタ
ル酸、トリメシン酸などの芳香族多価カルボン酸、アジ
ピン酸、セバシン酸などの脂肪族多価カルボン酸等を併
用することができる。その使用量は、芳香族三塩基酸無
水物に対して５０重量％以下とすることが好ましい。The aromatic tribasic acid anhydride used in the present invention includes trimellitic anhydride. In addition to this aromatic tribasic acid anhydride, acid components include fatty acid tribasic acid anhydrides such as butanetricarboxylic anhydride, aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, and trimesic acid, adipic acid, and sebacic acid. Aliphatic polycarboxylic acids such as these can be used in combination. The amount used is preferably 50% by weight or less based on the aromatic tribasic acid anhydride.
前記芳香族ジイソシアネートと芳香族三塩基酸無水物の
使用割合は、モル比で芳香族ジイソシアネート／芳香族
三塩基酸無水物＝０．８〜１．３とするのが好ましい。The ratio of the aromatic diisocyanate and aromatic tribasic acid anhydride used is preferably such that the molar ratio of aromatic diisocyanate/aromatic tribasic acid anhydride is 0.8 to 1.3.
使用割合がこの範囲以外では高分子量のポリアミドイミ
ド樹脂が得られないことがある。芳香族ジイソシアネー
トおよび芳香族三塩基酸無水物以外のイソシアネートや
酸を併用する場合には、それらの使用量を芳香族ジイソ
シアネートまたは芳香族三塩基酸無水物の使用量に加算
して上記範囲内とすることが好ましい。If the proportion used is outside this range, a high molecular weight polyamide-imide resin may not be obtained. If an isocyanate or acid other than aromatic diisocyanate and aromatic tribasic acid anhydride is used together, the amount used should be added to the amount used of aromatic diisocyanate or aromatic tribasic acid anhydride to ensure that it is within the above range. It is preferable to do so.
前記芳香族ジイソシアネートと芳香族三塩基酸無水物の
反応溶媒としては、Ｎ−メチル−２−ピロリドン、ジメ
チルアセトアミド、ジメチルホルムアミドなどの塩基性
極性溶媒が使用される。塩基性極性溶媒を使用せず、フ
ェノール系溶媒などを使用すると造膜性が低下する。こ
の溶媒の使用量は、反応時の溶液粘度、経済性などの点
から芳香族ジイソシアネートと芳香族三塩基酸無水物の
総量１００重量部に対して７０〜２００重量部の範囲で
用いるのが好ましい。合成温度は特に制限はないが通常
６０〜２００°Ｃの範囲で行われ、反応の進行は炭酸ガ
スの発生により確認できる。場合によっては、トリエチ
ルアミン、Ｎ−メチル−モルホリン、ｌ、８−ジアザビ
シクロ（５，４゜０）ウンデセン−７塩などの塩基性触
媒を使用してもよい。As a reaction solvent for the aromatic diisocyanate and aromatic tribasic acid anhydride, a basic polar solvent such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, etc. is used. If a phenolic solvent or the like is used instead of a basic polar solvent, film-forming properties will deteriorate. The amount of this solvent to be used is preferably in the range of 70 to 200 parts by weight based on 100 parts by weight of the total amount of aromatic diisocyanate and aromatic tribasic acid anhydride in terms of solution viscosity during reaction, economic efficiency, etc. . The synthesis temperature is not particularly limited, but is usually carried out in the range of 60 to 200°C, and the progress of the reaction can be confirmed by the generation of carbon dioxide gas. Optionally, basic catalysts such as triethylamine, N-methyl-morpholine, 1,8-diazabicyclo(5,4°0) undecene-7 salt may be used.
前記方法によって得られたポリアミドイミド樹脂は、適
当な粘度になるように、Ｎ−メチル−２−ピロリドン、
ジメチルアセトアミド、ジメチルホルムアミドなどの塩
基性極性溶媒、キシレンなどの芳香族炭化水素、メチル
エチルケトン、メチルイソブチルケトンなどのケトン類
などを加えて希釈することもできる。The polyamideimide resin obtained by the above method is treated with N-methyl-2-pyrrolidone,
It can also be diluted by adding basic polar solvents such as dimethylacetamide and dimethylformamide, aromatic hydrocarbons such as xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
本発明に使用されるフェノキシ樹脂は、前記−般弐Ｉで
示される構造を主成分とする。該フェノキシ樹脂の分子
量には特に制限はないが、通常は数平均分子量が２０，
０００以上のものが使用され、例えば、市販品であるＵ
ＣＣ社製ＰＫＨＨ。The phenoxy resin used in the present invention has the structure represented by -General I as a main component. There is no particular restriction on the molecular weight of the phenoxy resin, but usually the number average molecular weight is 20,
000 or more are used, for example, commercially available U
PKHH manufactured by CC.
東部化成社製ＹＰ−５０などがあげられる。Examples include YP-50 manufactured by Tobu Kasei Co., Ltd.
フェノキシ樹脂の使用量は、ポリアミドイミド樹脂１０
０重量部に対して１〜２０重量部が好ましく、特に５〜
ｌＯ重量部が好ましい。使用量が少なすぎると、曲げ性
が十分でないことがあり、逆に多すぎると耐熱性、耐薬
品性、耐溶剤性が低下することがある。The amount of phenoxy resin used is 10% of polyamideimide resin.
It is preferably 1 to 20 parts by weight, especially 5 to 0 parts by weight.
10 parts by weight are preferred. If the amount used is too small, bendability may not be sufficient, whereas if the amount is too large, heat resistance, chemical resistance, and solvent resistance may deteriorate.
本発明の耐熱性樹脂組成物は、前記ポリアミドイミド樹
脂およびフェノキシ樹脂の他、用途に応じて各種の硬化
剤、触媒、外観改質剤を併用してもよい。The heat-resistant resin composition of the present invention may contain, in addition to the polyamideimide resin and phenoxy resin, various curing agents, catalysts, and appearance modifiers depending on the application.
本発明の耐熱性樹脂組成物を金属板に塗布焼き付けする
ことにより、曲げ性および加工性に優れた耐熱性樹脂塗
装金属板が得られる。塗装法には特に制限がなく、塗装
物の形状に応じてスプレー塗装、ハケ塗り、ローラ塗り
などが行われる。焼付温度は、１５０〜４５０°Ｃの範
囲が好ましく、低温であれば長時間、高温であれば短時
間加熱する。また塗膜厚には特に制限がないが、通常３
〜３０μｍに塗装される。また基材の金属板にも特に制
限はなく、アルミニウム、鉄、ステンレス、銅などが使
用されるが、鉄およびアルミニウムが特に好ましい。密
着性のレベルを向上するために、ブラスト処理や化学的
表面処理をしたり、各種プライマーを下塗りすることも
できる。By coating and baking the heat-resistant resin composition of the present invention on a metal plate, a heat-resistant resin-coated metal plate with excellent bendability and workability can be obtained. There are no particular restrictions on the coating method, and spray coating, brush coating, roller coating, etc. are performed depending on the shape of the object to be coated. The baking temperature is preferably in the range of 150 to 450°C, and heating is performed for a long time if the temperature is low, and for a short time if the temperature is high. There is no particular limit to the coating thickness, but it is usually 3.
~30μm coated. Further, there is no particular restriction on the metal plate of the base material, and aluminum, iron, stainless steel, copper, etc. are used, and iron and aluminum are particularly preferred. To improve the level of adhesion, it can be blasted, chemically surface treated, or primed with various primers.
以下、本発明を実施例により詳しく説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
なお、倒置部とあるのは重量部である。Note that "inverted part" refers to parts by weight.
実施例１
４．４゛−ジフェニルメタンジイソシアネート２５０ｇ
、ｌ−リメリット酸無水物１９２ｇおよびＮ−メチル−
２−ピロリドン６６３ｇを２２のフラスコに仕込み、攪
拌しながら約４時間で温度を１３０ ’Ｃに上昇し、つ
いで１３０ ’Ｃで３時間保温し、ポリアミドイミド樹
脂を得た。ついでキシレン２００ｇを添加してポリアミ
ドイミド樹脂溶液を得た。この溶液の不揮発分（２００
’ｃ−２ｈ）は３５重量％であり、粘度は５１ポアズ（
３０”Ｃ）であった。Example 1 250 g of 4.4′-diphenylmethane diisocyanate
, 192 g of l-limellitic anhydride and N-methyl-
663 g of 2-pyrrolidone was charged into a No. 22 flask, and the temperature was raised to 130'C over about 4 hours while stirring, and then kept at 130'C for 3 hours to obtain a polyamideimide resin. Then, 200 g of xylene was added to obtain a polyamideimide resin solution. The non-volatile content of this solution (200
'c-2h) is 35% by weight, and the viscosity is 51 poise (
30"C).
このポリアミドイミド樹脂溶液３００ｇに、フェノキシ
樹脂ＰＫＨＨ（ＵＣＣ社製） ５．２５ ｇ（ポリアミ
ドイミド樹脂１００部に対して５部）を添加し、均一に
なるまで加熱攪拌して耐熱性樹脂組成物を得た。To 300 g of this polyamide-imide resin solution, 5.25 g (5 parts per 100 parts of polyamide-imide resin) of phenoxy resin PKHH (manufactured by UCC) was added, and the heat-resistant resin composition was heated and stirred until uniform. Obtained.
実施例２
実施例１で得たポリアミドイミド樹脂溶液３００ｇに、
フェノキシ樹脂ＹＰ−５０（東部化成社製）１０．５ｇ
（ポリアミドイミド樹脂１００部に対して１０部）を添
加し、均一になるまで加熱攪拌して耐熱性樹脂組成物を
得た。Example 2 To 300 g of the polyamideimide resin solution obtained in Example 1,
Phenoxy resin YP-50 (manufactured by Tobu Kasei Co., Ltd.) 10.5g
(10 parts to 100 parts of polyamide-imide resin) was added, and the mixture was heated and stirred until uniform, to obtain a heat-resistant resin composition.
実施例３
４．４１−ジフェニルメタンジイソシアネート２６２．
５ｇ、トリメリット酸無水物１７２．８ｇ。Example 3 4.41-diphenylmethane diisocyanate 262.
5g, trimellitic anhydride 172.8g.
セバシンＭ １７．４ ｇおよびＮ−メチル−２−ピロ
リドン６７９ｇを２１のフラスコに仕込み、攪拌しなが
ら約４時間で温度を１２５°Ｃに上昇し、ついでｌ ２
５ ’Ｃで２時間保温し、ポリアミドイミド樹脂を得た
。ついでキシレン２１２ｇを添加してポリアミドイミド
樹脂溶液を得た。この溶液の不揮発分（２００°Ｃ−２
ｈ）は３５重量％であった。17.4 g of Sebacin M and 679 g of N-methyl-2-pyrrolidone were charged into 21 flasks, the temperature was raised to 125° C. over about 4 hours with stirring, and then 125 g of N-methyl-2-pyrrolidone was charged.
The mixture was kept warm at 5'C for 2 hours to obtain a polyamideimide resin. Then, 212 g of xylene was added to obtain a polyamideimide resin solution. Non-volatile content of this solution (200°C-2
h) was 35% by weight.
このポリアミドイミド樹脂溶液３００ｇに、フェノキシ
樹脂ＰＫＨＨ，７，８８ｇ （ポリアミドイミド樹脂１
００部に対して７．５部）を添加し、均一になるまで加
熱撹拌して耐熱性樹脂組成物を得た。To 300 g of this polyamide-imide resin solution, add 7.88 g of phenoxy resin PKHH (polyamide-imide resin 1
00 parts) was added thereto, and the mixture was heated and stirred until uniform, to obtain a heat-resistant resin composition.
比較例１
実施例１で得られたポリアミドイミド樹脂溶液を耐熱性
樹脂組成物として用いた。Comparative Example 1 The polyamide-imide resin solution obtained in Example 1 was used as a heat-resistant resin composition.
〈試験例〉
実施例１〜３および比較例１で得られた耐熱性樹脂組成
物を用いて第１表に示す試作条件で耐熱性樹脂塗装金属
板を作製し、その特性を測定した。<Test Example> Using the heat-resistant resin compositions obtained in Examples 1 to 3 and Comparative Example 1, a heat-resistant resin-coated metal plate was produced under the trial production conditions shown in Table 1, and its characteristics were measured.
その結果を第２表に示した。The results are shown in Table 2.
第１表 第２表 ＊１：ＪＩＳ ＢＯ２０２に準じて行った。Table 1 Table 2 *1: Conducted according to JIS BO202.
＊２：曲げ試験
塗装金属板を塗装面を外側にして折り曲げる。ついで、
塗装に使用した金属板と同じ金属板を内側にはさみ、８
０ｋｇ／ｃｄで５秒押しつぶし、塗膜に亀裂が発生する
かどうか１０倍の拡大鏡で観察する。亀裂が発生しなく
なるまで、はさむ金属板の枚数を増やして試験し、亀裂
が発生しなくなった時点の金属板の枚数で示した。（例
えば１枚で亀裂が発生したときはｌＴ１３枚で亀裂が発
生したときは３Ｔと記す）
＊３：２００°Ｃで５０時間加熱劣化させたときの密着
性（クロスカット残率、％）
＊４：メチルエチルケトンを含浸したガーゼで塗膜表面
を摩擦し、塗膜の外観変化を観察（摩擦回数１００回）
。*2: Bending test A painted metal plate is bent with the painted side facing outward. Then,
Sandwich the same metal plate used for painting inside and
Crush for 5 seconds at 0 kg/cd and observe with a 10x magnifying glass to see if any cracks occur in the coating. The test was conducted by increasing the number of metal plates sandwiched together until no cracks occurred, and the number of metal plates at the time no cracks occurred was expressed. (For example, if a crack occurs in one sheet, write it as 1T. If a crack occurs in 13 sheets, write it as 3T.) *3: Adhesion after heating and deteriorating at 200°C for 50 hours (crosscut residual rate, %) * 4: Rub the paint film surface with gauze impregnated with methyl ethyl ketone and observe changes in the appearance of the paint film (100 times of rubbing)
.
第２表から、実施例１〜３で得られた樹脂の塗装板は、
比較例１で得られた塗装板に比較して曲げ性が著しく向
上していることが示される。From Table 2, the resin coated plates obtained in Examples 1 to 3 are as follows:
It is shown that the bendability is significantly improved compared to the coated plate obtained in Comparative Example 1.
本発明の耐熱性樹脂組成物によれば、曲げ性および加工
性に優れた耐熱性樹脂塗装金属板を得ることができる。According to the heat-resistant resin composition of the present invention, a heat-resistant resin-coated metal plate with excellent bendability and workability can be obtained.
しかもこの金属板は、優れた耐熱性、耐溶剤性、耐薬品
性をも有しているため、過酷な加工が要求される分野、
例えば自動車、家電用などのプレコートメタル、缶用材
料等に特に有用である。Moreover, this metal plate has excellent heat resistance, solvent resistance, and chemical resistance, so it can be used in fields where harsh processing is required.
For example, it is particularly useful for pre-coated metals for automobiles, home appliances, etc., materials for cans, etc.
Claims (1)
と芳香族三塩基酸無水物を反応させて得られるポリアミ
ドイミド樹脂と、一般式 I ▲数式、化学式、表等があります▼ （式中、ｎは整数）で表される構造を主成分とするフェ
ノキシ樹脂とを含む耐熱性樹脂組成物。 ２、ポリアミドイミド樹脂１００重量部に対してフェノ
キシ樹脂が１〜２０重量部である請求項１記載の耐熱性
樹脂組成物。 ３、芳香族三塩基酸無水物が無水トリメリット酸である
請求項１または２記載の耐熱性樹脂組成物４、芳香族ジ
イソシアネートと芳香族三塩基酸無水物との使用割合が
、モル比で芳香族ジイソシアネート／芳香族三塩基酸無
水物＝０．８〜１．３である請求項１ないし３記載の耐
熱性樹脂組成物。 ５、請求項１ないし４記載の耐熱性樹脂組成物を金属板
に塗布焼き付けして得られる耐熱性樹脂塗装金属板。 ６、金属板の材質が鉄またはアルミニウムである請求項
５記載の耐熱性樹脂塗装金属板。[Claims] 1. A polyamide-imide resin obtained by reacting an aromatic diisocyanate and an aromatic tribasic acid anhydride in the presence of a basic polar solvent, and the general formula I ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ A heat-resistant resin composition containing a phenoxy resin whose main component is a structure represented by (where n is an integer). 2. The heat-resistant resin composition according to claim 1, wherein the phenoxy resin is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyamide-imide resin. 3. The heat-resistant resin composition according to claim 1 or 2, wherein the aromatic tribasic acid anhydride is trimellitic anhydride. 4. The heat-resistant resin composition according to claim 1, wherein the ratio of aromatic diisocyanate/aromatic tribasic acid anhydride is 0.8 to 1.3. 5. A heat-resistant resin-coated metal plate obtained by coating and baking the heat-resistant resin composition according to claims 1 to 4 on a metal plate. 6. The heat-resistant resin-coated metal plate according to claim 5, wherein the metal plate is made of iron or aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16724089A JPH0331361A (en) | 1989-06-28 | 1989-06-28 | Heat-resistant resin composition and metal plate coated with heat-resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16724089A JPH0331361A (en) | 1989-06-28 | 1989-06-28 | Heat-resistant resin composition and metal plate coated with heat-resistant resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0331361A true JPH0331361A (en) | 1991-02-12 |
Family
ID=15846059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16724089A Pending JPH0331361A (en) | 1989-06-28 | 1989-06-28 | Heat-resistant resin composition and metal plate coated with heat-resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0331361A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8708148B2 (en) | 2003-11-11 | 2014-04-29 | Graphics Packaging International, Inc. | Nestable container with uniform stacking features |
| US9457509B2 (en) | 2011-09-09 | 2016-10-04 | Graphic Packaging International, Inc. | Tool for forming a three dimensional article or container |
| US9694553B2 (en) | 2009-06-17 | 2017-07-04 | Graphic Packaging International, Inc. | Tool for forming a three dimensional container or construct |
-
1989
- 1989-06-28 JP JP16724089A patent/JPH0331361A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8708148B2 (en) | 2003-11-11 | 2014-04-29 | Graphics Packaging International, Inc. | Nestable container with uniform stacking features |
| US9315292B2 (en) | 2003-11-11 | 2016-04-19 | Graphic Packaging International, Inc. | Nestable container with uniform stacking features |
| US9694553B2 (en) | 2009-06-17 | 2017-07-04 | Graphic Packaging International, Inc. | Tool for forming a three dimensional container or construct |
| US9457509B2 (en) | 2011-09-09 | 2016-10-04 | Graphic Packaging International, Inc. | Tool for forming a three dimensional article or container |
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