JPH02235916A - Production of heat-resistant resin and heat-resistant resin composition - Google Patents
Production of heat-resistant resin and heat-resistant resin compositionInfo
- Publication number
- JPH02235916A JPH02235916A JP1055846A JP5584689A JPH02235916A JP H02235916 A JPH02235916 A JP H02235916A JP 1055846 A JP1055846 A JP 1055846A JP 5584689 A JP5584689 A JP 5584689A JP H02235916 A JPH02235916 A JP H02235916A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- aromatic
- resistant resin
- resin
- acid anhydride
- 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
- 229920006015 heat resistant resin Polymers 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011342 resin composition Substances 0.000 title claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 27
- 239000000203 mixture Substances 0.000 abstract description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 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 3
- 238000009835 boiling Methods 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical class C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000004962 Polyamide-imide Substances 0.000 description 11
- 229920002312 polyamide-imide Polymers 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- -1 acid anhydride chloride Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 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
- 150000002576 ketones Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 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
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide 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
- 239000011253 protective coating Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyurethanes Or Polyureas (AREA)
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の製造法に関し、さらに詳しくは各
種基材の絶縁被覆、保護コートなどに好適な耐熱性樹脂
の製造法および該耐熱性樹脂を用いた耐熱性樹脂組成物
に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a heat-resistant resin, and more specifically, a method for producing a heat-resistant resin suitable for insulating coatings, protective coatings, etc. for various base materials, and the heat-resistant resin. The present invention relates to a heat-resistant resin composition using a thermoplastic resin.
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、各種基材のコート剤として、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。Polyamide-imide resin has excellent heat resistance, chemical resistance, and solvent resistance, so it is widely used as a coating agent for various base materials, such as for enamel wire festivals and heat-resistant paints.
ポリアミドイミド樹脂の製造法としては、（１）ジイソ
シアネートと三塩基酸無水物を反応させる方法、（２）
ジアミンと三塩基酸無水物を反応させる方法、（３）ジ
アミンと三塩基酸無水物クロライドを反応させる方法な
どが知られている。これらのうち得られる樹脂の性能、
製造工程の簡易さなとの点から（１）の方法が広《用い
られ、実用化されている。Methods for producing polyamide-imide resin include (1) a method of reacting diisocyanate and tribasic acid anhydride; (2)
A method of reacting a diamine with a tribasic acid anhydride, and (3) a method of reacting a diamine with a tribasic acid anhydride chloride are known. Performance of the resin obtained among these,
Method (1) is widely used and put into practical use because of the simplicity of the manufacturing process.
前記シイソシアネートと三塩基酸無水物とを反応させて
ポリアミドイミト樹脂を製造する場合、ポリアミドイミ
１−゛樹脂の分子量を使用に耐ええる程度に増大させる
ためには合成溶媒としてＮ−メチル−２−ピロリトンを
使用する必要があり、現在、大半のポリアミドイミド樹
脂がＮ−メチル２−ピロリドンを合成溶媒として製造さ
れている。When producing a polyamideimide resin by reacting the above-mentioned cyisocyanate with a tribasic acid anhydride, N-methyl- It is necessary to use 2-pyrrolidone, and currently most polyamideimide resins are manufactured using N-methyl 2-pyrrolidone as a synthesis solvent.
しかしながら、Ｉ〈−メチル−２−ビロリドンは、価格
が高く、また沸点が２０２゜Ｃと高いため、ポリアミド
イミド樹脂のＮ−メチル−２−ピロリドン溶液からポリ
アミトイミト樹脂を析出硬化させる場合、高温に加熱し
て溶媒を蒸発ざせる必要があるという欠点があった。However, I<-methyl-2-pyrrolidone is expensive and has a boiling point as high as 202°C, so when polyamidoimide resin is precipitated and cured from an N-methyl-2-pyrrolidone solution, it must be heated to a high temperature. The drawback was that the solvent had to be evaporated.
本発明の目的は、前記従来技術の問題点を解決し、合成
溶媒として、Ｎ−メチル−２−ピロリドンと比較して価
格が安く、かつ沸点の低いジメチルボルムアミド（ｍｐ
−１．３５゜Ｃ）を用いて高分了量のボリアミ１・イミ
１〜樹ｊ指を合成することかできる耐熱性樹脂の製造法
および該製造法によって得られた樹脂を用いた耐熱性樹
脂Ｎ１［１成物を提供ずることにある。An object of the present invention is to solve the problems of the prior art, and to use dimethylbormamide (mp
-1.35°C) A method for producing a heat-resistant resin capable of synthesizing a high-resolution amount of polyamide 1, iris 1 to resin, and heat resistance using the resin obtained by the production method The purpose of the present invention is to provide a resin N1 product.
〔課題を解決するだめの手段］
本発明は、芳香族ジイソシア不一トと芳香族二塩基酸無
水物とを反応させて耐熱性樹脂を製造するに際し、合成
溶媒としてジメチルボルムアミトを用い、かつ一般式（
Ｉ）
（ただし、式中、Ａは、フェノールまたは脂肪族酸残基
である）で表される１．８−シアザビシク口（５．４．
０）ウンデセン−７塩の存在下で反応させることを特徴
とする耐熱性樹脂の製造法およびその製造法によって得
られた樹脂を含む耐熱性樹脂組成物に関する。[Means for Solving the Problems] The present invention uses dimethylborum amide as a synthesis solvent when producing a heat-resistant resin by reacting an aromatic diisocyanito and an aromatic dibasic acid anhydride, and General formula (
I) 1.8-cyazabicyl (5.4.
0) A method for producing a heat-resistant resin characterized by carrying out the reaction in the presence of undecene-7 salt, and a heat-resistant resin composition containing the resin obtained by the method.
本発明に用いられる芳香族ジイソシア不一トとしては、
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“シフェニルエーテルジ
イソシアネート、キシリレンジイソシア不一ト、３，３
′−ジフェニルメタンジイソシアネ−１・などが挙げら
れる。これらの芳香族ジイソシアネートの他、１・リレ
ンジイソシアネート、４．４′−ジフェニルメタンジイ
ソシアネートの三景体などのポリイソシア不一ト、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。The aromatic diisocyanate used in the present invention includes:
4,4゜-diphenylmethane diisocyanate, tolylene diisocyanate, 4',4''cyphenyl ether diisocyanate, xylylene diisocyanate, 3,3
'-diphenylmethane diisocyanate-1. In addition to these aromatic diisocyanates, polyisocyanates such as 1-lylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and non-aromatic diisocyanates such as hexamethylene diisocyanate can be partially used in combination.
本発明に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挙げられる。該芳香族三塩基酸無
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、トリノシン酸などの芳香族多価カルボン酸、アジピ
ン酸、セハシン酸などの脂肪族多価カルボン酸等を併用
することもできる。The aromatic tribasic acid anhydride used in the present invention includes trimellitic anhydride. In addition to the 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 trinosinic acid, adipic acid, and sehasic acid. It is also possible to use aliphatic polycarboxylic acids such as .
前記芳香族シ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（芳香族シイソシアネ−１・／芳香
族三塩基酸無水物）で０． ８〜１．３とするのが好ま
しい。使用割合がこの範囲以外では、高分子量のポリア
ミトイミト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塩基酸無水物以外のイソシア不
−トや酸を併用する場合は、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。The ratio of the aromatic shiisocyanate and the aromatic tribasic acid anhydride used is a molar ratio (aromatic shiisocyanate-1/aromatic tribasic acid anhydride) of 0. It is preferable to set it as 8-1.3. If the usage ratio is outside this range, a high molecular weight polyamitimite resin may not be obtained. If an isocyanate or acid other than aromatic diisocyanate and aromatic basic acid anhydride is used together, the amount used shall be added to the amount of aromatic diisocyanate or aromatic tribasic acid anhydride within the above range. It is preferable that
本発明においては、合成溶媒としてジメヂルホルムアミ
ドが使用されるが、Ｎ−メチル−２−ピロリトンやキシ
レンなどの芳香族炭化水素を併用することもできる。ジ
メチルホルムアミ１・の使用量は特に制限がないが、合
成時の溶液粘度、経済性などの点から、芳香族ジイソシ
アネ−１〜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。In the present invention, dimethylformamide is used as a synthesis solvent, but aromatic hydrocarbons such as N-methyl-2-pyrrolitone and xylene can also be used in combination. There is no particular restriction on the amount of dimethylformamide 1 to be used, but from the viewpoint of solution viscosity during synthesis, economic efficiency, etc., it may be used per 100 parts by weight of the total amount of aromatic diisocyanes 1 to 1 and aromatic tribasic acid anhydride. It is preferable to use it in a range of 70 to 200 parts by weight.
本発明Ｃこ用いられる前記一般式（１）で表される１，
８−ジアザビシクロ（５．４．０）ウンテセン−７塩と
しては、例えばフェノール塩、オクチル酸塩、オレイン
酸塩などが挙げられる。これらは併用されてもよい。そ
の使用量は、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０．０５〜２．０重
量部の範囲が好ましく、０．１〜１．０重量部の範囲が
より好ましい。1 represented by the general formula (1) used in the present invention C,
Examples of the 8-diazabicyclo(5.4.0)unthecene-7 salt include phenol salt, octylate, and oleate. These may be used in combination. The amount used is preferably in the range of 0.05 to 2.0 parts by weight, and preferably in the range of 0.1 to 1.0 parts by weight, based on 100 parts by weight of the total amount of aromatic diisocyanate and aromatic tribasic acid anhydride. More preferred.
本発明における耐熱性樹脂は、前記芳香族ジイソシアネ
ートと芳香族三塩基酸無水物とをジメチルホルムアミド
を合成溶媒として１．８−ジアザビシク口（５，４．０
）ウンデセン−７塩の存在下で反応させて得られる。こ
の反応は、通常１２０〜１５５゜Ｃの温度で行なわれる
。空気中の水分の影響を低減するため、窒素などの雰囲
気下で行なうのが好ましい。The heat-resistant resin in the present invention is produced by synthesizing the aromatic diisocyanate and aromatic tribasic acid anhydride using dimethylformamide as a synthesis solvent.
) Obtained by reaction in the presence of undecene-7 salt. This reaction is normally carried out at a temperature of 120-155°C. In order to reduce the influence of moisture in the air, it is preferable to carry out the process under an atmosphere of nitrogen or the like.
前記方法によって得られたジメチルホルムアミドを含む
耐熱性樹脂組成物は、適当な粘度になるようにジメチル
ホルムアミド、Ｎ−メチル−２ピロリドンなどの極性溶
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頻などを加え
て希釈することもできる。The heat-resistant resin composition containing dimethylformamide obtained by the above method is mixed with dimethylformamide, a polar solvent such as N-methyl-2-pyrrolidone, an aromatic hydrocarbon such as xylene, methyl ethyl ketone, methyl isobutyl, etc. to obtain an appropriate viscosity. It can also be diluted by adding ketone complexes such as ketones.
前記耐熱性樹脂組成物には、用途に応じて各種の添加剤
を加えることもできる。該組成物の硬化剤としては、ビ
スフェノール型またはノポラック型のエボキシ樹脂、メ
ラミン樹脂、フェノール樹脂、ブロックイソシアネート
などの熱硬化性樹脂でポリアミドイミド樹脂と相溶性の
あるものが使用される。また塗膜表面の外観改質のため
各種金属塩、例えばオクテン酸亜鉛、ナフテン酸コバル
ト、ジブチル錫ラウレート、フッ素、シリコーン、脂肪
族系の各種界面活性剤を使用することができる。Various additives can also be added to the heat-resistant resin composition depending on the use. As the curing agent of the composition, thermosetting resins such as bisphenol type or nopolac type epoxy resins, melamine resins, phenol resins, and block isocyanates, which are compatible with the polyamide-imide resin, are used. Further, various metal salts such as zinc octenoate, cobalt naphthenate, dibutyltin laurate, fluorine, silicone, and various aliphatic surfactants can be used to modify the appearance of the coating surface.
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.
実施例１
４ ４１−ジフェニルメタンジイソシアネート２６２．
５ｇ（１．０５モル）、無水トリメリット酸１９２ｇ（
１．００モル）、ジメチルホルムアミド５ ５ ５．
５ ｇおよび１，８−ジアザビシク口（５４，０）ウン
デセン−７−フェノール塩１． ３ ６ ｇを２ρのフ
ラスコに仕込み、撹拌しながら、約１時間で温度を１５
０゜Ｃに上昇し、次いで１ ５ ０ ’Ｃで５時間保温
し、ポリアミドイミド樹脂を得た。Example 1 4 41-diphenylmethane diisocyanate 262.
5g (1.05 mol), trimellitic anhydride 192g (
1.00 mol), dimethylformamide 5 5 5.
5 g and 1,8-diazabisic(54,0) undecene-7-phenol salt 1. Pour 36 g into a 2ρ flask, and while stirring, raise the temperature to 15 g in about 1 hour.
The temperature was raised to 0°C and then kept at 150'C for 5 hours to obtain a polyamideimide resin.
得られた樹脂の分子量を測定し、その結果を第１表に示
した。The molecular weight of the obtained resin was measured and the results are shown in Table 1.
実施例２
４．４’−ジフェニルメタンジイソシアネート２８７．
５ｇ（１．１５モル）、無水トリメリット酸１９２ｇ（
１．００モル）、ジメチルホルムアミド５ ８ ６．
１ ｇ、１．８−ジアザビシクロ（５，４．０）ウンデ
セン−７−オクチル酸塩１． ２ ０ ｇおよび１，８
−ジアザビシク口（５．４．０）ウンデセン−７−オレ
イン酸塩１． ２ ０ ｇを２ｌのフラスコに仕込み、
撹拌しながら、約２時間で温度を１５０’Ｃに上昇し、
次いで１５０゜Ｃで７時間保温し、ポリアミドイミド樹
脂を得た。得られた樹脂の分子量を測定し、その結果を
第１表に示した。Example 2 4.4'-diphenylmethane diisocyanate 287.
5g (1.15 mol), trimellitic anhydride 192g (
1.00 mol), dimethylformamide 5 8 6.
1 g, 1.8-diazabicyclo(5,4.0) undecene-7-octylate 1. 20 g and 1,8
-Diazabicic acid (5.4.0) undecene-7-oleate 1. Pour 20g into a 2L flask,
While stirring, the temperature was raised to 150'C for about 2 hours,
Next, the mixture was kept at 150°C for 7 hours to obtain a polyamide-imide resin. The molecular weight of the obtained resin was measured and the results are shown in Table 1.
実施例３
４，４′−ジフエニルメタンシイソシアネート２６２．
５ｇ（１．０５モル〕、無水トリメリソト酸１７２．８
ｇ（０．９０モル）、アジビン酸１ ４． ６ ｇ（０
．１０モル）、ジメチルホルムアミド５ ５ ０． ０
ｇおよび１，８−ジアザビシク口（５，４，Ｏ）ウンデ
セン−７−オクチル酸塩２、７５ｇを２！のフラスコに
仕込み、撹拌しながら、約２時間で温度を１５０゜Ｃに
上昇し、次いで１５０゜Ｃで７時間保温し、ポリアミド
イミド樹脂を得た。得られた樹脂の分子量を測定し、そ
の結果を第１表に示した。Example 3 4,4'-diphenylmethane cyisocyanate 262.
5g (1.05 mol), trimeristhotic anhydride 172.8
g (0.90 mol), adivic acid 1 4. 6 g (0
．． 10 mol), dimethylformamide 5 5 0. 0
g and 2.75 g of 1,8-diazabisic(5,4,O) undecene-7-octylate. The mixture was charged into a flask, and the temperature was raised to 150°C over about 2 hours while stirring, and then kept at 150°C for 7 hours to obtain a polyamide-imide resin. The molecular weight of the obtained resin was measured and the results are shown in Table 1.
比較例１
４，４１−ジフェニルメタンジイソシアネート２５０ｇ
（１．００モル）、無水トリメリット酸１９２ｇ（１．
００モル）およびＮ−メチル−２−ビロリドン６６３ｇ
を２ｌのフラスコに仕込み、撹拌しながら、約３時間で
温度を１３０゜Ｃに上昇し、次いで１３０゜Ｃで２時間
保温し、ポリアミドイミド樹脂を得た。得られた樹脂の
分子量を測定し、その結果を第１表に示した。Comparative Example 1 250 g of 4,41-diphenylmethane diisocyanate
(1.00 mol), trimellitic anhydride 192 g (1.00 mol), trimellitic anhydride 192 g (1.00 mol),
00 mol) and 663 g of N-methyl-2-pyrrolidone
The mixture was charged into a 2-liter flask, and the temperature was raised to 130°C over about 3 hours while stirring, and then kept at 130°C for 2 hours to obtain a polyamide-imide resin. The molecular weight of the obtained resin was measured and the results are shown in Table 1.
比較例２
４，４″−ジフェニルメタンジイソシアネート２６２．
５ｇ（１．０５モル）、無水トリメリソｌ・酸１．９２
ｇ（１．００モル）およひジメチルホルムアミド５ ５
５． ５ ｇを２Ａのフラスコに仕込み、撹拌しなが
ら、約１時間で温度を１５０゜Ｃに上昇し、次いで１５
０゜Ｃで５時間保温し、ポリアミｌ−イミト樹脂を得た
。得られた樹脂の分子量を測定し、その結果を第１表に
示した。Comparative Example 2 4,4″-diphenylmethane diisocyanate 262.
5g (1.05 mol), anhydrous trimerisol acid 1.92
g (1.00 mol) and dimethylformamide 5 5
5. 5 g was placed in a 2A flask, and while stirring, the temperature was raised to 150°C in about 1 hour, and then the temperature was increased to 150°C.
The mixture was kept at 0°C for 5 hours to obtain a polyamyl-imito resin. The molecular weight of the obtained resin was measured and the results are shown in Table 1.
第１表
第１表から、合成溶媒としてジメチルホル１、アミドを
使用して１．８−ジアザビシク口（５．４．０）ウンデ
セン−７塩の存在下で合成をすることにより、Ｎ−メチ
ル−２−ピロリドンを使用して合成したポリアミドイミ
ドと同じ分子量を有するポリアミドイミドが得られるこ
とが示される。Table 1 From Table 1, N-methyl- It is shown that a polyamideimide having the same molecular weight as the polyamideimide synthesized using 2-pyrrolidone is obtained.
〈試験例〉
実施例］〜３および比較例１、２て得られた樹脂溶液を
基板に塗布して２００″Ｃの温度で５分間加熱し、厚さ
約２０μｍの塗膜板をそれぞれ作製し、これらの塗膜板
のクロスカット残率、耐水性、曲げ試験および塗膜中の
溶剤残率を調べ、その結果を第２表に示した。<Test Example> The resin solutions obtained in Examples ~ 3 and Comparative Examples 1 and 2 were applied to a substrate and heated at a temperature of 200''C for 5 minutes to produce coated plates with a thickness of approximately 20 μm. The cross-cut retention rate, water resistance, bending test, and solvent retention rate in the coating film of these coated plates were investigated, and the results are shown in Table 2.
＊１： ボリスチレン換算数平均分子量（注）分子量の
測定法は以下の装置で測定した。*1: Number average molecular weight in terms of boristyrene (Note) Molecular weight was measured using the following device.
液体クロマ｝・グラフ：日立製作所製６５５八カラム：
日立化成工業社製、
Ｇ＞Ｓ３００ＭＤ−５
溶 媒：ジメチルボルムアミド：テトラヒＦ口フラン−
１＝１
１ ］
第 ２
表
＊１：ＪＩＳ Ｂ ０２０２（クロスカット残率）
較すると耐水性が向上し、また塗膜中の溶剤残率も半分
以下に低下することが示される。また比較例２で得られ
た樹脂の塗布板に比較するとクロスカット残率および曲
げ試験が著しく向上することが示される。Liquid chroma}・Graph: Hitachi 6558 column:
Manufactured by Hitachi Chemical Co., Ltd., G>S300MD-5 Solvent: Dimethylborumamide: Tetrahyfuran-
1=1 1] Table 2 *1: JIS B 0202 (Cross cut remaining rate)
Comparison shows that the water resistance is improved and the percentage of solvent remaining in the coating film is reduced to less than half. Furthermore, when compared with the resin coated plate obtained in Comparative Example 2, it is shown that the crosscut residual ratio and bending test are significantly improved.
本発明の製造法によれば、原料費が安く、かつ低沸点の
合成溶媒を用いて高分子量の耐熱性樹脂を製造すること
ができる。またこの樹脂を用いて得られる耐熱性樹脂組
成物は、低温で硬化しても、塗膜中の溶剤残率を低下で
きるので良好な性能が得られる。According to the production method of the present invention, a high molecular weight heat-resistant resin can be produced using low raw material costs and a synthetic solvent with a low boiling point. Furthermore, the heat-resistant resin composition obtained using this resin can provide good performance even when cured at low temperatures, since the solvent residual rate in the coating film can be reduced.
Ｗ２ ：塗膜板の質量W2: Mass of coated plate
Claims (1)
を反応させて耐熱性樹脂を製造するに際し、合成溶媒と
してジメチルホルムアミドを用い、かつ一般式（ I ） ▲数式、化学式、表等があります▼（ I ） （ただし、式中、Ａは、フェノールまたは脂肪族酸残基
である）で表される１，８−ジアザビシクロ（５、４、
０）ウンデセン−７塩の存在下で反応させることを特徴
とする耐熱性樹脂の製造法。 ２、芳香族ジイソシアネートと芳香族三塩基酸無水物と
の使用量が、モル比（芳香族ジイソシアネート／芳香族
三塩基酸無水物）で０．８〜１．３であることを特徴と
する請求項１記載の耐熱性樹脂の製造法。 ３、請求項１または２記載の製造法によって製造された
耐熱性樹脂を含む耐熱性樹脂組成物。[Claims] 1. When producing a heat-resistant resin by reacting an aromatic diisocyanate and an aromatic tribasic acid anhydride, dimethylformamide is used as a synthesis solvent, and the general formula (I) ▲Mathematical formula, chemical formula , tables, etc. ▼(I) (wherein A is a phenol or aliphatic acid residue) 1,8-diazabicyclo(5,4,
0) A method for producing a heat-resistant resin, which comprises reacting in the presence of undecene-7 salt. 2. A claim characterized in that the amounts of aromatic diisocyanate and aromatic tribasic acid anhydride used are in a molar ratio (aromatic diisocyanate/aromatic tribasic acid anhydride) of 0.8 to 1.3. Item 1. A method for producing a heat-resistant resin according to item 1. 3. A heat-resistant resin composition comprising a heat-resistant resin produced by the production method according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1055846A JPH02235916A (en) | 1989-03-08 | 1989-03-08 | Production of heat-resistant resin and heat-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1055846A JPH02235916A (en) | 1989-03-08 | 1989-03-08 | Production of heat-resistant resin and heat-resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02235916A true JPH02235916A (en) | 1990-09-18 |
Family
ID=13010391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1055846A Pending JPH02235916A (en) | 1989-03-08 | 1989-03-08 | Production of heat-resistant resin and heat-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02235916A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125310A1 (en) * | 2010-04-05 | 2011-10-13 | サンアプロ株式会社 | Catalyst for production of polyurethane resin and method for producing polyurethane resin |
-
1989
- 1989-03-08 JP JP1055846A patent/JPH02235916A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125310A1 (en) * | 2010-04-05 | 2011-10-13 | サンアプロ株式会社 | Catalyst for production of polyurethane resin and method for producing polyurethane resin |
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