JP2010121001A - Polyamideimide resin-based heat-resistant resin composition, coating film using the same, heat-resistant coating material, and plate with coating film - Google Patents
Polyamideimide resin-based heat-resistant resin composition, coating film using the same, heat-resistant coating material, and plate with coating film Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 57
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title abstract description 5
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 2
- -1 diisocyanate compound Chemical class 0.000 abstract description 20
- 239000004135 Bone phosphate Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 6
- 239000002798 polar solvent Substances 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 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 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KEZPMZSDLBJCHH-UHFFFAOYSA-N n-(4-anilinophenyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C=C1)=CC=C1NC1=CC=CC=C1 KEZPMZSDLBJCHH-UHFFFAOYSA-N 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
Description
本発明は、ポリアミドイミド樹脂系耐熱性樹脂組成物及びこれを用いた塗膜、耐熱性塗料、塗膜板に関する。 The present invention relates to a polyamide-imide resin heat-resistant resin composition, a coating film using the same, a heat-resistant coating material, and a coating film plate.
一般にポリアミドイミド樹脂は、耐熱性、耐薬品性及び耐溶剤性に優れているため、エナメル線用ワニスや各種塗料の塗膜成分として広く用いられ、各種基板に保護塗膜を形成している。従来のポリアミドイミド樹脂としては、例えば、４，４-ジフェニルメタンジイソシアネ-トと無水トリメリット酸との反応により得られるポリアミドイミド樹脂（例えば、特許文献１、特許文献２を参照）が知られている。
In general, polyamide-imide resins are excellent in heat resistance, chemical resistance and solvent resistance, and are therefore widely used as coating film components for enameled wire varnish and various paints, and form protective coating films on various substrates. As a conventional polyamideimide resin, for example, a polyamideimide resin obtained by reaction of 4,4-diphenylmethane diisocyanate and trimellitic anhydride (see, for example,
近年、潤滑性、非粘着性を要する自動車及び家電・厨房器具部品用の耐熱塗料分野では塗料の塗装方法が塗装工程省略、工期短縮、公害対策の面から、従来のポストコートからプレコート法に代替されつつある。そこで、塗膜としては耐熱性および密着性に優れ、さらには加工性（曲げ性）に優れることが要求されてきている。
ところが、現状ポリアミドイミド樹脂を塗膜成分とする耐熱保護塗膜は、耐熱性および密着性には優れるものの加工性が低下し、特に、硬化温度が３５０℃以上であるとその傾向が著しいという欠点があった。
In recent years, in the field of heat-resistant paints for automobiles, home appliances, and kitchen appliance parts that require lubricity and non-adhesiveness, the coating method is replaced with the pre-coating method instead of the conventional post-coating method in terms of omitting the painting process, shortening the work period, and preventing pollution. It is being done. Therefore, it has been required that the coating film is excellent in heat resistance and adhesion, and further in workability (bendability).
However, the current heat-resistant protective coating film comprising polyamideimide resin as a coating film component is excellent in heat resistance and adhesion, but the workability is lowered, and particularly when the curing temperature is 350 ° C. or higher, the tendency is remarkable. was there.
本発明は、３５０℃以上での高温硬化後の耐熱性および密着性、さらには加工性に優れたポリアミドイミド樹脂系耐熱性樹脂組成物及びこの耐熱性樹脂組成物を塗膜成分とする耐熱性塗料、塗膜、家電・厨房部品用塗膜板を提供するものである。 The present invention relates to a heat-resistant and adhesive property after high-temperature curing at 350 ° C. or higher, and a polyamide-imide resin-based heat-resistant resin composition excellent in workability, and heat resistance using the heat-resistant resin composition as a coating film component. The present invention provides a coating plate for paints, coating films, home appliances and kitchen parts.
本発明は、［１］（Ａ）ポリアミドイミド樹脂と、（Ｂ）老化防止剤を含有してなる耐熱性樹脂組成物に関する。
また、本発明は、［２］（Ａ）ポリアミドイミド樹脂の数平均分子量が、１０，０００〜５０，０００である上記［１］に記載のポリアミドイミド樹脂系耐熱性樹脂組成物にも関する。
さらに、本発明は、［３］（Ａ）ポリアミドイミド樹脂１００質量部に対し、（Ｂ）老化防止剤を０．０１〜１０質量部含有する上記［１］又は［２］に記載のポリアミドイミド樹脂系耐熱性樹脂組成物に関する。
また、本発明は、［４］老化防止剤がオクチル化ジフェニルアミンである上記［１］〜［３］のいずれかに記載のポリアミドイミド樹脂系耐熱性樹脂組成物に関する。
さらに、本発明は、［５］上記［１］〜［４］のいずれかに記載のポリアミドイミド樹脂系耐熱性樹脂組成物を塗布及び加熱して成形された塗膜に関する。
また、本発明は、［６］上記［１］〜［４］のいずれかに記載のポリアミドイミド樹脂系耐熱性樹脂組成物を表面に塗布及び加熱して成形された塗膜を有する塗膜板に関する。
また、本発明は、［７］上記［１］〜［４］のいずれかに記載のポリアミドイミド樹脂系耐熱性樹脂組成物及び有機溶媒を含有する耐熱性塗料に関する。
また、本発明は、［８］上記［１］〜［４］のいずれかに記載のポリアミドイミド樹脂系耐熱性樹脂組成物と各種固体潤滑剤とから成る塗膜を表面に塗布及び加熱して成形された塗膜を有する自動車または家電・厨房部品用塗膜板に関する。
The present invention relates to a heat resistant resin composition comprising [1] (A) a polyamideimide resin and (B) an anti-aging agent.
The present invention also relates to the polyamideimide resin heat-resistant resin composition according to the above [1], wherein the number average molecular weight of [2] (A) the polyamideimide resin is 10,000 to 50,000.
Furthermore, the present invention provides [3] (A) Polyamideimide as described in [1] or [2] above, containing 0.01 to 10 parts by mass of an anti-aging agent with respect to 100 parts by mass of the polyamideimide resin. The present invention relates to a resin-based heat resistant resin composition.
The present invention also relates to the polyamideimide resin heat-resistant resin composition according to any one of the above [1] to [3], wherein [4] the antioxidant is octylated diphenylamine.
Furthermore, the present invention relates to [5] a coating film formed by applying and heating the polyamideimide resin heat-resistant resin composition according to any one of [1] to [4].
The present invention also provides [6] a coated plate having a coated film formed by applying and heating the polyamideimide resin heat-resistant resin composition according to any one of [1] to [4] on the surface. About.
The present invention also relates to [7] a heat-resistant coating material containing the polyamideimide resin-based heat-resistant resin composition according to any one of [1] to [4] and an organic solvent.
The present invention also includes [8] coating and heating on the surface a coating film comprising the polyamideimide resin heat-resistant resin composition according to any one of [1] to [4] above and various solid lubricants. The present invention relates to a coating film plate for automobiles or home appliances / kitchen parts having a molded coating film.
本発明のポリアミドイミド樹脂系耐熱性樹脂組成物を塗膜成分として用いた塗料は、３５０℃以上での高温硬化において、耐熱性および密着性、さらには加工性に優れた塗膜を形成することが可能であり、各種基板への保護コ−ト、絶縁皮膜などに有用であり、特に、自動車または家電・厨房器具用に適用される潤滑、非粘着皮膜の主成分として有用である。 The paint using the polyamide-imide resin heat-resistant resin composition of the present invention as a coating film component should form a coating film excellent in heat resistance, adhesion, and workability in high-temperature curing at 350 ° C. or higher. It is useful for protective coatings on various substrates, insulating coatings, and the like, and particularly useful as a main component of a lubrication and non-adhesive coating applied to automobiles, home appliances and kitchen appliances.
本発明に用いられる（Ａ）ポリアミドイミド樹脂は、一般に下記一般式（Ｉ）で示される繰り返し構造単位を有する。 The (A) polyamideimide resin used in the present invention generally has a repeating structural unit represented by the following general formula (I).
Ｒ１は、芳香環を有する炭素数６〜３０の３価の有機基が好ましく、炭素数６〜２０のものがより好ましく、炭素数６〜１５のものが、さらに好ましい。Ｒ２としては、芳香環を有する炭素数６〜３０の２価の有機基が好ましく、炭素数６〜２０のものがより好ましく、炭素数６〜１８のものがさらに好ましい。ｎは、一般式（Ｉ）で示す繰り返し構造単位の数であり、Ｒ１及びＲ２の構造によって異なるが、一般的に１０〜１００とするのが好ましい。 R 1 is preferably a trivalent organic group having 6 to 30 carbon atoms having an aromatic ring, more preferably having 6 to 20 carbon atoms, and further preferably having 6 to 15 carbon atoms. R 2 is preferably a C 6-30 divalent organic group having an aromatic ring, more preferably 6-20 carbon atoms, and even more preferably 6-18 carbon atoms. n is the number of repeating structural units represented by the general formula (I), and is preferably 10 to 100 although it varies depending on the structures of R 1 and R 2 .
本発明に用いられるポリアミドイミド樹脂は、塩基性極性溶媒中で、ジイソシアネート化合物又はジアミン化合物を、三塩基酸無水物又は三塩基酸無水物クロライドとを反応させて得られるものが好ましい。ジイソシアネ-ト化合物又はジアミン化合物と、三塩基酸無水物又は三塩基酸無水物クロライドは、いずれも芳香族化合物を使用することが好ましく、例えば以下の化合物を用いることができる。
ジイソシアネート化合物としては、４，４′−ジフェニルメタンジイソシアネ−ト、キシリレンジイソシアネ−ト、３，３′−ジフェニルメタンジイソシアネ−ト、３，３′−ジメトキシビフェニル−４，４′−ジイソシアネ−ト、ビフェニル−３，４′−ジイソシアネ−ト、２，２′−ジエチルビフェニル−４，４′−ジイソシアネ−ト、フェニレンジイソシアネ−ト等が挙げられる。本発明において好ましい化合物は、４，４′−ジフェニルメタンジイソシアネ−ト、フェニレンジイソシアネ−トであり、さらに好ましくは、４，４′−ジフェニルメタンジイソシアネ−トである。
The polyamideimide resin used in the present invention is preferably obtained by reacting a diisocyanate compound or a diamine compound with a tribasic acid anhydride or tribasic acid anhydride chloride in a basic polar solvent. The diisocyanate compound or diamine compound and the tribasic acid anhydride or tribasic acid anhydride chloride are preferably aromatic compounds. For example, the following compounds can be used.
Examples of the diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-diphenylmethane diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate. -Biphenyl-3,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, phenylene diisocyanate and the like. Preferred compounds in the present invention are 4,4'-diphenylmethane diisocyanate and phenylene diisocyanate, and more preferably 4,4'-diphenylmethane diisocyanate.
また、ジアミンとしては、４，４′−ジアミノジフェニルメタン、４，４′−ジアミノジフェニルエーテル、、４，４′−ジアミノジフェニルスルホン、４，４′−ジアミノベンゾフェノン、４，４′−ジアミノジフェニルプロパン、３，３′−ジアミノジフェニルスルホン、４，４′−ジアミノジフェニルヘキサフルオロプロパン、キシリレンジアミン、フェニレンジアミン等が挙げられる。
本発明において好ましい化合物は、４，４′−ジアミノジフェニルメタン、４，４′−ジアミノジフェニルエーテルであり、さらに好ましくは、４，４′−ジアミノジフェニルメタンである。
Examples of the diamine include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylpropane, 3 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylhexafluoropropane, xylylenediamine, phenylenediamine and the like.
Preferred compounds in the present invention are 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether, and more preferably 4,4'-diaminodiphenylmethane.
また、三塩基酸無水物としては、トリメリット酸無水物等が挙げられ、三塩基酸無水物クロライドとしては、トリメリット酸無水物クロライド等が挙げられる。 Examples of the tribasic acid anhydride include trimellitic acid anhydride and the like, and examples of the tribasic acid anhydride chloride include trimellitic acid anhydride chloride and the like.
ポリアミドイミド樹脂を合成する際に、ジカルボン酸、テトラカルボン酸二無水物等をポリアミドイミド樹脂の特性を損なわない範囲で同時に反応させることができる。
ジカルボン酸としては、テレフタル酸、イソフタル酸、アジピン酸、ジクエン酸、フタルジイミドジカルボン酸、２，４′−ナフタレンジカルボン酸、２，５′−チオフェンジカルボン酸等が挙げられる。
テトラカルボン酸二無水物としては、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物、ジフェニルスルホン酸二無水物等が挙げられる。
本発明において好ましいジカルボン酸は、テレフタル酸、イソフタル酸、アジピン酸であり、さらに好ましくは、テレフタル酸である。
また、本発明において好ましいテトラカルボン酸二無水物は、ベンゾフェノンテトラカルボン酸二無水物、ピロメリット酸二無水物、ビフェニルテトラカルボン酸二無水物であり、さらに好ましくは、ベンゾフェノンテトラカルボン酸二無水物である。
When synthesizing the polyamideimide resin, dicarboxylic acid, tetracarboxylic dianhydride, and the like can be reacted at the same time as long as the properties of the polyamideimide resin are not impaired.
Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, dicitric acid, phthaldiimide dicarboxylic acid, 2,4′-naphthalenedicarboxylic acid, 2,5′-thiophenedicarboxylic acid, and the like.
Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, diphenylsulfonic dianhydride, and the like.
Preferred dicarboxylic acids in the present invention are terephthalic acid, isophthalic acid, and adipic acid, and more preferably terephthalic acid.
Further, preferred tetracarboxylic dianhydrides in the present invention are benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, and more preferably benzophenone tetracarboxylic dianhydride. It is.
本発明に用いられるポリアミドイミド樹脂は、塩基性極性溶媒中でジイソシアネート化合物またはジアミン化合物と、三塩基酸無水物又は三塩基酸無水物クロライドを反応させて得ることができる。
合成反応において、ジイソシアネ−ト化合物またはジアミン化合物、三塩基酸無水物または三塩基酸水物クロライド、および必要に応じて使用するジカルボン酸およびテトラカルボン酸二無水物の量は、生成されるポリアミドイミド樹脂の分子量、架橋度の観点から、酸成分の総量１．０モルに対してジイソシアネート化合物又はジアミン化合物を０．８〜１．１モルとすることが好ましく、０．９５〜１．０８モルとすることがより好ましく、特に、１．０〜１．０８モル使用されることが好ましい。また、酸成分中、ジカルボン酸及びテトラカルボン酸二無水物は、これらの総量が０〜５０モル％、さらに好ましくは０〜３０モル％の範囲で使用されるのが好ましい。塩基性極性溶媒としては、Ｎ-メチル-２-ピロリドンなどの高沸点溶媒を用いるのが好ましい。また、塩基性極性溶媒の使用量にとくに制限はないが、ジイソシアネ−ト化合物またはジアミン化合物と、三塩基酸二無水物または三塩基酸二無水物クロライドの総量１００質量部に対して１００〜５００質量部とするのが好ましい。反応温度は、通常、８０〜２００℃である。
The polyamideimide resin used in the present invention can be obtained by reacting a diisocyanate compound or diamine compound with a tribasic acid anhydride or tribasic acid anhydride chloride in a basic polar solvent.
In the synthesis reaction, the amount of diisocyanate compound or diamine compound, tribasic acid anhydride or tribasic acid chloride, and dicarboxylic acid and tetracarboxylic dianhydride used as required From the viewpoint of the molecular weight of the resin and the degree of crosslinking, the diisocyanate compound or the diamine compound is preferably 0.8 to 1.1 mol with respect to 1.0 mol of the total amount of the acid component, and 0.95 to 1.08 mol It is more preferable to use 1.0 to 1.08 mol in particular. In the acid component, the total amount of dicarboxylic acid and tetracarboxylic dianhydride is preferably 0 to 50 mol%, more preferably 0 to 30 mol%. As the basic polar solvent, a high boiling point solvent such as N-methyl-2-pyrrolidone is preferably used. Moreover, there is no restriction | limiting in particular in the usage-amount of a basic polar solvent, but 100-500 with respect to 100 mass parts of total amounts of a diisocyanate compound or a diamine compound, and a tribasic acid dianhydride or a tribasic acid dianhydride chloride. It is preferable to set it as a mass part. The reaction temperature is usually 80 to 200 ° C.
本発明に用いられるポリアミドイミド樹脂は、数平均分子量が１０，０００〜５０，０００のものが好ましい。数平均分子量が１０，０００未満では、塗膜としたときの、塗膜の耐熱性や機械的特性等の諸特性が低下する傾向があり、５０，００００を超えると、塗料として適正な濃度で溶媒に溶解したときに粘度が高くなり、塗装時の作業性に劣る傾向がある。このことから、数平均分子量は１２，０００〜３０，０００とすることが好ましく、１８，０００〜２５，０００とすることが特に好ましい。 The polyamideimide resin used in the present invention preferably has a number average molecular weight of 10,000 to 50,000. When the number average molecular weight is less than 10,000, the properties such as heat resistance and mechanical properties of the coating film tend to decrease when the coating film is formed. When the number average molecular weight exceeds 50,0000, the coating composition has an appropriate concentration. When dissolved in a solvent, the viscosity increases and the workability during coating tends to be poor. Therefore, the number average molecular weight is preferably 12,000 to 30,000, and particularly preferably 18,000 to 25,000.
なお、ポリアミドイミド樹脂の数平均分子量は、樹脂合成時にサンプリングし、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により、標準ポリスチレンの検量線を用いて測定し、目的の数平均分子量になるまで合成を継続することにより、所轄の範囲に調整することができる。 The number average molecular weight of the polyamideimide resin is sampled at the time of resin synthesis, measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve, and the synthesis is continued until the target number average molecular weight is reached. It can be adjusted to the scope of jurisdiction.
本発明に用いられる（Ｂ）老化防止剤は、耐熱性樹脂組成物の焼付け時の樹脂熱劣化を防ぎ、得られた塗膜の加工性を向上させる。
老化防止剤としては、４，４-ブチリデンビス（３-メチル-６-ｔ-ブチルフェノ−ル）、３，５-ジ-t-ブチル-４-ヒドロキシベンジルホスホン酸ジエチルエステル、ｐ-クレゾールとジシクロペンタジエンのブチル化反応生成物などのフェノール系老化防止剤、ｐ-（p-トルエンスルホニルアミド）ジフェニルアミン、６-エトキシ-１，２-ジヒロ-２，２，４-トリメチルキノリン、Ｎ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン、アルキル化ジフェニルアミンなどのアミン系老化防止剤を挙げられる。
このような老化防止剤としては、下記構造式で示されるオクチル化ジフェニルアミンが好ましい。
The anti-aging agent (B) used in the present invention prevents resin thermal deterioration during baking of the heat-resistant resin composition and improves the workability of the obtained coating film.
Anti-aging agents include 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, p-cresol and dicyclohexane. Phenol type antioxidants such as butylated reaction products of pentadiene, p- (p-toluenesulfonylamido) diphenylamine, 6-ethoxy-1,2-dihiro-2,2,4-trimethylquinoline, N, N'- Examples thereof include amine-based antioxidants such as di-2-naphthyl-p-phenylenediamine and alkylated diphenylamine.
As such an antioxidant, octylated diphenylamine represented by the following structural formula is preferable.
老化防止剤の添加量は、上記の（Ａ）ポリアミドイミド樹脂１００質量部に対して、好ましくは０．０１〜１０質量部であり、より好ましくは０．１〜５質量部であり、さらに好ましくは０．５〜３質量である。なお、老化防止剤の添加量が、上記ポリアミドイミド樹脂１００質量部に対して０．０１質量部未満では老化防止剤の効果が十分に発現せず、１０質量部を超えると塗膜の耐熱性が低下する傾向がある。 The addition amount of the anti-aging agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably with respect to 100 parts by mass of the (A) polyamideimide resin. Is 0.5-3 mass. In addition, when the addition amount of the anti-aging agent is less than 0.01 parts by mass with respect to 100 parts by mass of the polyamideimide resin, the effect of the anti-aging agent is not sufficiently exhibited. Tends to decrease.
上記の（Ａ）ポリアミドイミド樹脂に上記（Ｂ）老化防止剤を添加する方法には特に制限はない。たとえば、有機溶剤に溶解させた（Ａ）ポリアミドイミド樹脂溶液に（Ｂ）老化防止剤を直接または、有機溶剤に溶解もしくは分散させたものを添加し、混合する方法がある。 There is no restriction | limiting in particular in the method of adding said (B) anti-aging agent to said (A) polyamideimide resin. For example, there is a method of adding and mixing (B) an anti-aging agent directly or dissolved or dispersed in an organic solvent into (A) a polyamidoimide resin solution dissolved in an organic solvent.
本発明のポリアミドイミド樹脂系耐熱性樹脂組成物には、有機溶媒を含むことができるが、通常、固形分を２０〜４０質量％含有する状態の耐熱性樹脂組成物として用いる。
発明の耐熱性樹脂組成物を各種基材に直接塗布するか、または他の塗膜成分の上に塗布、焼付け塗膜を得ることができる。
本発明のポリアミドイミド樹脂系耐熱性樹脂組成物を用いた場合には、硬化温度が３５０℃以上の高温で焼付ても、樹脂自身の熱劣化が抑制されるため、耐熱性および密着性、さらには加工性に優れた塗膜を得ることができる。
The polyamideimide resin heat-resistant resin composition of the present invention can contain an organic solvent, but is usually used as a heat-resistant resin composition containing 20 to 40% by mass of a solid content.
The heat-resistant resin composition of the invention can be applied directly to various substrates, or can be applied and baked on other coating components.
When the polyamide-imide resin heat-resistant resin composition of the present invention is used, even if the curing temperature is baked at a high temperature of 350 ° C. or higher, the thermal deterioration of the resin itself is suppressed. Can obtain a coating film excellent in processability.
本発明のポリアミドイミド樹脂系耐熱性組成物は、例えばエナメル線の絶縁皮膜や、自動車及び厨房関連の耐熱フッ素樹脂用バインダー成分として有用である。
以下に、本発明を実施例により、さらに具体的に説明する。ただし、本発明は、いかなる意味においてもこれらの実施例に制限されるものではない。
The polyamide-imide resin heat-resistant composition of the present invention is useful, for example, as an enameled wire insulating film or a binder component for heat-resistant fluororesins related to automobiles and kitchens.
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples in any sense.
次に本発明の実施例について説明するが、本発明はこれらの実施例に制限されるものではなく、発明の主旨に基づいたこれら以外の多くの実施態様を含むことは言うまでもない。 Next, examples of the present invention will be described. However, the present invention is not limited to these examples, and it is needless to say that the present invention includes many other embodiments based on the gist of the invention.
（実施例１）
無水トリメリット酸１９２．１ｇ（１．００モル）、４，４′-ジフェニルメタンジイソシアネート２５２．８ｇ（１．０１モル）およびＮ−メチル−２−ピロリドン６６７．４ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、この混合物を、乾燥させた窒素気流中で、反応により生ずる炭酸ガスの急激な発泡に注意しながら約６時間かけて徐々に昇温して１３０℃まで昇温した。該混合物を、１３０℃にて８時間保温し、数平均分子量が２２５００のポリアミドイミド樹脂溶液（樹脂分濃度：３０質量％）を得た。
次に、このポリアミドイミド樹脂溶液１００質量部にオクチル化ジフェニルアミン[ＮＯＣＲＡＣ ＡＤ-Ｆ、大内新興化学工業株式会社製商品名]を０．８質量部、直接添加して、ポリアミドイミド樹脂系耐熱性樹脂組成物を得た。
Example 1
Add 192.1 g (1.00 mol) trimellitic anhydride, 252.8 g (1.01 mol) 4,4'-diphenylmethane diisocyanate and 667.4 g N-methyl-2-pyrrolidone to a thermometer, stirrer and condenser. The mixture was placed in a equipped flask, and the mixture was gradually heated to 130 ° C. over about 6 hours in a dry nitrogen stream while paying attention to the sudden foaming of carbon dioxide gas generated by the reaction. The mixture was kept at 130 ° C. for 8 hours to obtain a polyamideimide resin solution having a number average molecular weight of 22500 (resin concentration: 30% by mass).
Next, 0.8 parts by mass of octylated diphenylamine [NOCRAC AD-F, trade name of Ouchi Shinsei Chemical Co., Ltd.] is directly added to 100 parts by mass of this polyamideimide resin solution, and the polyamideimide resin heat resistance is increased. A resin composition was obtained.
（実施例２）
無水トリメリット酸１３４．５ｇ（０．７０モル）、ジフェニルスルホン酸二無水物１０７．５ｇ（０．３０モル）、４，４′-ジフェニルメタンジイソシアネート２５６．５ｇ（１．０２５モル）、Ｎ−メチル−２−ピロリドン１６４２．１ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で、反応により生ずる炭酸ガスの急激な発泡に注意しながら約７時間かけて徐々に昇温して１４５℃まで昇温した。該混合物を、１４５℃にて１０時間保温して数平均分子量が２８８００のポリアミドイミド樹脂溶液（樹脂分濃度：２５質量％）を得た。次に、このポリアミドイミド樹脂溶液１００質量部にオクチル化ジフェニルアミン[ＮＯＣＲＡＣ ＡＤ-Ｆ、大内新興化学工業株式会社製商品名]を０．４質量部溶解させたＮ-メチル-２-ピロリドン溶液４０質量部を添加して、ポリアミドイミド樹脂系耐熱性樹脂組成物を得た。
(Example 2)
Trimellitic anhydride 134.5 g (0.70 mol), diphenylsulfonic dianhydride 107.5 g (0.30 mol), 4,4'-diphenylmethane diisocyanate 256.5 g (1.025 mol), N-methyl 2-Pyrrolidone (1642.1 g) was placed in a flask equipped with a thermometer, stirrer, and cooling tube, and gradually dried over about 7 hours while paying attention to the sudden foaming of carbon dioxide generated by the reaction in a dried nitrogen stream. The temperature was raised to 145 ° C. The mixture was kept at 145 ° C. for 10 hours to obtain a polyamideimide resin solution having a number average molecular weight of 28800 (resin concentration: 25% by mass). Next, an N-methyl-2-pyrrolidone solution 40 in which 0.4 parts by mass of octylated diphenylamine [NOCRAC AD-F, trade name of Ouchi Shinsei Chemical Co., Ltd.] was dissolved in 100 parts by mass of this polyamideimide resin solution 40 Mass parts were added to obtain a polyamide-imide resin heat-resistant resin composition.
（実施例３）
４，４´-ジアミノジフェニルエ-テル２００．２ｇ（１．００モル）、無水トリメリット酸１９２．１ｇ（１．００モル）、Ｎ-メチル-２-ピロリドン９０４ｇおよびホウ酸４．０ｇを温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で、約３時間かけて徐々に昇温して２００℃まで昇温した。該混合物を、２００℃にて１５時間保温して数平均分子量が１９５００のポリアミドイミ樹脂溶液（樹脂分濃度：４０質量％）を得た。次に、このポリアミドイミド樹脂溶液１００質量部にオクチル化ジフェニルアミン[ＮＯＣＲＡＣ ＡＤ-Ｆ、大内新興化学工業株式会社製商品名]を０．３質量部、直接添加して、ポリアミドイミド樹脂系耐熱性樹脂組成物を得た。
(Example 3)
200.2 g (1.00 mol) of 4,4′-diaminodiphenyl ether, 192.1 g (1.00 mol) of trimellitic anhydride, 904 g of N-methyl-2-pyrrolidone and 4.0 g of boric acid The mixture was placed in a flask equipped with a meter, a stirrer, and a cooling tube, and gradually heated up to 200 ° C. over about 3 hours in a dried nitrogen stream. The mixture was kept at 200 ° C. for 15 hours to obtain a polyamide-imi resin solution having a number average molecular weight of 19,500 (resin concentration: 40% by mass). Next, 0.3 parts by mass of octylated diphenylamine [NOCRAC AD-F, trade name of Ouchi Shinsei Chemical Co., Ltd.] is directly added to 100 parts by mass of this polyamideimide resin solution, and the polyamideimide resin heat resistance is increased. A resin composition was obtained.
（比較例１）
実施例１において、オクチル化ジフェニルアミンを加えなかったことを除いては、実施例１と同様にしてポリアミドイミド樹脂溶液を得た。
(Comparative Example 1)
In Example 1, a polyamideimide resin solution was obtained in the same manner as in Example 1 except that octylated diphenylamine was not added.
（比較例２）
無水トリメリット酸１３４．５ｇ（０．７０モル）、ジフェニルスルホン酸二無水物１０７．５ｇ（０．３０モル）、４，４，-ジフェニルメタジイソシアネ-ト２５６．５ｇ（１．０２５モル）及びＮ-メチル-２-ピロリドン６０９．３ｇ温度計、攪拌機、冷却管を備えたフラスコに入れ、乾燥させた窒素気流中で、反応により生ずる炭酸ガスの急激な発泡に注意しながら約７時間かけて徐々に昇温し１４５℃まで昇温した。
該混合物を１４５℃にて１２時間保温し、数平均分子量が３１０００のポリアミドイミド樹脂溶液を得た。
(Comparative Example 2)
Trimellitic anhydride 134.5 g (0.70 mol), diphenylsulfonic dianhydride 107.5 g (0.30 mol), 4,4, -diphenyl metadiisocyanate 256.5 g (1.025 mol) And N-methyl-2-pyrrolidone 609.3 g in a flask equipped with a thermometer, a stirrer, and a condenser, and in a dry nitrogen stream, taking about 7 hours while paying attention to the sudden foaming of carbon dioxide generated by the reaction The temperature was gradually raised to 145 ° C.
The mixture was kept at 145 ° C. for 12 hours to obtain a polyamideimide resin solution having a number average molecular weight of 31,000.
実施例１〜３および比較例１〜２で得られたポリアミドイミド樹脂系耐熱性樹脂組成物又はポリアミドイミド樹脂溶液を基材（アルミニウム基材、ＪＩＳ Ｈ４０００、未研磨品、厚み＝０．５ｍｍ、アセトン脱脂処理）に塗布した後、３５０℃で３０分間硬化させて塗膜厚約１０μｍの塗膜板を作製し、密着性および加工性（曲げ性）を試験した。 The polyamide-imide resin heat-resistant resin composition or polyamide-imide resin solution obtained in Examples 1 to 3 and Comparative Examples 1 to 2 was used as a substrate (aluminum substrate, JIS H4000, unpolished product, thickness = 0.5 mm, After application to acetone (degreasing treatment), it was cured at 350 ° C. for 30 minutes to prepare a coating plate having a coating thickness of about 10 μm, and the adhesion and workability (bendability) were tested.
密着性；旧ＪＩＳ Ｋ５４００（％、クロスカット残率）に準拠し測定した。
加工性;Ｔベント法・折り曲げ試験により測定した。図１に示すようなスペ−サ−３をはさみ、１８０度折り曲げた時の基板２上の塗膜に発生する微小クラックの有無を拡大鏡で１０倍に拡大して観察し判定した。
スペ−サ−厚みを変えて試験し、微小クラックの発生しないスペ−サの最小厚が基板の厚みの何倍であるかを（倍率）Ｔと記載し、スペ−サ無しで微小クラックの発生しない場合は０Ｔとした。例えば、表１に示すような場合は、２Ｔと判定した。
それらの測定結果を纏めて表２に示した。
Adhesiveness: Measured according to the old JIS K5400 (%, crosscut residual rate).
Workability: Measured by T-bent method and bending test. The presence or absence of microcracks generated in the coating film on the substrate 2 when sandwiched between the
Tested by changing the thickness of the spacer, the number of times the minimum thickness of the spacer that does not generate microcracks is indicated as (magnification) T, and the occurrence of microcracks without a spacer When not, it was set to 0T. For example, in the case shown in Table 1, it was determined to be 2T.
The measurement results are summarized in Table 2.
２）下記方法に示す、Ｔベント法・折り曲げ試験、により測定した。
2) Measured by T vent method / bending test shown in the following method.
表１から、実施例１〜３のポリアミドイミド樹脂系耐熱性樹脂組成物から得られた塗膜は比較例１〜２より得られた塗膜と比較して、高温（３５０℃）硬化後の密着性および加工性が優れていることが示される。 From Table 1, the coating films obtained from the polyamide-imide resin heat-resistant resin compositions of Examples 1 to 3 were compared with the coating films obtained from Comparative Examples 1 and 2, after being cured at a high temperature (350 ° C.). It shows that adhesion and workability are excellent.
１ 塗膜
２ 基板
３ スペ−サ−
1 Coating 2
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