JP2713056B2 - Polyimide resin and method for producing the same - Google Patents
Polyimide resin and method for producing the sameInfo
- Publication number
- JP2713056B2 JP2713056B2 JP4260784A JP26078492A JP2713056B2 JP 2713056 B2 JP2713056 B2 JP 2713056B2 JP 4260784 A JP4260784 A JP 4260784A JP 26078492 A JP26078492 A JP 26078492A JP 2713056 B2 JP2713056 B2 JP 2713056B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide resin
- group
- represented
- formula
- polyimide
- 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.)
- Expired - Fee Related
Links
- 229920001721 polyimide Polymers 0.000 title claims description 72
- 239000009719 polyimide resin Substances 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 19
- 150000003377 silicon compounds Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004427 diamine group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 22
- -1 hydroxysilyl group Chemical group 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000005372 silanol group Chemical group 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 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 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 3
- 229960004065 perflutren Drugs 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JFEXPVDGVLNUSC-UHFFFAOYSA-N 3-(3-aminophenyl)sulfanylaniline Chemical compound NC1=CC=CC(SC=2C=C(N)C=CC=2)=C1 JFEXPVDGVLNUSC-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- NAUSGUYYKKTJTC-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)-3,5-dimethylphenyl]methyl]-2,6-dimethylphenoxy]aniline Chemical compound C=1C(C)=C(OC=2C=CC(N)=CC=2)C(C)=CC=1CC(C=C1C)=CC(C)=C1OC1=CC=C(N)C=C1 NAUSGUYYKKTJTC-UHFFFAOYSA-N 0.000 description 1
- KODXTKOQSKLENE-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)-3-chlorophenyl]methyl]-2-chlorophenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C(=C1)Cl)=CC=C1CC(C=C1Cl)=CC=C1OC1=CC=C(N)C=C1 KODXTKOQSKLENE-UHFFFAOYSA-N 0.000 description 1
- GJCJZNPUDLWINR-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)-3-methylphenyl]methyl]-2-methylphenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C(C)=CC=1CC(C=C1C)=CC=C1OC1=CC=C(N)C=C1 GJCJZNPUDLWINR-UHFFFAOYSA-N 0.000 description 1
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-UHFFFAOYSA-N 0.000 description 1
- XZOQPRNOAGCWNT-UHFFFAOYSA-N 4-[[(3,4-dicarboxyphenyl)-dimethylsilyl]oxy-dimethylsilyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 XZOQPRNOAGCWNT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UNNBMJJDHLMGQF-UHFFFAOYSA-N C1CC2C(CC1[SiH](C3=CC=CC=C3)O)C(=O)OC2=O Chemical compound C1CC2C(CC1[SiH](C3=CC=CC=C3)O)C(=O)OC2=O UNNBMJJDHLMGQF-UHFFFAOYSA-N 0.000 description 1
- CJUFAXPRXXDEME-UHFFFAOYSA-N C1CC2C(CC1[SiH](CO)C3=CC=CC=C3)C(=O)OC2=O Chemical compound C1CC2C(CC1[SiH](CO)C3=CC=CC=C3)C(=O)OC2=O CJUFAXPRXXDEME-UHFFFAOYSA-N 0.000 description 1
- ZRXDCABZJZRGCO-UHFFFAOYSA-N C1CC2C(CC1[Si](C3=CC=CC=C3)(C4=CC=CC=C4)O)C(=O)OC2=O Chemical compound C1CC2C(CC1[Si](C3=CC=CC=C3)(C4=CC=CC=C4)O)C(=O)OC2=O ZRXDCABZJZRGCO-UHFFFAOYSA-N 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZIXLDMFVRPABBX-UHFFFAOYSA-N alpha-methylcyclopentanone Natural products CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、分子末端にシラノール
基を有するので、ポリアルコキシシラン、ポリヒドロキ
シシラン、水酸基含有ポリジオルガノシロキサンなどの
架橋剤と反応して硬化できるため、熱硬化性組成物の成
分として有用なポリイミド樹脂及びその製造方法に関す
る。The present invention relates to a thermosetting composition which has a silanol group at the molecular terminal and can be cured by reacting with a crosslinking agent such as polyalkoxysilane, polyhydroxysilane, hydroxyl group-containing polydiorganosiloxane. And a method for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、電子部品などの絶縁保護膜として耐熱性や電気的・
機械的特性に優れたポリイミド樹脂が利用されている
が、保護膜形成に際し、一般にポリイミド樹脂は有機溶
剤に不要なためにその前駆体であるポリアミック酸の溶
液を用い、これを基材に塗布した後、加熱硬化して目的
とするポリイミド樹脂皮膜を形成する方法が採用されて
いる。2. Description of the Related Art Conventionally, as an insulating protective film for electronic parts and the like, heat resistance and electrical and electrical properties have been improved.
Polyimide resin with excellent mechanical properties is used, but when forming the protective film, the polyimide resin is generally used in a solution of the precursor polyamic acid because it is unnecessary for the organic solvent, it was applied to the substrate Thereafter, a method of forming a desired polyimide resin film by heating and curing is adopted.
【０００３】しかし、この従来のポリアミック酸の溶液
を用いる方法においては、ポリアミック酸溶液の粘度が
非常に高いため、作業性に劣り、また、加熱硬化に際し
て３００℃を超える高温が必要であるという問題点があ
る。However, in the conventional method using a polyamic acid solution, the workability is poor because the viscosity of the polyamic acid solution is very high, and a high temperature exceeding 300 ° C. is required for heat curing. There is a point.
【０００４】これらの問題点のうち、ポリアミック酸の
硬化によりポリイミド皮膜を形成する場合に必要な３０
０℃以上という高温の熱処理を省くために、シロキサン
結合を有するポリイミド樹脂自身を溶剤に溶解したもの
（特公昭６１−８３２２８号公報、特公昭６１−１１８
４２４号公報、特公昭６１−１１８４２５号公報）、あ
るいはアルコキシシリル基を有するイミド樹脂（特公昭
５５−３５０７６号公報、特公昭５５−３５０７７号公
報）を用いてポリイミド樹脂皮膜を形成する方法などの
提案が種々なされている。[0004] Among these problems, 30 required when a polyimide film is formed by curing of a polyamic acid.
In order to eliminate heat treatment at a high temperature of 0 ° C. or higher, polyimide resin having a siloxane bond is dissolved in a solvent (Japanese Patent Publication No. 61-83228, Japanese Patent Publication No. 61-118).
424, JP-B-61-118425) or a method of forming a polyimide resin film using an imide resin having an alkoxysilyl group (JP-B-55-35076, JP-B-55-35077). Various proposals have been made.
【０００５】しかし、これらの方法によって得られるポ
リイミド樹脂皮膜は、前者は本質的に耐溶剤性に劣ると
いう問題があり、一方後者は、水の添加によるアルコキ
シシランの加水分解が必要であるが、この加水分解後の
保存安定性が悪いという問題がある。However, the polyimide resin film obtained by these methods has a problem that the former is essentially inferior in solvent resistance, while the latter requires hydrolysis of alkoxysilane by addition of water. There is a problem that storage stability after this hydrolysis is poor.
【０００６】本発明は、上記事情に鑑みなされたもの
で、溶剤に溶解した場合に低粘度で作業性に優れ、比較
的低温度で硬化すると共に、耐熱性、耐溶剤性などに優
れた硬化皮膜を与えるポリイミド樹脂、及びかかるポリ
イミド樹脂を容易確実に得ることができる製造方法を提
供することを目的とする。The present invention has been made in view of the above circumstances, and has a low viscosity and excellent workability when dissolved in a solvent, cures at a relatively low temperature, and has excellent heat resistance and solvent resistance. It is an object of the present invention to provide a polyimide resin for providing a film and a manufacturing method capable of easily and reliably obtaining such a polyimide resin.
【０００７】[0007]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を重ねた結果、下記構造
式（３）で表されるポリイミドと下記構造式（４）で表
されるシリコン化合物とを反応させることにより、下記
構造式（１）で表されるシラノール基を末端に有する新
規なポリイミド樹脂が容易確実に得られること、更にこ
の式（１）で表されるポリイミド樹脂を脱水することに
より下記構造式（２）で表されるポリイミド樹脂が容易
確実に得られことを知見した。The present inventors have made intensive studies to achieve the above object, and as a result, have obtained a polyimide represented by the following structural formula (3) and a polyimide represented by the following structural formula (4). By reacting with a silicon compound, a novel polyimide resin having a silanol group at the terminal represented by the following structural formula (1) can be easily and reliably obtained, and further a polyimide resin represented by this formula (1) It has been found that a polyimide resin represented by the following structural formula (2) can be easily and surely obtained by dehydrating.
【０００８】[0008]
【化４】 Embedded image
【化１９】（但し、式中Ｒ１、Ｒ２は互いに同一又は異
種の炭素数１〜１０のアルキル基、アルケニル基、アリ
ール基及びハロゲン置換アルキル基から選ばれる１価の
基、Ｘは炭素数６〜３０の芳香族環含有ジアミン残基及
びケイ素原子数２〜２０のシロキサン、シルエチレン又
はシルフェニレン構造を有するシリコーンジアミン残基
から選ばれる２価の基、Ｙは、 から選ばれる４価の基、ｎは１〜２０の整数である。）Wherein R 1 and R 2 are the same or different and each is a monovalent group selected from an alkyl group, an alkenyl group, an aryl group and a halogen-substituted alkyl group having 1 to 10 carbon atoms; Y is a divalent group selected from an aromatic ring-containing diamine residue having a number of 6 to 30 and a siloxane having 2 to 20 silicon atoms, and a silicone diamine residue having a silethylene or silphenylene structure. And n is an integer of 1 to 20. )
【０００９】即ち、上記式（３）で表されるポリイミド
と式（４）で表されるシリコン化合物とを反応させて式
（１）で表されるポリイミド樹脂を得る方法によれば、
ポリイミド合成の際、シラノール基を含む酸無水物をポ
リイミド末端に重合させるため、シラノール基の導入が
容易で、しかも確実に導入されること、更に、式（１）
で表されるポリイミド樹脂を脱水することにより容易確
実に式（２）で表されるポリイミド樹脂を合成できるこ
と、このようにして合成された上記式（１）及び式
（２）で表されるポリイミド樹脂は、溶剤に溶解した場
合に低粘度で作業性に優れると共に、末端にシラノール
基を有するので、ポリアルコキシシラン、ポリヒドロキ
シシラン、あるいは水酸基含有ポリジオルガノシロキサ
ンなどのヒドロキシシリル基、アルコキシシリル基など
を有する化合物を架橋剤として、３００℃より低い温度
で容易に硬化し、耐溶剤性、耐熱性、機械的強度、電気
的特性などに優れた硬化皮膜を形成できるため、電子部
品などの保護膜として好適に使用できる熱硬化性組成物
の成分として有用であることを見い出し、本発明をなす
に至ったものである。That is, according to the method of reacting the polyimide represented by the formula (3) with the silicon compound represented by the formula (4) to obtain the polyimide resin represented by the formula (1),
In the synthesis of the polyimide, an acid anhydride containing a silanol group is polymerized at the polyimide terminal, so that the silanol group can be easily and reliably introduced. Further, the formula (1)
That the polyimide resin represented by the formula (2) can be easily and reliably synthesized by dehydrating the polyimide resin represented by the formula: and the polyimide represented by the above formulas (1) and (2) thus synthesized. The resin has a low viscosity and excellent workability when dissolved in a solvent, and has a silanol group at the end, so that a hydroxysilyl group such as polyalkoxysilane, polyhydroxysilane, or hydroxyl group-containing polydiorganosiloxane, an alkoxysilyl group, etc. As a crosslinking agent, a compound having the following formula can be easily cured at a temperature lower than 300 ° C. to form a cured film having excellent solvent resistance, heat resistance, mechanical strength, and electrical properties. The present invention has been found to be useful as a component of a thermosetting composition that can be suitably used as the present invention, and has led to the present invention.
【００１０】従って、本発明は、上記式（１）及び式
（２）で表されるポリイミド樹脂、並びに上記式（３）
で表されるポリイミドと式（４）で表されるシリコン化
合物とを反応させることを特徴とする式（１）で表され
るポリイミド樹脂の製造方法及び式（１）で表されるポ
リイミド樹脂を脱水することを特徴とする式（２）で表
されるポリイミド樹脂の製造方法を提供する。Accordingly, the present invention provides a polyimide resin represented by the above formulas (1) and (2), and a polyimide resin represented by the above formula (3)
A method for producing a polyimide resin represented by the formula (1), characterized by reacting a polyimide represented by the formula (1) with a silicon compound represented by the formula (4), and a polyimide resin represented by the formula (1). Provided is a method for producing a polyimide resin represented by the formula (2), which is characterized by dehydration.
【００１１】以下、本発明について更に詳しく説明する
と、本発明のポリイミド樹脂は、下記式（１）で表され
るポリイミド樹脂と、この式（１）で表されるポリイミ
ド樹脂を脱水することにより得られる下記式（２）で表
されるポリイミド樹脂である。Hereinafter, the present invention will be described in more detail. The polyimide resin of the present invention is obtained by dehydrating a polyimide resin represented by the following formula (1) and a polyimide resin represented by the following formula (1). Is a polyimide resin represented by the following formula (2).
【００１２】[0012]
【化５】 Embedded image
【００１３】ここで、上記式中、Ｒ１、Ｒ２は互いに同
一又は異種の炭素数１〜１０、好ましくは炭素数１〜６
のアルキル基、アルケニル基、アリール基又はハロゲン
化アルキル基であり、例えばメチル基、エチル基、プロ
ピル基、ブチル基などのアルキル基；ビニル基、アリル
基、ブテニル基などのアルケニル基；フェニル基、トリ
ル基などのアリール基；あるいはこれらの基の炭素原子
に結合した水素原子の一部又は全部をハロゲン原子で置
換したクロロメチル基、クロロプロピル基、３，３，３
−トリフルオロプロピル基などが挙げられる。また、Ｘ
は２価の有機基、Ｙは４価の有機基であり、これらの
Ｘ、Ｙについては後に詳述する。更に、ｎは１〜２０の
整数である。In the above formula, R 1 and R 2 are the same or different and have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
An alkyl group, an alkenyl group, an aryl group or a halogenated alkyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an alkenyl group such as a vinyl group, an allyl group or a butenyl group; An aryl group such as a tolyl group; or a chloromethyl group, a chloropropyl group, in which a part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, 3,3,3
-Trifluoropropyl group and the like. Also, X
Is a divalent organic group, and Y is a tetravalent organic group. These X and Y will be described later in detail. Further, n is an integer of 1 to 20.
【００１４】上記式（１）及び式（２）で表されるポリ
イミド樹脂は、下記構造式（３）で表されるポリイミド
と下記構造式（４）で表されるシリコン化合物とを有機
溶剤中で反応させた後、有機溶剤を蒸発させることによ
って得ることができる。The polyimide resin represented by the above formulas (1) and (2) is obtained by mixing a polyimide represented by the following structural formula (3) and a silicon compound represented by the following structural formula (4) in an organic solvent. And then evaporating the organic solvent.
【００１５】[0015]
【化６】 Embedded image
【００１６】ここで、上記式（３）で表されるポリイミ
ドは、下記構造式（５）で表されるるテトラカルボン酸
二無水物と下記構造式（６）で表されるジアミンとを所
定の割合、即ち式（５）で表されるテトラカルボン酸二
無水物ｎ個に対してジアミン（ｎ＋１）個を反応させ、
下記構造式（７）で表されるポリアミック酸を得、これ
を常法に従って脱水することにより得ることができる。Here, the polyimide represented by the above formula (3) is obtained by combining a tetracarboxylic dianhydride represented by the following structural formula (5) and a diamine represented by the following structural formula (6) in a predetermined manner. A ratio, that is, n tetracarboxylic dianhydrides represented by the formula (5) are reacted with (n + 1) diamines,
It can be obtained by obtaining a polyamic acid represented by the following structural formula (7) and dehydrating the same according to a conventional method.
【００１７】[0017]
【化７】 （上記反応式中、ｎは１以上の整数である。）Embedded image (In the above reaction formula, n is an integer of 1 or more.)
【００１８】上記式中、Ｙは４価の有機基であり、上記
式（５）で表されるテトラカルボン酸二無水物に由来す
るものである。具体的にＹとテトラカルボン酸二無水物
を示すと次の通りである。In the above formula, Y is a tetravalent organic group, which is derived from the tetracarboxylic dianhydride represented by the above formula (5). Specific examples of Y and tetracarboxylic dianhydride are as follows.
【００１９】[0019]
【化８】 Embedded image
【００２０】なお、Ｙは１種であっても２種以上の組み
合わせでも良い。Incidentally, Y may be one kind or a combination of two or more kinds.
【００２１】また、上記式中、Ｘは２価の有機基であ
り、式（６）で表されるジアミンに由来するものであ
る。このジアミンを具体的に示すと、ｐ−フェニレンジ
アミン、ｍ−フェニレンジアミン、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、２，２’−ビス（４−アミノフェニル）プロパ
ン、４，４’−ジアミノジフェニルスルホン、４，４’
−ジアミノジフェニルスルフィド、１，４−ビス（３−
アミノフェノキシ）ベンゼン、１，４−ビス（４−アミ
ノフェノキシ）ベンゼン、１，４−ビス（ｍ−アミノフ
ェニルスルホニル）ベンゼン、１，４−ビス（ｐ−アミ
ノフェニルスルホニル）ベンゼン、１，４−ビス（ｍ−
アミノフェニルチオエーテル）ベンゼン、１，４−ビス
（ｐ−アミノフェニルチオエーテル）ベンゼン、２，２
−ビス［４−（４−アミノフェノキシ）フェニル］プロ
パン、２，２−ビス［３−メチル−４−（４−アミノフ
ェノキシ）フェニル］プロパン、２，２−ビス［３−ク
ロロ−４−（４−アミノフェノキシ）フェニル］プロパ
ン、１，１−ビス［４−（４−アミノフェノキシ）フェ
ニル］エタン、１，１−ビス［３−メチル−４−（４−
アミノフェノキシ）フェニル］エタン、１，１−ビス
［３−クロロ−４−（４−アミノフェノキシ）フェニ
ル］エタン、１，１−ビス［３，５−ジメチル−４−
（４−アミノフェノキシ）フェニル］エタン、ビス［４
−（４−アミノフェノキシ）フェニル］メタン、ビス
［３−メチル−４−（４−アミノフェノキシ）フェニ
ル］メタン、ビス［３−クロロ−４−（４−アミノフェ
ノキシ）フェニル］メタン、ビス［３，５−ジメチル−
４−（４−アミノフェノキシ）フェニル］メタン、ビス
［４−（４−アミノフェノキシ）フェニル］スルホン、
２，２−ビス［４−（４−アミノフェノキシ）フェニ
ル］パーフルオロプロパンから選ばれる炭素数６〜３０
の芳香族含有ジアミンである。In the above formula, X is a divalent organic group and is derived from the diamine represented by the formula (6). Specific examples of this diamine include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, , 4'-Diaminodiphenyl sulfone, 4,4 '
-Diaminodiphenyl sulfide, 1,4-bis (3-
Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4- Screw (m-
Aminophenylthioether) benzene, 1,4-bis (p-aminophenylthioether) benzene, 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- ( 4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4-]
(4-aminophenoxy) phenyl] ethane, bis [4
-(4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3 , 5-dimethyl-
4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone,
C6-C30 selected from 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane
Is an aromatic-containing diamine.
【００２２】そのほかのＸを与えるジアミン化合物は、
下記式で示されるケイ素原子数２〜２０のシロキサン、
シルエチレン又はシルフェニレン構造を有するシリコン
ジアミンである。Other diamine compounds providing X are:
A siloxane having 2 to 20 silicon atoms represented by the following formula,
It is a silicon diamine having a silethylene or silphenylene structure.
【００２３】[0023]
【化９】 Embedded image
【００２４】[0024]
【化１０】 Embedded image
【００２５】なお、Ｘは、上記ジアミン残基の１種であ
っても２種以上の組み合わせであっても良く、従って式
（６）で表されるジアミンとしては上記ジアミンの１種
を単独で又は２種以上を組み合わせても良い。X may be one kind of the above-described diamine residues or a combination of two or more kinds thereof. Therefore, as the diamine represented by the formula (6), one kind of the above-mentioned diamines may be used alone. Alternatively, two or more kinds may be combined.
【００２６】一方、上記式（３）のポリイミドと反応さ
せるシリコン化合物としては下記式（４）で表されるも
のを使用する。On the other hand, as the silicon compound to be reacted with the polyimide of the above formula (3), a compound represented by the following formula (4) is used.
【００２７】[0027]
【化１１】 Embedded image
【００２８】上記式中、Ｒ1、Ｒ2は上記と同様の意味を
示し、本発明においてはこのようなＲ1、Ｒ2を有するシ
リコン化合物の１種を単独で又は２種以上を併用して用
いることができる。In the above formula, R 1 and R 2 have the same meanings as described above. In the present invention, one of these silicon compounds having R 1 and R 2 may be used alone or in combination of two or more. Can be used.
【００２９】上記式（３）で表されるポリイミドと式
（４）で表されるシリコン化合物とを反応させる際、有
機溶剤中で行うことができ、反応後有機溶剤を蒸発させ
ることのより式（１）で表されるポリイミド樹脂を得る
ことができる。The reaction between the polyimide represented by the formula (3) and the silicon compound represented by the formula (4) can be carried out in an organic solvent, and after the reaction, the organic solvent is evaporated. The polyimide resin represented by (1) can be obtained.
【００３０】この反応に使用できる有機溶剤としては、
例えばテトラヒドロフラン、１，４−ジオキサン、ジエ
チレングリコールジメチルエーテル、ジエチレングリコ
ールジエチルエーテルなどのエーテル類；メチルセロソ
ルブ、エチルセロソルブ、ブチルセロソルブなどのセロ
ソルブ類；アセトン、メチルエチルケトン、メチルイソ
ブチルケトン、シクロペンタノン、シクロヘキサノンな
どのケトン類；γ−ブチロラクトン、ブチルセロソルブ
アセテート、ブチルアセテート、エチルアセテートなど
のエステル類；Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−
ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド
などのアミド類が挙げられ、これらの１種を単独で又は
２種以上を混合して用いることができる。The organic solvents that can be used in this reaction include:
For example, ethers such as tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; Esters such as γ-butyrolactone, butyl cellosolve acetate, butyl acetate, ethyl acetate; N-methyl-2-pyrrolidone, N, N-
Amides such as dimethylacetamide and N, N-dimethylformamide can be mentioned, and one of these can be used alone or in combination of two or more.
【００３１】この式（３）で表されるポリイミドと式
（４）で表されるシリコン化合物との反応に際し、これ
らのモル比［式（３）で表されるポリイミド／式（４）
で表されるシリコン化合物］は、約１．９〜２．１の範
囲とすることが好ましい。また、反応温度は−２０〜７
０℃、特に０〜５０℃の範囲が好ましく、反応時間は通
常０．５〜１０時間である。In the reaction between the polyimide represented by the formula (3) and the silicon compound represented by the formula (4), their molar ratios [polyimide represented by the formula (3) / polyimide represented by the formula (4)]
Is preferably in the range of about 1.9 to 2.1. The reaction temperature is -20 to 7
The temperature is preferably in the range of 0 ° C, particularly 0 to 50 ° C, and the reaction time is usually 0.5 to 10 hours.
【００３２】この反応後、有機溶剤を蒸発させることに
より、本発明の式（１）で表されるポリイミド樹脂を得
ることができる。なお、使用した有機溶剤の蒸発が困難
である場合には、反応溶液をメタノールなどの中に流し
込むことにより再沈殿させ、これを乾燥するなどして式
（１）で表されるポリイミド樹脂を単離することもでき
る。After the reaction, the polyimide resin represented by the formula (1) of the present invention can be obtained by evaporating the organic solvent. When it is difficult to evaporate the used organic solvent, the reaction solution is poured into methanol or the like to reprecipitate, and then dried to dry the polyimide resin represented by the formula (1). It can also be released.
【００３３】また、式（２）で表されるポリイミド樹脂
は、式（１）で表されるポリイミド樹脂を単離すること
なく反応溶液をそのまま、あるいは単離した式（１）で
表されるポリイミド樹脂を再度有機溶剤に溶解し、無水
酢酸と、ピリジン、第３級アミンなどのイミド化剤を加
え、イミド化反応を行って脱水することにより合成する
ことができる。この時の反応温度は０〜１００℃、好ま
しくは８０℃以下で、反応時間は０．５〜５時間であ
る。反応温度が高すぎるとシラノールが縮合するおそれ
が生じる場合がある。反応後、溶液をメタノールなどの
中に流し込むことにより再沈殿させ、これを乾燥するな
どして式（２）で表されるポリイミド樹脂を単離するこ
とができる。Further, the polyimide resin represented by the formula (2) is represented by the formula (1) in which the reaction solution is isolated without isolating the polyimide resin represented by the formula (1) or isolated. The polyimide resin can be synthesized by dissolving again in an organic solvent, adding acetic anhydride, an imidizing agent such as pyridine and a tertiary amine, and performing an imidization reaction to dehydrate the polyimide resin. At this time, the reaction temperature is 0 to 100 ° C, preferably 80 ° C or lower, and the reaction time is 0.5 to 5 hours. If the reaction temperature is too high, the silanol may be condensed. After the reaction, the solution is re-precipitated by pouring the solution into methanol or the like, and the polyimide resin represented by the formula (2) can be isolated by drying or the like.
【００３４】このような式（１）及び式（２）で表され
るポリイミド樹脂は、末端にシラノール基を有するの
で、例えばヒドロキシシリル基あるいはアルコキシシリ
ル基を含有するポリアルコキシシラン、ポリヒドロキシ
シラン、水酸基含有ポリジオルガノシロキサンなどの架
橋剤と好ましくは有機溶剤中で混合して熱硬化性組成物
を調製することができる。この溶液は比較的低粘度であ
り、作業性に優れたものである。また、この熱硬化性組
成物は約１００〜２５０℃の比較的低温度で容易に加硫
することができる。Since the polyimide resin represented by the formulas (1) and (2) has a silanol group at the terminal, for example, a polyalkoxysilane, a polyhydroxysilane, a polysiloxysilane containing a hydroxysilyl group or an alkoxysilyl group, A thermosetting composition can be prepared by mixing with a crosslinking agent such as a hydroxyl group-containing polydiorganosiloxane, preferably in an organic solvent. This solution has a relatively low viscosity and is excellent in workability. The thermosetting composition can be easily vulcanized at a relatively low temperature of about 100 to 250C.
【００３５】この場合、有機溶剤としては、本発明の式
（１）と式（２）で表されるポリイミド樹脂を溶解する
有機溶剤として例示したものを挙げることができ、これ
らの１種を単独で又は２種以上を混合して使用すること
ができる。In this case, examples of the organic solvent include those exemplified as the organic solvents for dissolving the polyimide resins represented by the formulas (1) and (2) of the present invention. Or a mixture of two or more.
【００３６】また、有機溶剤に溶解する場合の固形分量
は１〜６０％、特に５〜４０％の範囲とすることが好ま
しい。The solid content when dissolved in an organic solvent is preferably in the range of 1 to 60%, particularly preferably 5 to 40%.
【００３７】なお、式（１）で表されるポリイミド樹脂
を用いて熱硬化性組成物を調製した場合、式（１）で表
されるポリイミド樹脂の両末端にアミック酸が残存して
いるため、この組成物を塗布した後、十分な加熱硬化に
より、このアミック酸部分が閉環する。When a thermosetting composition is prepared using the polyimide resin represented by the formula (1), the amic acid remains at both ends of the polyimide resin represented by the formula (1). After the composition is applied, the amic acid portion is closed by sufficient heat curing.
【００３８】[0038]
【発明の効果】本発明のポリイミド樹脂は、末端にシラ
ノール基を有するので、ヒドロキシシリル基やアルコキ
シシリル基などを含有する架橋剤により比較的低温で硬
化し、優れた物性を有する硬化物を与えるため、熱硬化
性組成物の成分として有用であり、また本発明のポリイ
ミド樹脂の製造方法によれば、ポリイミドの末端にシラ
ノール基を容易確実に導入することができる。Since the polyimide resin of the present invention has a silanol group at the terminal, it is cured at a relatively low temperature by a crosslinking agent containing a hydroxysilyl group or an alkoxysilyl group, and gives a cured product having excellent physical properties. Therefore, it is useful as a component of a thermosetting composition, and according to the method for producing a polyimide resin of the present invention, a silanol group can be easily and reliably introduced into a polyimide terminal.
【００３９】[0039]
【実施例】以下、実施例を示し、本発明を具体的に示す
が、本発明は下記の実施例に制限されるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００４０】［実施例１］撹拌機、温度計及び窒素置換
装置を取り付けたフラスコ中に酸無水物成分として２，
２−ビス（３，４−ベンゼンジカルボン酸アンヒドリ
ド）パーフルオロプロパン９．５ｇ（０．０２１モ
ル）、溶剤としてジエチレングリコールジメチルエーテ
ル２０ｇを仕込み、これにジアミン成分として２，２−
ビス［４−（４−アミノフェノキシ）フェニル］プロパ
ン１１．６ｇ（０．０２８モル）をジエチレングリコー
ルジメチルエーテル５０ｇに溶解したアミン溶液を滴下
した。滴下終了後、更に５０℃で１２時間撹拌し、次に
フラスコに水分受容器付き還流冷却器を取り付けた後、
キシレン２０ｇを加え、反応系を１４０℃に昇温してそ
の温度を４時間保持した。この反応によって０．８ｇの
水が発生した。[Example 1] In a flask equipped with a stirrer, a thermometer and a nitrogen purging apparatus, 2
9.5 g (0.021 mol) of 2-bis (3,4-benzenedicarboxylic anhydride) perfluoropropane and 20 g of diethylene glycol dimethyl ether as a solvent were charged, and 2,2-diamine as a diamine component was added thereto.
An amine solution in which 11.6 g (0.028 mol) of bis [4- (4-aminophenoxy) phenyl] propane was dissolved in 50 g of diethylene glycol dimethyl ether was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 50 ° C. for 12 hours, and then a reflux condenser with a water receiver was attached to the flask.
20 g of xylene was added, the temperature of the reaction system was raised to 140 ° C., and the temperature was maintained for 4 hours. The reaction produced 0.8 g of water.
【００４１】上記操作によって得られた反応溶液を冷却
後、メタノール中に投じて再沈澱し、その後乾燥して下
記構造式（５−ａ）を有するポリイミド化合物２０．０
ｇを得た。After cooling the reaction solution obtained by the above operation, the reaction solution was poured into methanol for reprecipitation, and then dried to obtain a polyimide compound having the following structural formula (5-a) 20.0.
g was obtained.
【００４２】[0042]
【化１２】 Embedded image
【００４３】このポリイミド化合物の赤外吸収スペクト
ルを測定したところ、アミド結合に由来する吸収が１７
８０ｃｍ-1と１７２０ｃｍ-1に確認された。When the infrared absorption spectrum of this polyimide compound was measured, the absorption derived from the amide bond was 17%.
It has been confirmed to 80cm -1 and 1720cm -1.
【００４４】次に、上記ポリイミド化合物１９．９ｇを
ジエチレングリコールジメチルエーテルに再溶解し、こ
の溶液にシリコン化合物として４−（ヒドロキシフェニ
ルシリル）−シクロヘキサン−１，２ジカルボン酸無水
物４．９ｇ（０．０１４モル）をジエチレングリコール
ジメチルエーテル２０ｇに溶解した溶液を滴下し、５０
℃で１２時間撹拌を続けた。Next, 19.9 g of the above polyimide compound was redissolved in diethylene glycol dimethyl ether, and 4.9 g (0.014 g) of 4- (hydroxyphenylsilyl) -cyclohexane-1,2-dicarboxylic anhydride as a silicon compound was dissolved in this solution. Mol) in 20 g of diethylene glycol dimethyl ether was added dropwise.
Stirring was continued at 12 ° C. for 12 hours.
【００４５】撹拌後、反応溶液をメタノール中に投入
し、再沈澱を行い、目的とする下記構造式（１−ａ）を
有するポリイミド樹脂２１．５ｇを得た（収率８５
％）。After stirring, the reaction solution was poured into methanol and reprecipitated to obtain 21.5 g of the desired polyimide resin having the following structural formula (1-a) (yield: 85).
%).
【００４６】[0046]
【化１３】 Embedded image
【００４７】また、上記と同様の操作で上記ポリイミド
樹脂（１−ａ）の反応溶液を合成した後、再沈澱による
単離を行わず、反応溶液に無水酢酸４５ｇ、ピリジン１
７ｇを加え、反応系を４０℃に昇温してその温度を２時
間保持した。この操作を行ってから反応溶液をメタノー
ル中に投入し、再沈殿することにより下記構造式（２−
ａ）を有するポリイミド樹脂２１．３ｇを得た（収率８
５％）。After synthesizing a reaction solution of the polyimide resin (1-a) by the same operation as described above, 45 g of acetic anhydride and pyridine 1 were added to the reaction solution without isolation by reprecipitation.
7 g was added, the temperature of the reaction system was raised to 40 ° C, and the temperature was maintained for 2 hours. After performing this operation, the reaction solution is poured into methanol and reprecipitated to obtain the following structural formula (2-
21.3 g of a polyimide resin having a) was obtained (yield: 8).
5%).
【００４８】[0048]
【化１４】 Embedded image
【００４９】この生成物の赤外吸収スペクトルを観測し
たところ、シラノールに由来する吸収が３４２０ｃｍ-1
に観測され、目的とするポリイミド樹脂の生成が確認さ
れた。When the infrared absorption spectrum of this product was observed, the absorption derived from silanol was 3420 cm -1.
The formation of the desired polyimide resin was confirmed.
【００５０】［実施例２］実施例１の方法に従い、酸無
水物成分として１，３−ビス（３，４−ジカルボキシフ
ェニル）−１，１，３，３−テトラメチルジシロキサン
ジアンヒドリド５．０ｇ（０．０１２モル）、ジアミン
成分として２，２−ビス［４−（４−アミノフェノキ
シ）フェニル］プロパン７．２ｇ（０．０１８モル）、
シリコン化合物として４−（ヒドロキシメチルフェニル
シリル）−シクロヘキサン−１，２ージカルボン酸無水
物３．４ｇ（０．０１２モル）、溶剤としてＮ−メチル
−２−ピロリドン７０ｇを用いて目的とする下記構造式
（１−ｂ）を有するポリイミド樹脂１２．０ｇを得た
（収率７９％）。Example 2 According to the method of Example 1, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride 5 was used as an acid anhydride component. 2.0 g (0.012 mol), 7.2 g (0.018 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as a diamine component,
The following structural formula was obtained using 3.4 g (0.012 mol) of 4- (hydroxymethylphenylsilyl) -cyclohexane-1,2-dicarboxylic anhydride as a silicon compound and 70 g of N-methyl-2-pyrrolidone as a solvent. 12.0 g of a polyimide resin having (1-b) was obtained (yield 79%).
【００５１】[0051]
【化１５】 Embedded image
【００５２】また、実施例１と同様に更に脱水反応を行
うことにより、下記構造式（２−ｂ）を有するポリイミ
ド樹脂１２．５ｇを得た（収率８３％）。Further, 12.5 g of a polyimide resin having the following structural formula (2-b) was obtained by further performing a dehydration reaction in the same manner as in Example 1 (83% yield).
【００５３】[0053]
【化１６】 Embedded image
【００５４】［実施例３］実施例１の方法に従い、酸無
水物成分としてベンゾフェノンテトラカルボン酸二無水
物６．４ｇ（０．０２０モル）及び３，３’，４，４’
−ビフェニルテトラカルボン酸二無水物５．９ｇ（０．
０２０モル）、ジアミン成分として２，２−ビス（３，
４−ベンゼンジカルボン酸アンヒドリド）パーフルオロ
プロパン２５．９ｇ（０．０５０モル）、シリコン化合
物として４−（ヒドロキシジフェニルシリル）−シクロ
ヘキサン−１，２−ジカルボン酸無水物７．０ｇ（０．
０２０モル）、溶剤としてジエチレングリコールジメチ
ルエーテル４００ｇを用い、目的とする下記構造式（１
−ｃ）を有するポリイミド樹脂３５．０ｇを得た（収率
８０％）。Example 3 According to the method of Example 1, 6.4 g (0.020 mol) of benzophenonetetracarboxylic dianhydride and 3,3 ′, 4,4 ′ were used as acid anhydride components.
-Biphenyltetracarboxylic dianhydride 5.9 g (0.
020 mol) and 2,2-bis (3,3
25.9 g (0.050 mol) of 4-benzenedicarboxylic acid anhydride) perfluoropropane, and 7.0 g (0.50 g) of 4- (hydroxydiphenylsilyl) -cyclohexane-1,2-dicarboxylic anhydride as a silicon compound.
020 mol) and 400 g of diethylene glycol dimethyl ether as a solvent.
As a result, 35.0 g of a polyimide resin having -c) was obtained (yield: 80%).
【００５５】[0055]
【化１７】 Embedded image
【００５６】また、実施例１と同様に更に脱水反応を行
うことにより、下記構造式（２−ｃ）を有するポリイミ
ド樹脂３６．５ｇを得た（収率８４％）。Further, a dehydration reaction was further carried out in the same manner as in Example 1 to obtain 36.5 g of a polyimide resin having the following structural formula (2-c) (yield: 84%).
【００５７】[0057]
【化１８】 Embedded image
Claims (4)
樹脂。 【化１】 （但し、式中Ｒ１、Ｒ２は互いに同一又は異種の炭素数
１〜１０のアルキル基、アルケニル基、アリール基及び
ハロゲン置換アルキル基から選ばれる１価の基、Ｘは炭
素数６〜３０の芳香族環含有ジアミン残基及びケイ素原
子数２〜２０のシロキサン、シルエチレン又はシルフェ
ニレン構造を有するシリコーンジアミン残基から選ばれ
る２価の基、Ｙは、 から選ばれる４価の基、ｎは１〜２０の整数である。）1. A polyimide resin represented by the following structural formula (1). Embedded image (Wherein, R 1 and R 2 are the same or different and each is a monovalent group selected from an alkyl group, an alkenyl group, an aryl group and a halogen-substituted alkyl group having 1 to 10 carbon atoms, and X is 6 to 30 carbon atoms. An aromatic ring-containing diamine residue and a siloxane having 2 to 20 silicon atoms, a divalent group selected from silicone diamine residues having a silethylene or silphenylene structure, Y is And n is an integer of 1 to 20. )
樹脂。 【化２】 （但し、式中Ｒ１、Ｒ２は互いに同一又は異種の炭素数
１〜１０のアルキル基、アルケニル基、アリール基及び
ハロゲン置換アルキル基から選ばれる１価の基、Ｘは炭
素数６〜３０の芳香族環含有ジアミン残基及びケイ素原
子数２〜２０のシロキサン、シルエチレン又はシルフェ
ニレン構造を有するシリコーンジアミン残基から選ばれ
る２価の基、Ｙは、 から選ばれる４価の基、ｎは１〜２０の整数である。）2. A polyimide resin represented by the following structural formula (2). Embedded image (Wherein, R 1 and R 2 are the same or different and each is a monovalent group selected from an alkyl group, an alkenyl group, an aryl group and a halogen-substituted alkyl group having 1 to 10 carbon atoms, and X is 6 to 30 carbon atoms. An aromatic ring-containing diamine residue and a siloxane having 2 to 20 silicon atoms, a divalent group selected from silicone diamine residues having a silethylene or silphenylene structure, Y is And n is an integer of 1 to 20. )
と下記構造式（４）で表されるシリコン化合物とを反応
させることを特徴とする請求項１記載のポリイミド樹脂
の製造方法。 【化３】 （但し、式中Ｒ１、Ｒ２は互いに同一又は異種の炭素数
１〜１０のアルキル基、アルケニル基、アリール基及び
ハロゲン置換アルキル基から選ばれる１価の基、Ｘは炭
素数６〜３０の芳香族環含有ジアミン残基及びケイ素原
子数２〜２０のシロキサン、シルエチレン又はシルフェ
ニレン構造を有するシリコーンジアミン残基から選ばれ
る２価の基、Ｙは、 から選ばれる４価の基、ｎは１〜２０の整数である。）3. The method for producing a polyimide resin according to claim 1, wherein a polyimide represented by the following structural formula (3) is reacted with a silicon compound represented by the following structural formula (4). Embedded image (Wherein, R 1 and R 2 are the same or different and each is a monovalent group selected from an alkyl group, an alkenyl group, an aryl group and a halogen-substituted alkyl group having 1 to 10 carbon atoms, and X is 6 to 30 carbon atoms. An aromatic ring-containing diamine residue and a siloxane having 2 to 20 silicon atoms, a divalent group selected from silicone diamine residues having a silethylene or silphenylene structure, Y is And n is an integer of 1 to 20. )
ことを特徴とする請求項２記載のポリイミド樹脂の製造
方法。4. The method for producing a polyimide resin according to claim 2, wherein the polyimide resin according to claim 1 is dehydrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4260784A JP2713056B2 (en) | 1992-09-03 | 1992-09-03 | Polyimide resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4260784A JP2713056B2 (en) | 1992-09-03 | 1992-09-03 | Polyimide resin and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0680778A JPH0680778A (en) | 1994-03-22 |
| JP2713056B2 true JP2713056B2 (en) | 1998-02-16 |
Family
ID=17352689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4260784A Expired - Fee Related JP2713056B2 (en) | 1992-09-03 | 1992-09-03 | Polyimide resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2713056B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573811B (en) * | 2021-12-29 | 2023-12-22 | 宁波博雅聚力新材料科技有限公司 | Imide slurry, synthesis method thereof and composition containing imide slurry |
-
1992
- 1992-09-03 JP JP4260784A patent/JP2713056B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0680778A (en) | 1994-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS61118424A (en) | Soluble silicone-imide polymer | |
| JP2606402B2 (en) | Curable resin and method for producing the same | |
| JP4614349B2 (en) | Polyimide having alcoholic hydroxyl group and method for producing the same | |
| JP2722915B2 (en) | Curable resin, method for producing the same, and protective film for electronic component | |
| JP2949568B2 (en) | Novel polyimide and method for producing the same | |
| JP2619515B2 (en) | Silicon polyimide precursor composition | |
| JPH04351667A (en) | Curable resin composition and protective film for electronic component | |
| JP2713056B2 (en) | Polyimide resin and method for producing the same | |
| JP2764674B2 (en) | Polyimide silicone resin precursor composition | |
| JP2874014B2 (en) | Curable resin composition and protective film for electronic component | |
| JP6103992B2 (en) | Polyimide | |
| JP2713057B2 (en) | Polyimide resin and method for producing the same | |
| JP2712993B2 (en) | Curable resin, solution thereof, production method thereof, and protective film for electronic component | |
| JPH08302015A (en) | New polyimide and its production | |
| JPH0940777A (en) | Polyimide/siloxane block copolymer, varnish containing it and method of using it | |
| JP5499312B2 (en) | NOVEL POLYIMIDE SILICON HAVING ALCOHOLIC HYDROXY AND PROCESS FOR PRODUCING THE SAME | |
| JP2004149777A (en) | Transparent polyimide silicone resin containing thermosetting group | |
| JP5352527B2 (en) | Novel polyimide and method for producing the same | |
| JP2010106206A (en) | Polyimide precursor solution composition | |
| JP2551214B2 (en) | Curable resin solution composition, method for producing the same, and protective film for electronic parts | |
| JP3299777B2 (en) | Polyimide film and method for producing the same | |
| TWI391423B (en) | Polyimide having an alcoholic hydroxyl group and a process for producing the same | |
| JPS5956453A (en) | Composition for protecting semiconductor element | |
| JPH08231718A (en) | Curable polyimide resin, its production and composition containing the same | |
| JPH07238227A (en) | Curable polyimide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081031 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |