JPH029050B2 - - Google Patents
Info
- Publication number
- JPH029050B2 JPH029050B2 JP55075910A JP7591080A JPH029050B2 JP H029050 B2 JPH029050 B2 JP H029050B2 JP 55075910 A JP55075910 A JP 55075910A JP 7591080 A JP7591080 A JP 7591080A JP H029050 B2 JPH029050 B2 JP H029050B2
- Authority
- JP
- Japan
- Prior art keywords
- organic group
- unsaturated
- general formula
- weight
- resin composition
- 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 - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000011342 resin composition Substances 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 239000004962 Polyamide-imide Substances 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 229920002312 polyamide-imide Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- -1 poly(phenylmethylene) bismaleimide Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- QDEQBRUNBFJJPW-UHFFFAOYSA-N 1-(3-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC(N2C(C=CC2=O)=O)=C1 QDEQBRUNBFJJPW-UHFFFAOYSA-N 0.000 description 1
- CVKDEEISKBRPEQ-UHFFFAOYSA-N 1-(4-nitrophenyl)pyrrole-2,5-dione Chemical compound C1=CC([N+](=O)[O-])=CC=C1N1C(=O)C=CC1=O CVKDEEISKBRPEQ-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VCFJLCCBKJNFKQ-UHFFFAOYSA-N 3-[4-(2,5-dioxopyrrol-3-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC(=CC=2)C=2C(NC(=O)C=2)=O)=C1 VCFJLCCBKJNFKQ-UHFFFAOYSA-N 0.000 description 1
- SLJJEYCPTRKHFI-UHFFFAOYSA-N 3-[6-(2,5-dioxopyrrol-3-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CCCCCCC=2C(NC(=O)C=2)=O)=C1 SLJJEYCPTRKHFI-UHFFFAOYSA-N 0.000 description 1
- KAWODUAUIIOGGH-UHFFFAOYSA-N 3-[[4-[(2,5-dioxopyrrol-3-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(CC=2C=CC(CC=3C(NC(=O)C=3)=O)=CC=2)=C1 KAWODUAUIIOGGH-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- 239000004642 Polyimide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IQBLYMCFIBYFFT-UHFFFAOYSA-N ethene pyrrole-2,5-dione Chemical compound C=C.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 IQBLYMCFIBYFFT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】
本発明は、耐熱性に優れ、良好な機械的特性、
および加工性を有する熱硬化性樹脂組成物に関す
る。[Detailed description of the invention] The present invention has excellent heat resistance, good mechanical properties,
and a thermosetting resin composition having processability.
一般にポリイミド系樹脂は、耐熱性や耐薬品性
などに優れているところから、特に高温で使用さ
れるフイルム、電線被覆、積層板、塗料、接着
剤、成形品等の用途に広く用いられている。 In general, polyimide resins have excellent heat resistance and chemical resistance, so they are widely used in applications such as films, electric wire coatings, laminates, paints, adhesives, and molded products that are used at high temperatures. .
このようなポリイミド系樹脂のうち、マレイミ
ド系化合物の単独重合物は耐熱性に優れている
が、その分子構造から機械的特性に乏しい傾向が
あり、このため他の材料と共重合させることによ
り、その耐熱性ある程度、犠牲にしながら機械的
強度を改良して使用しているのが現状である。 Among such polyimide-based resins, homopolymers of maleimide-based compounds have excellent heat resistance, but due to their molecular structure, they tend to have poor mechanical properties. Therefore, by copolymerizing with other materials, Currently, it is used by sacrificing its heat resistance to some extent while improving its mechanical strength.
又、一方芳香族系のポリイミド樹脂やポリアミ
ドイミド樹脂は、機械的特性、耐熱性共に優れて
いるが加工性に難点があり、フイルム、電線被覆
等には種々応用されているが、成形積層用等とし
ては製造に高温、高圧を要し、フエノール樹脂、
エポキシ樹脂等の一般的な熱硬化性樹脂の加工設
備をそのまま利用出来ず、特殊な設備を必要とす
るため、極く一部の分野にしか用いられない実情
にある。 On the other hand, aromatic polyimide resins and polyamide-imide resins have excellent mechanical properties and heat resistance, but have difficulties in processability, and are used in various applications such as films and wire coatings, but they are not suitable for molding and laminating. etc., which require high temperature and pressure to manufacture, such as phenolic resin,
Since processing equipment for general thermosetting resins such as epoxy resins cannot be used as is, and special equipment is required, it is only used in a few fields.
本発明は上記事情に鑑みてなされたもので耐熱
性、加工性に優れた熱硬化性樹脂組成物を提供し
ようとするものである。 The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a thermosetting resin composition having excellent heat resistance and processability.
すなわち、本発明は
(A)一般式
（式中R1はｎ価の有機基、X1，X2，はそれぞ
れ水素原子、ハロゲン原子又は有機基から選ばれ
た同一又は異なる一価の原子又は基を表わし、ｎ
は２以上の整数を表わす。）
で表わされるポリマレイミド類と、
(B)，(イ)一般式
R2（―NCO）n
（式中、R2はｍ価の有機基を表わし、ｍは２
以上の整数を表わす。）
で表わされるポリイソシアネート類および(ロ)一般
式
R3（―COOH）p
（式中、R3は炭素―炭素二重結合を含むｐ価
の有機基を表わし、ｐは２以上の整数を表わす。）
で表わされるポリカルボン酸類および(ハ)一般式
（式中、R4はｑ価の有機基を表わし、ｑは２
以上の整数を表わす。）
で表わされるポリカルボン酸無水物類を反応させ
て得られる不飽和ポリアミドイミド樹脂とを混合
して成る熱硬化性樹脂組成物に関する。 That is, the present invention provides (A) general formula (In the formula, R 1 is an n-valent organic group, X 1 and X 2 each represent the same or different monovalent atoms or groups selected from a hydrogen atom, a halogen atom, or an organic group, and n
represents an integer greater than or equal to 2. ) Polymaleimide represented by (B), (a) general formula R 2 (-NCO) n (wherein R 2 represents an m-valent organic group, m is 2
represents an integer greater than or equal to ) and (b) general formula R 3 (-COOH) p (wherein R 3 represents a p-valent organic group containing a carbon-carbon double bond, and p represents an integer of 2 or more. ) Polycarboxylic acids represented by (c) general formula (In the formula, R 4 represents a q-valent organic group, and q is 2
represents an integer greater than or equal to ) It relates to a thermosetting resin composition formed by mixing an unsaturated polyamideimide resin obtained by reacting a polycarboxylic acid anhydride represented by the following formula.
本発明における(A)のポリマレイミド類として
は、エチレンジマレイミド、ヘキサメチレンジマ
レイミド、ｍ―又はＰ―フエニレンジマレイミ
ド、４，4′―ジフエニルメタンジマレイミド、
４，4′―ジシクロヘキシルメタンジマレイミド、
ｍ―、又はＰ―キシリレンジマレイミド、４，
4′―ジフエニルシクロヘキサンジマレイミド、
４，4′―ジフエニレンジマレイミド、ポリ（フエ
ニルメチレン）ビスマレイミド、Ｎ・N′―ジチ
オビス（Ｎ―フエニルマレイミド）のようなジマ
レイミド化合物を使用することが望ましい。 Examples of the polymaleimide (A) in the present invention include ethylene dimaleimide, hexamethylene dimaleimide, m- or P-phenylene dimaleimide, 4,4'-diphenylmethane dimaleimide,
4,4′-dicyclohexylmethane dimaleimide,
m- or p-xylylene dimaleimide, 4,
4′-diphenylcyclohexane dimaleimide,
It is desirable to use dimaleimide compounds such as 4,4'-diphenylene dimaleimide, poly(phenylmethylene) bismaleimide, N.N'-dithiobis(N-phenylmaleimide).
なお、必要に応じてＮ―フエニルマレイミド、
Ｎ―３―クロロフエニルマレイミド、Ｎ―４―ニ
トロフエニルマレイミドのようなモノマレイミド
化合物を併用することも可能である。 In addition, N-phenylmaleimide,
It is also possible to use monomaleimide compounds such as N-3-chlorophenylmaleimide and N-4-nitrophenylmaleimide.
この場合、モノマレイミド化合物の配合割合
は、マレイミド化合物の全量に対して20重量％以
下とすることが望ましい。 In this case, the blending ratio of the monomaleimide compound is preferably 20% by weight or less based on the total amount of the maleimide compound.
本発明において、(B)の不飽和ポリアミドイミド
樹脂製造の出発物質として使用する(イ)のポリイソ
シアネート類としては、４，4′―ジフエニルメタ
ンジイソシアネート、４，4′―ジフエニルエーテ
ルジイソシアネート、ｍ―又はＰ―フエニレンジ
イソシアネート、４，4′―ジフエニルスルホンジ
イソシアネート、４，4′―ジフエニレンジイソシ
アネート、１，５―ナフタレンジイソシアネー
ト、ｍ―又はＰキシリレンジイソシアネート、ヘ
キサメチレンジイソシアネート、４，4′―ジシク
ロヘキシルメタンジイソシアネート、１，４―シ
クロヘキサンジイソシアネート、或いは、これら
の分子中に、アルキル、ハロゲン、アルコキシ、
ニトロ、カルボアルコキシ基のような非反応性の
置換基を有するジイソシアネート類があり、これ
らを単独で又は２種以上を混合して用いる。 In the present invention, the polyisocyanates (A) used as starting materials for producing the unsaturated polyamideimide resin (B) include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, m- or P-phenylene diisocyanate, 4,4'-diphenylsulfone diisocyanate, 4,4'-diphenylene diisocyanate, 1,5-naphthalene diisocyanate, m- or P-xylylene diisocyanate, hexamethylene diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, or alkyl, halogen, alkoxy,
There are diisocyanates having non-reactive substituents such as nitro and carbalkoxy groups, and these are used alone or in combination of two or more.
また、(ロ)の炭素―炭素２重結合を有するポリカ
ルボン酸類としては、マレイン酸、フマル酸、イ
タコン酸、シトラコン酸等があり、これらを単独
で又は２種以上を混合して用いる。(ハ)のポリカル
ボン酸無水物類としては、ピロメリツト酸、３，
3′・４，4′―ベンゾフエノンテトラカルボン酸等
の無水物特に二無水物を使用するのが望ましい。 Further, (b) polycarboxylic acids having a carbon-carbon double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., and these may be used alone or in combination of two or more. (c) Polycarboxylic acid anhydrides include pyromellitic acid, 3,
It is preferred to use anhydrides, especially dianhydrides, such as 3'.4,4'-benzophenonetetracarboxylic acid.
ここで(ロ)の不飽和カルボン酸類の配合割合は、
これと(ハ)のテトラカルボン酸無水物類から成る酸
成分の全量に対して５〜90モル％、より好ましく
は10〜80モル％とする。 Here, the blending ratio of unsaturated carboxylic acids (b) is:
The amount is preferably 5 to 90 mol %, more preferably 10 to 80 mol %, based on the total amount of the acid component consisting of this and the tetracarboxylic anhydride (c).
不飽和カルボン酸類の割合が上記範囲外では、
５モル％未満の場合得られる熱硬化性樹脂組成物
の機械的強度が低下してしまい、逆に90モル％を
越える場合には、耐熱性の低下がみられ、いずれ
の場合も好ましくない。 If the proportion of unsaturated carboxylic acids is outside the above range,
If the amount is less than 5 mol%, the mechanical strength of the resulting thermosetting resin composition will be reduced, and if it exceeds 90 mol%, the heat resistance will be reduced, and both cases are unfavorable.
本発明において、前記(イ)のポリイソシアネート
類、(ロ)のポリカルボン酸類および(ハ)のポリカルボ
ン酸無水物類を反応させて不飽和ポリアミドイミ
ド樹脂を製造する際の反応溶媒としては、非プロ
トン系有機極性溶媒、例えばＮ―メチル―２―ピ
ロリドン、ジメチルアセトアミド、ジメチルホル
ムアミド、テトラメチル尿素等が好適している。 In the present invention, the reaction solvent for producing an unsaturated polyamideimide resin by reacting the polyisocyanates (a), the polycarboxylic acids (b), and the polycarboxylic acid anhydrides (c) are: Aprotic organic polar solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, tetramethylurea and the like are suitable.
反応温度及び反応時間は用いる化合物の組み合
わせ溶媒等によつて異なるが、50〜160℃好まし
くは、60〜150℃で、遊離発生してくる炭酸ガス
を反応系から除去しながら、所望する高分子量の
不飽和ポリアミドイミド樹脂を得るに十分な時
間、通常は１〜６時間反応させる。 The reaction temperature and reaction time vary depending on the combined solvent of the compound used, etc., but are set at 50 to 160°C, preferably 60 to 150°C, to achieve the desired high molecular weight while removing liberated carbon dioxide from the reaction system. The reaction is carried out for a sufficient period of time, usually from 1 to 6 hours, to obtain an unsaturated polyamideimide resin.
(イ)のイソシアネート成分と(ロ)，(ハ)の酸成分との
反応の割合は、ほぼ等モルずつとするが、10％を
限度としてどちらかの成分を過剰に用いて反応さ
せることもできる。 The reaction ratio between the isocyanate component (a) and the acid components (b) and (c) should be approximately equal moles, but it is also possible to use an excess of either component up to 10%. can.
本発明の熱硬化性樹脂組成物は、このようにし
て得られた(B)の不飽和ポリアミド樹脂溶液と(A)の
ポリマレイミド類とを溶解混合することにより得
られる。 The thermosetting resin composition of the present invention is obtained by dissolving and mixing the unsaturated polyamide resin solution (B) thus obtained and the polymaleimide (A).
ここで両者の混合割合は、(A)のポリマレイミド
類の100重量部に対して、(B)の不飽和ポリアミド
イミド樹脂を20〜400重量部、より好ましくは25
〜300重量部の割合とする。 Here, the mixing ratio of the two is 20 to 400 parts by weight, more preferably 25 parts by weight of the unsaturated polyamideimide resin (B) to 100 parts by weight of the polymaleimide (A).
~300 parts by weight.
混合の割合が上記範囲外では、不飽和ポリアミ
ドイミド樹脂の割合が20重量部を下回る場合機械
的強度が低下してしまい、逆に400重量部を越え
た場合には、加工性が低下して、成形加工の際の
作業性が改善されないようになる。このようにし
て得られる樹脂溶液にガラスクロス、積層品成形
用基材等を浸漬させるか、又はこれら基材に樹脂
溶液を塗布した後、溶媒を揮散除去して得たプリ
プレグを重ね合わせ、170〜〜250℃の温度で、加
圧加熱成形を行なうことにより優れた耐熱性や電
気特性を備えた積層品を得ることができる。又、
成形材料に応用する場合には、樹脂溶液を大過剰
の水中に注ぎ入れ樹脂分を分離乾燥する事により
優れた耐熱性と機械的特性を有する成形用粉末を
得ることができる。 If the mixing ratio is outside the above range, mechanical strength will decrease if the proportion of unsaturated polyamideimide resin is less than 20 parts by weight, and conversely, if it exceeds 400 parts by weight, processability will decrease. , the workability during molding process will not be improved. Glass cloth, substrates for forming laminates, etc. are immersed in the resin solution obtained in this way, or the resin solution is applied to these substrates, and then the prepreg obtained by volatilizing and removing the solvent is superimposed. By performing pressure and heat molding at a temperature of ~250°C, a laminate with excellent heat resistance and electrical properties can be obtained. or,
When applied to molding materials, a molding powder with excellent heat resistance and mechanical properties can be obtained by pouring the resin solution into a large excess of water and separating and drying the resin component.
このようにして得られる熱硬化性樹脂組成物に
は、硬化を促進するために例えば、過酸化物類、
第三級アミン類、イミダゾール類等の硬化剤を添
加する事ができる。硬化剤の添加量は樹脂組成物
の0.01〜３重量％程度の範囲で成形条件に応じて
任意に選択される。 The thermosetting resin composition thus obtained may contain, for example, peroxides,
Curing agents such as tertiary amines and imidazoles can be added. The amount of the curing agent added is arbitrarily selected in the range of about 0.01 to 3% by weight of the resin composition depending on the molding conditions.
更に上記組成物にはタルク、アルミナ、シリコ
ン、ジルコン、石英ガラス粉、ガラス繊維等の充
填剤やカーボンブラツク、ベンガラ等の着色剤、
グリシドオキシプロピルトリエトキシシラン等の
カツプリング剤、ステアリン酸等の離型剤も適宜
添加することができる。 Furthermore, the above composition may contain fillers such as talc, alumina, silicon, zircon, quartz glass powder, and glass fiber, and colorants such as carbon black and red iron.
A coupling agent such as glycidoxypropyltriethoxysilane and a mold release agent such as stearic acid may also be added as appropriate.
本発明の熱硬化性樹脂組成物は耐熱性、機械的
特性および加工性を兼ね備えており、工業上きわ
めて有用である。 The thermosetting resin composition of the present invention has heat resistance, mechanical properties, and processability, and is extremely useful industrially.
以下、本発明の実施例について記載する。 Examples of the present invention will be described below.
実施例 １
ジフエニルメタンジイソシアネート50.0ｇ
（0.2モル）、ピロメリツト酸二無水物32.7ｇ（0.15
モル）、フマル酸5.8ｇ（0.05モル）を、Ｎ―メチ
ル―２―ピロリドン250ｇと共に反応容器に収容
し、窒素気流下で加熱した。温度が、60℃以上に
なると炭酸ガスを発生し、反応を開始する。更に
温度を上げ80℃に１時間保つた後、６時間かけて
140℃まで昇温し反応を停止した。得られた粘稠
な樹脂溶液に４，4′―ジフエニルメタンジマレイ
ミド79.7ｇとＮ―メチル―２―ピロリドン50ｇを
添加し、均一な樹脂溶液を得た。この溶液をアミ
ノシラン処理したガラスクロス（250×250×0.18
mm）に塗布し、室温で30分間、風乾した後、170
℃で15分間乾燥しプリプレグを得た。このプリプ
レグを９枚重ねて200℃に加熱したプレスにより
50Kg／cm2で１時間加圧成形し、厚さ1.6mmの積層
板を得た。Example 1 Diphenylmethane diisocyanate 50.0g
(0.2 mol), pyromellitic dianhydride 32.7 g (0.15
5.8 g (0.05 mol) of fumaric acid and 250 g of N-methyl-2-pyrrolidone were placed in a reaction vessel and heated under a nitrogen stream. When the temperature reaches 60°C or higher, carbon dioxide gas is generated and the reaction begins. After increasing the temperature further and keeping it at 80℃ for 1 hour, it was heated for 6 hours.
The reaction was stopped by raising the temperature to 140°C. 79.7 g of 4,4'-diphenylmethane dimaleimide and 50 g of N-methyl-2-pyrrolidone were added to the resulting viscous resin solution to obtain a uniform resin solution. This solution was applied to a glass cloth (250 x 250 x 0.18) treated with aminosilane.
mm) and air-dried for 30 minutes at room temperature.
A prepreg was obtained by drying at ℃ for 15 minutes. By stacking nine sheets of prepreg and pressing them at 200℃,
Pressure molding was performed for 1 hour at 50 kg/cm 2 to obtain a laminate with a thickness of 1.6 mm.
この積層板を更に220℃で５時間アフターキユ
アし、曲げ強度を測定したところ室温で57Kg／
mm2、200℃でも55Kg／mm2の強度を保持し、250℃で
500時間加圧した後も54Kg／mm2の優れた値を示し
た。 This laminate was further after-cured at 220℃ for 5 hours, and the bending strength was measured at room temperature, which was 57kg/
mm 2 , maintains a strength of 55Kg/mm 2 even at 200℃, and maintains a strength of 55Kg/mm 2 even at 250℃.
Even after 500 hours of pressurization, it showed an excellent value of 54 Kg/mm 2 .
実施例 ２
ジフエニルメタンジイソシアネート50.0ｇ
（0.2モル）、３，3′・４，4′―ベンゾフエノンテト
ラカルボン酸二無水物34.8ｇ（0.1モル）、フマル
酸11.6ｇ（0.1モル）をＮ―メチル―２―ピロリ
ドン250ｇと共に室素気流下で加熱した。温度が
60℃以上になると炭酸ガスを発生し反応を開始す
る。更に温度を上げ80℃に１時間保つた後、６時
間かけて140℃まで昇温し、反応を停止した。こ
の後60℃まで冷却し４，4′―ジフエニルメタンジ
マレイミド204.7ｇと２―エチル―４―メチルイ
ミダゾール2.9ｇを添加して均一な樹脂溶液を得
た。Example 2 Diphenylmethane diisocyanate 50.0g
(0.2 mol), 34.8 g (0.1 mol) of 3,3'-4,4'-benzophenonetetracarboxylic dianhydride, and 11.6 g (0.1 mol) of fumaric acid were placed in a room together with 250 g of N-methyl-2-pyrrolidone. Heated under a stream of bare air. temperature
When the temperature exceeds 60℃, carbon dioxide gas is generated and the reaction begins. The temperature was further raised and kept at 80°C for 1 hour, and then raised to 140°C over 6 hours to stop the reaction. Thereafter, the mixture was cooled to 60°C, and 204.7 g of 4,4'-diphenylmethane dimaleimide and 2.9 g of 2-ethyl-4-methylimidazole were added to obtain a uniform resin solution.
この樹脂溶液を大量の水中に注入し、粉末状の
沈殿物を得た。この沈殿物を過、水洗を繰り返
した後、減圧下に60℃で、10時間、乾燥して成形
材料を得た。このものを200℃に加熱した金型に
入れ、120Kg／cm2の圧力で成形したところ、３分
間の成形で型から取り出す時に十分な硬度を保つ
ていた。その後、230℃で５時間アフターキユア
した後、成形物の曲げ強度を測定した。その結
果、室温で13.2Kg／mm2、200℃でも12.5Kg／mm2の
強度を保持し、250℃で、500時間加熱した後も
13.0Kg／mm2の優れた値を示した。 This resin solution was poured into a large amount of water to obtain a powdery precipitate. The precipitate was filtered, washed repeatedly with water, and then dried under reduced pressure at 60° C. for 10 hours to obtain a molding material. When this product was placed in a mold heated to 200°C and molded at a pressure of 120 kg/cm 2 , it maintained sufficient hardness when removed from the mold after 3 minutes of molding. Thereafter, after curing at 230° C. for 5 hours, the bending strength of the molded product was measured. As a result, it maintains a strength of 13.2Kg/mm 2 at room temperature and 12.5Kg/mm 2 at 200℃, and even after heating at 250℃ for 500 hours.
It showed an excellent value of 13.0Kg/ mm2 .
Claims (1)
れ水素原子、ハロゲン原子または有機基から選ば
れた同一または異なる一価の原子または基を表わ
し、ｎは２以上の整数を表わす。） で表わされるポリマレイミド類 100重量部と、 (B) (イ) 一般式 R2（―NCO）n （式中、R2はｍ価の有機基を表わし、ｍ
は２以上の整数を表わす。）で表わされるポ
リイソシアネート類および (ロ) 一般式 R3（―COOH）p （式中、R3は炭素―炭素二重結合を含む
ｐ価の有機基を表わし、ｐは２以上の整数を
表わす。） で表わされるポリカルボン酸類および (ハ) 一般式 （式中、R4はｑ価の有機基を表わし、ｑ
は２以上の整数を表わす。）で表わされるポ
リカルボン酸無水物類 を反応させて得られる不飽和ポリアミドイミ
ド樹脂 20〜400重量部と を混合して成る熱硬化性樹脂組成物。 ２ (B)、(ロ)のポリカルボン酸類の配合量が、不飽
和ポリアミドイミド樹脂の出発物質の酸成分の全
量に対し、５〜90モル％を占めることを特徴とす
る特許請求の範囲第１項記載の熱硬化性樹脂組成
物。[Claims] 1 (A) General formula (In the formula, R 1 is an n-valent organic group, X 1 and X 2 each represent the same or different monovalent atoms or groups selected from a hydrogen atom, a halogen atom, or an organic group, and n is an integer of 2 or more. 100 parts by weight of a polymaleimide represented by
represents an integer greater than or equal to 2. ) and (b) general formula R 3 (-COOH) p (wherein R 3 represents a p-valent organic group containing a carbon-carbon double bond, and p is an integer of 2 or more. ) Polycarboxylic acids represented by (c) general formula (In the formula, R 4 represents a q-valent organic group, and q
represents an integer greater than or equal to 2. 20 to 400 parts by weight of an unsaturated polyamideimide resin obtained by reacting a polycarboxylic acid anhydride represented by the following: A thermosetting resin composition. 2. Claim No. 2 characterized in that the blending amount of the polycarboxylic acids (B) and (B) is 5 to 90 mol% based on the total amount of the acid component of the starting material of the unsaturated polyamideimide resin. Thermosetting resin composition according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7591080A JPS572316A (en) | 1980-06-05 | 1980-06-05 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7591080A JPS572316A (en) | 1980-06-05 | 1980-06-05 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS572316A JPS572316A (en) | 1982-01-07 |
| JPH029050B2 true JPH029050B2 (en) | 1990-02-28 |
Family
ID=13589955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7591080A Granted JPS572316A (en) | 1980-06-05 | 1980-06-05 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS572316A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07119088B2 (en) * | 1985-04-18 | 1995-12-20 | 日立化成工業株式会社 | Manufacturing method of printed wiring board |
| JPS62153313A (en) * | 1985-12-27 | 1987-07-08 | Japan Synthetic Rubber Co Ltd | Organic solvent-soluble polyimide and its production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4837246A (en) * | 1971-09-16 | 1973-06-01 | ||
| JPS52994A (en) * | 1975-06-19 | 1977-01-06 | Ciba Geigy Ag | Imide grouppcontaining crosslinked polymer and preparation thereof |
| JPS5489623A (en) * | 1977-12-27 | 1979-07-16 | Asahi Chemical Ind | Heat resistant photoresist composition and production thereof |
-
1980
- 1980-06-05 JP JP7591080A patent/JPS572316A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4837246A (en) * | 1971-09-16 | 1973-06-01 | ||
| JPS52994A (en) * | 1975-06-19 | 1977-01-06 | Ciba Geigy Ag | Imide grouppcontaining crosslinked polymer and preparation thereof |
| JPS5489623A (en) * | 1977-12-27 | 1979-07-16 | Asahi Chemical Ind | Heat resistant photoresist composition and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS572316A (en) | 1982-01-07 |
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