JPH05310889A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH05310889A JPH05310889A JP11384092A JP11384092A JPH05310889A JP H05310889 A JPH05310889 A JP H05310889A JP 11384092 A JP11384092 A JP 11384092A JP 11384092 A JP11384092 A JP 11384092A JP H05310889 A JPH05310889 A JP H05310889A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- filler
- heat resistance
- resin composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims description 21
- 239000000945 filler Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 9
- QXEVNIWTXCIZIS-UHFFFAOYSA-N (2-ethyl-3-methylphenyl)-phenylmethanediamine Chemical compound CCC1=C(C)C=CC=C1C(N)(N)C1=CC=CC=C1 QXEVNIWTXCIZIS-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- ZOQVDXYAPXAFRW-UHFFFAOYSA-N 2,5-diethyl-1h-imidazole Chemical compound CCC1=CNC(CC)=N1 ZOQVDXYAPXAFRW-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012153 distilled water Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract description 2
- 239000010445 mica Substances 0.000 abstract description 2
- 229910052618 mica group Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エポキシ樹脂組成物に
関する。本発明のエポキシ樹脂組成物を使用して製造し
たプリント配線板用積層板は、耐熱性に優れている。FIELD OF THE INVENTION The present invention relates to an epoxy resin composition. The laminated board for a printed wiring board manufactured using the epoxy resin composition of the present invention has excellent heat resistance.
【０００２】[0002]
【従来の技術】プリント配線板用エポキシ樹脂組成物
は、エポキシ樹脂、硬化剤及び硬化促進剤からなってお
り、これに必要に応じて、変性剤、難燃化剤、充填材を
加えている。樹脂として、ビスフェノールＡ型が主に用
いられ、硬化剤として芳香族アミン系、硬化促進剤とし
て、ルイス酸、イミダゾール系がある。芳香族アミン系
の硬化剤を使用した積層板の耐熱性を向上させるため、
硬化促進剤の添加量を多くしている。2. Description of the Related Art An epoxy resin composition for printed wiring boards comprises an epoxy resin, a curing agent and a curing accelerator, and if necessary, a modifier, a flame retardant and a filler are added thereto. . Bisphenol A type is mainly used as a resin, an aromatic amine type as a curing agent, and a Lewis acid or imidazole type as a curing accelerator. In order to improve the heat resistance of a laminate using an aromatic amine-based curing agent,
The addition amount of the curing accelerator is increased.
【０００３】[0003]
【発明が解決しようとする課題】硬化促進剤の添加量を
多くすることによって耐熱性はある程度向上するが、硬
化促進剤の添加量を多くしすぎると逆に耐熱性が低下す
る。耐熱性を向上させるために酸を加える方法が知られ
ているが、絶縁性が低下するため、プリント配線板用に
は適さない。本発明は、プリント配線板用エポキシ樹脂
組成物の耐熱性をさらに向上させることを目的とする。The heat resistance is improved to some extent by increasing the addition amount of the curing accelerator, but the heat resistance is decreased conversely if the addition amount of the curing accelerator is too large. A method of adding an acid to improve heat resistance is known, but it is not suitable for a printed wiring board because the insulating property is deteriorated. An object of the present invention is to further improve the heat resistance of the epoxy resin composition for printed wiring boards.
【０００４】[0004]
【課題を解決するための手段】本発明は、エポキシ樹
脂、芳香族アミン系硬化剤、硬化促進剤及び酸性充填材
を含有してなるエポキシ樹脂組成物である。本発明で、
酸性充填材とは、充填材５ｇに蒸留水１００ｍｌを加
え、３０分間撹拌した後の濾液のｐＨが２〜４を示すも
のをいう。The present invention is an epoxy resin composition containing an epoxy resin, an aromatic amine curing agent, a curing accelerator and an acidic filler. In the present invention,
The acidic filler means that the pH of the filtrate after adding 100 ml of distilled water to 5 g of the filler and stirring for 30 minutes shows 2 to 4.
【０００５】この充填材は、担体を酸の水溶液に浸漬
し、水洗処理し、乾燥して得られる。ｐＨが、４以上の
場合には、系内の硬化を進めるまでには至らず耐熱性が
向上しない。又、２以下であると、耐熱性は向上する
が、電気的な絶縁性に影響が出る。又添加量は、２〜２
０部（重量部）が適当であり、２部以下では効果がなく
２０部以上では他の特性が悪くなる。好ましくは、３．
５〜８．０部、最も好ましい量は６〜７部である。担体
としては、マイカ、カオリンやクレ−など粘土鉱物、ア
ルミナ、水酸化アルミニウムのような無機担体、ポリエ
チレン粒子、ポリエステル粒子、ナイロン粒子などの熱
可塑性樹脂の粒子、エポキシ樹脂、フェノール樹脂など
の熱硬化性樹脂粒子などの有機担体で担体の粒度０．１
〜１０μｍ、通常１〜２μｍのものを使用する。酸とし
ては、塩酸、硫酸及び硝酸などの無機酸が使用できる。This filler is obtained by immersing the carrier in an aqueous solution of acid, washing with water and drying. When the pH is 4 or higher, the curing in the system does not proceed and the heat resistance is not improved. On the other hand, when it is 2 or less, the heat resistance is improved, but the electrical insulation is affected. Moreover, the addition amount is 2 to 2.
0 part (parts by weight) is suitable, 2 parts or less are not effective, and 20 parts or more are detrimental to other properties. Preferably 3.
5 to 8.0 parts, most preferably 6 to 7 parts. Examples of the carrier include mica, clay minerals such as kaolin and clay, inorganic carriers such as alumina and aluminum hydroxide, particles of thermoplastic resin such as polyethylene particles, polyester particles and nylon particles, thermosetting of epoxy resin and phenol resin. Particle size of the carrier is 0.1 with organic carrier such as water-soluble resin particles.
Those having a thickness of 10 μm, usually 1 to 2 μm are used. As the acid, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid can be used.
【０００６】[0006]
【作用】本発明の特徴は、ｐＨ＝２〜４の充填剤を添加
することであり、上記酸を、樹脂組成物に直接添加する
方法とは異なる。酸を直接添加すると、酸中に含まれる
陰イオンが樹脂組成物中に均一に存在し、確かに耐熱性
は向上するが、絶縁性が低下する。これは、酸中に含ま
れる陰イオンによる。本発明では、充填剤近傍にのみ、
陰イオンが存在しにくいために、絶エン性の低下がな
く、高い耐熱性の有する積層板が得られる。A feature of the present invention is that a filler having a pH of 2 to 4 is added, which is different from the method of directly adding the acid to the resin composition. When the acid is directly added, the anions contained in the acid are uniformly present in the resin composition and the heat resistance is certainly improved, but the insulating property is lowered. This is due to the anion contained in the acid. In the present invention, only in the vicinity of the filler,
Since the presence of anions is less likely to occur, the laminated sheet having high heat resistance and no deterioration in insulating property can be obtained.
【０００７】ｐＨ２〜４の充填剤を前記したエポキシ樹
脂組成物に添加すると、ゲルタイムが変化する。特に硬
化系として、芳香族アミン系、硬化促進剤としてルイス
酸系を使用する場合に顕著である。この原因は、エポキ
シ基とアミノ基との反応が基本的にイオン反応であり、
系内のｐＨ値に大きく依存するためである。芳香族アミ
ンの場合は、ｐＨが小さいすなわち酸性域に入ると反応
が促進される。When a filler having a pH of 2 to 4 is added to the above epoxy resin composition, the gel time changes. In particular, it is remarkable when an aromatic amine type is used as a curing system and a Lewis acid type is used as a curing accelerator. The cause is that the reaction between the epoxy group and the amino group is basically an ionic reaction,
This is because it largely depends on the pH value in the system. In the case of an aromatic amine, the reaction is promoted when the pH is low, that is, when it enters the acidic range.
【０００８】硬化促進剤を増量することにより耐熱を向
上させる従来法に比べ、硬化促進剤とｐＨの小さい充填
剤を併用することにより絶縁性を損なうことなく耐熱性
を向上することができる。Compared with the conventional method in which the heat resistance is improved by increasing the amount of the curing accelerator, the heat resistance can be improved without impairing the insulating property by using the curing accelerator together with the filler having a low pH.
【０００９】[0009]
実施例１ エポキシ樹脂１００部（重量部、以下同じ）、メチルエ
チルジアミノジフェニルメタン１当量、ＢＦ3・モノエ
チルアミン錯体０．５部、ｐＨ３に調整したＡｌ2Ｏ3・
２ＳｉＯ2・２Ｈ2Ｏ１０部を配合してエポキシ樹脂組成
物とした。この組成物を、常法により有機質紙に含浸
し、プリプレグとし、プレス成形して、積層板を得た。Example 1 100 parts of epoxy resin (parts by weight, the same applies hereinafter), 1 equivalent of methylethyldiaminodiphenylmethane, 0.5 part of BF 3 .monoethylamine complex, Al 2 O 3 .adjusted to pH 3
An epoxy resin composition was prepared by mixing 10 parts of 2SiO 2 · 2H 2 O. An organic paper was impregnated with this composition by a conventional method to prepare a prepreg, which was press-molded to obtain a laminated plate.
【００１０】実施例２ エポキシ樹脂１００部、ジエチルメタトルエンジアミン
１当量、ＢＦ3・モノエチルアミン錯体０．５部、ｐＨ
３に調整したクレー１０部を配合してエポキシ樹脂組成
物とした。この組成物を、常法により有機質紙に含浸
し、プリプレグとし、プレス成形して、積層板を得た。Example 2 100 parts of epoxy resin, 1 equivalent of diethyl metatoluenediamine, 0.5 part of BF 3 · monoethylamine complex, pH
An epoxy resin composition was prepared by mixing 10 parts of the clay adjusted to 3. An organic paper was impregnated with this composition by a conventional method to prepare a prepreg, which was press-molded to obtain a laminated plate.
【００１１】実施例３ エポキシ樹脂１００部、メチルエチルジアミノジフェニ
ルメタン１当量、２−エチル−４エチルイミダゾール
０．２部、ｐＨ３に調整したＡｌ2Ｏ3・２ＳｉＯ2・２
Ｈ2Ｏ１０部を配合してエポキシ樹脂組成物とした。こ
の組成物を、常法により有機質紙に含浸し、プリプレグ
とし、プレス成形して、積層板を得た。Example 3 100 parts of epoxy resin, 1 equivalent of methylethyldiaminodiphenylmethane, 0.2 part of 2-ethyl-4ethylimidazole, Al 2 O 3 .2SiO 2 .2 adjusted to pH 3
An epoxy resin composition was prepared by blending 10 parts of H 2 O. An organic paper was impregnated with this composition by a conventional method to prepare a prepreg, which was press-molded to obtain a laminated plate.
【００１２】比較例１ エポキシ樹脂１００部、メチルエチルジアミノジフェニ
ルメタン１当量、ＢＦ3・モノエチルアミン錯体０．５
部、中性のＡｌ2Ｏ3・２ＳｉＯ2・２Ｈ2Ｏ１０部を配合
してエポキシ樹脂組成物とした。この組成物を、常法に
より有機質紙に含浸し、プリプレグとし、プレス成形し
て、積層板を得た。Comparative Example 1 100 parts of epoxy resin, 1 equivalent of methylethyldiaminodiphenylmethane, 0.5 of BF 3 · monoethylamine complex
Parts, and the epoxy resin composition by blending the Al 2 O 3 · 2SiO 2 · 2H 2 O10 parts neutral. An organic paper was impregnated with this composition by a conventional method to prepare a prepreg, which was press-molded to obtain a laminated plate.
【００１３】比較例２ エポキシ樹脂１００部、メチルエチルジアミノジフェニ
ルメタン１当量、ＢＦ3・モノエチルアミン錯体０．８
部、中性のＡｌ2Ｏ3・２ＳｉＯ2・２Ｈ2Ｏ１０部を配合
してエポキシ樹脂組成物とした。この組成物を、常法に
より有機質紙に含浸し、プリプレグとし、プレス成形し
て、積層板を得た。Comparative Example 2 Epoxy resin 100 parts, methylethyldiaminodiphenylmethane 1 equivalent, BF 3 · monoethylamine complex 0.8
Parts, and the epoxy resin composition by blending the Al 2 O 3 · 2SiO 2 · 2H 2 O10 parts neutral. An organic paper was impregnated with this composition by a conventional method to prepare a prepreg, which was press-molded to obtain a laminated plate.
【００１４】比較例３ エポキシ樹脂１００部、メチルエチルジアミノジフェニ
ルメタン１当量、ＢＦ3・モノエチルアミン錯体０．８
部、濃硫酸とメチルエチルケトンの混合溶液（重量比で
１：３）を０．１部配合してエポキシ樹脂組成物とし
た。この組成物を常法により、有機質紙に含浸し、プリ
プレグとし、プレス成形して、積層板を得た。Comparative Example 3 100 parts of epoxy resin, 1 equivalent of methylethyldiaminodiphenylmethane, BF 3 · monoethylamine complex 0.8
Parts, and 0.1 part of a mixed solution of concentrated sulfuric acid and methyl ethyl ketone (1: 3 by weight ratio) was mixed to prepare an epoxy resin composition. This composition was impregnated into organic paper by a conventional method to prepare a prepreg and press-molded to obtain a laminated board.
【００１５】以上の積層板についてのはんだ耐熱性及び
絶縁性並びにエポキシ樹脂組成物のゲルタイムを調べ
た。その結果を表１に示す。The solder heat resistance and insulation properties of the above laminates and the gel time of the epoxy resin composition were examined. The results are shown in Table 1.
【００１６】[0016]
【表１】 注 はんだ耐熱性：測定温度２７０℃ 絶縁性：ＪＩＳ２穴法処理後、Ｌ＝１０10 [Table 1] Note Solder heat resistance: Measurement temperature 270 ° C Insulation: After JIS 2-hole method, L = 10 10
【００１７】[0017]
【発明の効果】本発明によれば、硬化反応を促進する酸
を担体に含ませて配合するため、絶縁性を低下すること
なく耐熱性を高めることができる。EFFECTS OF THE INVENTION According to the present invention, an acid that accelerates the curing reaction is contained in a carrier and mixed, so that the heat resistance can be increased without lowering the insulating property.
Claims (1)
硬化促進剤及び酸性充填材を含有してなるエポキシ樹脂
組成物。1. An epoxy resin, an aromatic amine-based curing agent,
An epoxy resin composition comprising a curing accelerator and an acidic filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11384092A JPH05310889A (en) | 1992-05-07 | 1992-05-07 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11384092A JPH05310889A (en) | 1992-05-07 | 1992-05-07 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05310889A true JPH05310889A (en) | 1993-11-22 |
Family
ID=14622374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11384092A Pending JPH05310889A (en) | 1992-05-07 | 1992-05-07 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05310889A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI628223B (en) * | 2016-12-30 | 2018-07-01 | 廣東生益科技股份有限公司 | Preparation method of benzoxazine-containing resin composition, prepreg and laminate made from same |
| TWI632196B (en) * | 2016-12-30 | 2018-08-11 | 廣東生益科技股份有限公司 | Halogen-free flame-retardant resin composition and prepreg and copper-clad laminate made of the same |
| WO2020175272A1 (en) * | 2019-02-26 | 2020-09-03 | 富士フイルム株式会社 | Adhesive agent for endoscope and cured product thereof, and endoscope and manufacturing method therefor |
-
1992
- 1992-05-07 JP JP11384092A patent/JPH05310889A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI628223B (en) * | 2016-12-30 | 2018-07-01 | 廣東生益科技股份有限公司 | Preparation method of benzoxazine-containing resin composition, prepreg and laminate made from same |
| TWI632196B (en) * | 2016-12-30 | 2018-08-11 | 廣東生益科技股份有限公司 | Halogen-free flame-retardant resin composition and prepreg and copper-clad laminate made of the same |
| US20180371232A1 (en) * | 2016-12-30 | 2018-12-27 | Shengyi Technology Co., Ltd. | Halogen-free Flame Retardant Resin Composition, Prepreg and Copper Clad Laminate Prepared Therefrom |
| US10513608B2 (en) | 2016-12-30 | 2019-12-24 | Shengyi Technology Co., Ltd. | Process for preparing resin composition comprising benzoxazine, prepreg and laminate prepared therefrom |
| WO2020175272A1 (en) * | 2019-02-26 | 2020-09-03 | 富士フイルム株式会社 | Adhesive agent for endoscope and cured product thereof, and endoscope and manufacturing method therefor |
| JPWO2020175272A1 (en) * | 2019-02-26 | 2021-10-21 | 富士フイルム株式会社 | Adhesives for endoscopes and cured products thereof, endoscopes and methods for manufacturing them |
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