JP2003064180A - Curable resin having dihydrobenzoxazine ring structure and heat-resistant cured resin - Google Patents
Curable resin having dihydrobenzoxazine ring structure and heat-resistant cured resinInfo
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- JP2003064180A JP2003064180A JP2002169203A JP2002169203A JP2003064180A JP 2003064180 A JP2003064180 A JP 2003064180A JP 2002169203 A JP2002169203 A JP 2002169203A JP 2002169203 A JP2002169203 A JP 2002169203A JP 2003064180 A JP2003064180 A JP 2003064180A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、硬化特性
に優れた硬化性樹脂を与える新規な樹脂に関するもので
あり、特に、ジヒドロベンゾキサジン環構造を有する新
規な樹脂及びその硬化樹脂に関するものである。TECHNICAL FIELD The present invention relates to a novel resin which gives a curable resin having excellent heat resistance and curing characteristics, and more particularly to a novel resin having a dihydrobenzoxazine ring structure and its cured resin. It is a thing.
【０００２】[0002]
【従来の技術】芳香族ポリエステル、芳香族ポリアミ
ド、芳香族ポリイミド等の様々な耐熱性樹脂が開発さ
れ、それぞれの樹脂特性に合った分野へ応用されてい
る。最近、プリント配線板用銅張積層板、多層配線板用
接着剤、半導体用封止材料、半導体実装用接着剤、半導
体搭載用モジュール、あるいは、自動車用、航空機用、
建築部材等に用いられる部品等に用いられる硬化性樹脂
において、高温・高湿下での安定性や信頼性に優れた樹
脂材料が求められている。また、環境低負荷化の観点か
ら、ハロゲンフリー難燃性を有する樹脂材料が強く望ま
れている。2. Description of the Related Art Various heat resistant resins such as aromatic polyester, aromatic polyamide and aromatic polyimide have been developed and applied to fields suitable for their respective resin characteristics. Recently, copper clad laminates for printed wiring boards, adhesives for multilayer wiring boards, sealing materials for semiconductors, adhesives for semiconductor mounting, semiconductor mounting modules, or for automobiles, aircraft,
In the curable resin used for parts used for building members and the like, a resin material excellent in stability and reliability under high temperature and high humidity is required. Further, from the viewpoint of environmental load reduction, a halogen-free flame-retardant resin material is strongly desired.
【０００３】近年、ジヒドロベンゾキサジン環を有する
樹脂が、従来のフェノール樹脂に比較して、硬化物の耐
熱性、耐湿性が良好な樹脂であることが報告されている
（H.Ishida, et al., J. Polym. Sci., Vol. 32, p921
(1994), H. Ishida, et al., J.Appl. Polym. Sci., V
ol. 61, 1595 (1996)）。また、これらの樹脂は、開環
重合反応性を有しているため、低硬化収縮性を示し、開
環反応後の硬化物は、低熱膨張性を有しているなど様々
な特徴を有することも示されている（H. Ishida, et a
l., J. Polym. Sci., Vol.34, 1019 (1994),）。更に、
これらは、エポキシ樹脂とも反応性を示し、硬化剤とし
て有効であることも示されている（特開平4-227922号公
報）。しかしながら、従来のこれらの樹脂及び樹脂組成
物は、ガラス転移温度が160℃程度で、耐熱性や難燃性
において特性が充分とはいえず、良好な特性を得るに
は、高い硬化温度と長い硬化時間を必要とするという欠
点を有していた。In recent years, it has been reported that a resin having a dihydrobenzoxazine ring is a resin having a heat resistance and a moisture resistance of a cured product which are better than those of a conventional phenol resin (H. Ishida, et al. al., J. Polym. Sci., Vol. 32, p921
(1994), H. Ishida, et al., J. Appl. Polym. Sci., V
ol. 61, 1595 (1996)). Further, since these resins have ring-opening polymerization reactivity, they exhibit low curing shrinkage, and the cured product after the ring-opening reaction has various characteristics such as low thermal expansion. Is also shown (H. Ishida, et a
L., J. Polym. Sci., Vol.34, 1019 (1994),). Furthermore,
It has been shown that these also show reactivity with an epoxy resin and are effective as a curing agent (JP-A-4-227922). However, these conventional resins and resin compositions have a glass transition temperature of about 160 ° C. and cannot be said to have sufficient characteristics in heat resistance and flame retardancy, and in order to obtain good characteristics, a high curing temperature and a long curing temperature are required. It had the drawback of requiring a curing time.
【０００４】更に、特公昭49-47378号公報、特開平2-69
567号公報、あるいは特開平4-227922号公報に示される
ようなジヒドロベンゾキサジン環を有する化合物を用い
た熱硬化性樹脂組成物は知られているが、これらは硬化
前においては、フィルムやシートあるいは繊維等として
用いることができず、硬化後の樹脂特性においては、充
分な耐熱性や機械的特性が得られなかった。Further, Japanese Patent Publication No. 49-47378 and Japanese Patent Laid-Open No. 2-69
No. 567, or thermosetting resin composition using a compound having a dihydrobenzoxazine ring as shown in JP-A-4-227922 is known, but these, before curing, a film or It could not be used as a sheet or a fiber, and in the resin properties after curing, sufficient heat resistance and mechanical properties were not obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、硬化後にお
いて耐熱性、難燃性において優れた特性を有する新規な
硬化性樹脂とその製造方法並びに耐熱性硬化樹脂を提供
することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel curable resin having excellent heat resistance and flame retardancy after curing, a method for producing the same, and a heat resistant cured resin. .
【０００６】[0006]
【課題を解決するための手段】本発明者は、前期目的を
達成するために鋭意研究を重ねた結果、繰り返し単位中
に、ジヒドロナフトキサジン構造を有する硬化性樹脂
が、耐熱性、機械的特性を大幅に向上した硬化樹脂を与
えることが可能であり、また、主鎖構造変化により特性
の改善も容易であることを見出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a curable resin having a dihydronaphthoxazine structure in a repeating unit was found to have heat resistance and mechanical properties. The present invention has been completed by finding that it is possible to provide a cured resin having significantly improved characteristics, and that it is easy to improve the characteristics by changing the main chain structure.
【０００７】すなわち、本発明は、 下記一般式（１）That is, the present invention provides the following general formula (1)
【化４】
（式中、Ar1は４価の芳香族基を示し、Ar2は２価の芳香
族基を示し、Rは水素又は炭素数１〜６の炭化水素基を
示し、ｎは分子中の平均の数であり、２〜５０の数を示
す）で表される構造を有する硬化性樹脂である。また、
本発明は、一般式（１）において、Ar1が下記一般式
（２）で表される４価の芳香族基である前記の硬化性樹
脂である。[Chemical 4] (In the formula, Ar 1 represents a tetravalent aromatic group, Ar 2 represents a divalent aromatic group, R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and n is an average in the molecule. And shows a number of 2 to 50)). Also,
The present invention is the above-mentioned curable resin, wherein Ar 1 in the general formula (1) is a tetravalent aromatic group represented by the following general formula (2).
【化５】
（式中、R1はそれぞれ独立に炭素数１〜６の有機基を示
し、mは０〜３の整数を示し、Xは存在しないか、-O-, -
SO2-, -S-, -CH2-, -C(CH3)2-、-C(CF3)2-又は下記一般
式（９）で表される４価の芳香族基を示す）[Chemical 5] (In the formula, each R 1 independently represents an organic group having 1 to 6 carbon atoms, m represents an integer of 0 to 3, X is absent, or -O-,-
SO 2- , -S-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2 -or a tetravalent aromatic group represented by the following general formula (9))
【化６】
（式中、R2は存在しないか炭素数1〜10の有機基を、R3
は炭素数1〜6の有機基を示し、kは1〜20の数を示す）[Chemical 6] (In the formula, R 2 is absent or an organic group having 1 to 10 carbon atoms is replaced by R 3
Represents an organic group having 1 to 6 carbon atoms, and k represents a number of 1 to 20)
【０００８】更に、本発明は、ＯＨ基に対しそのオルト
位に少なくとも１つの水素を有する下記一般式（３）で
表されるフェノール化合物、下記一般式（４）で表され
る芳香族ジアミン化合物と下記一般式（５）で表される
アルデヒド化合物を、フェノール化合物１モルに対し、
芳香族ジアミン化合物０．８〜１．２モルを使用し、フ
ェノール化合物と芳香族ジアミン化合物の合計２モルに
対し、アルデヒド化合物６〜１０モルを使用し、７０〜
１２０℃で反応させることを特徴とするジヒドロベンゾ
キサジン環を有する硬化性樹脂の製造方法である。
ＨＯ-Ar1-ＯＨ （３）
Ｈ2Ｎ-Ar2-ＮＨ2 （４）
Ｒ-ＣＨＯ （５）
（式中、Ar1は２価の芳香族基を示し、Ar2は２価の芳香
族基を示し、Rは水素又は炭素数１〜６の炭化水素基を
示す）また、本発明は、前記硬化性樹脂又は前記製造法
得られた硬化性樹脂を熱硬化させてなる耐熱性硬化樹脂
である。Furthermore, the present invention provides a phenol compound represented by the following general formula (3) having at least one hydrogen in the ortho position with respect to an OH group, and an aromatic diamine compound represented by the following general formula (4). And an aldehyde compound represented by the following general formula (5) with respect to 1 mol of the phenol compound:
The aromatic diamine compound is used in an amount of 0.8 to 1.2 mol, the aldehyde compound is used in an amount of 6 to 10 mol, and the total amount of the phenol compound and the aromatic diamine compound is 2 to 70 mol.
A method for producing a curable resin having a dihydrobenzoxazine ring, which comprises reacting at 120 ° C. HO-Ar 1 -OH (3) H 2 N-Ar 2 -NH 2 (4) R-CHO (5) (In the formula, Ar 1 represents a divalent aromatic group and Ar 2 represents a divalent aromatic. A group group, and R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms) Further, the present invention provides a heat-resistant cure obtained by thermosetting the curable resin or the curable resin obtained by the production method. It is a resin.
【０００９】本発明の硬化性樹脂は、上記一般式（１）
で表されるジヒドロベンゾキサジン環構造を含む繰り返
し単位を有する新規な樹脂であり、硬化前においても、
形状保持性を有し、フィルムやシートあるいは成型体、
繊維等として用いることができる。更に、本発明の樹脂
は、加熱により開環架橋重合反応を起こし、揮発分を発
生させることなくフェノール性水酸基を生成しながら優
れた特性を有する架橋構造を形成する。この硬化物は低
吸湿性、高いガラス転移温度、高強度・高弾性率更には
低硬化収縮率を示し、難燃性にも優れている。The curable resin of the present invention has the general formula (1) above.
Is a novel resin having a repeating unit containing a dihydrobenzoxazine ring structure represented by, even before curing,
It has shape retention and can be used as a film, sheet or molded product,
It can be used as a fiber or the like. Further, the resin of the present invention undergoes a ring-opening cross-linking polymerization reaction by heating to form a cross-linking structure having excellent properties while generating a phenolic hydroxyl group without generating a volatile component. This cured product exhibits low hygroscopicity, high glass transition temperature, high strength / high elastic modulus and low curing shrinkage, and is also excellent in flame retardancy.
【００１０】上記一般式（１）において、Ar1は、単環
又は２環以上の４価の芳香族基を示すが、-Ｏ-と結合す
る炭素に対していずれか一方のオルト位に置換可能な水
素を有するものであれば制限はなく、芳香族環にハロゲ
ン、アルキル基等の置換基を有することもできる。置換
基としては、水素又は炭素数１〜６の有機基が好まし
い。好ましくは上記一般式（２）で示される４価の芳香
族基である。上記一般式（２）において、R1はそれぞれ
独立に炭素数１〜６の有機基を示し、炭素数１〜６の有
機基としては、アルキル基、フェニル基、アルケニル基
又はこれらにハロゲン等が置換した基が挙げられるが、
炭素数１〜３の低級アルキル基が好ましい。これらの置
換基は一つ又は二つ以上のベンゼン環中に存在する場
合、同一であっても、異なっていてもよい。ｍは独立に
０〜３の整数を示すが、０又は１が好ましい。一般式
（２）において、Xは存在しないか、-O-, -SO2-, -S-,
-CH2-, -C(CH3) 2-又は-C(CF3)2-を示すが、存在しない
か、-O-,-S-, -CH2-又は-C(CH3)2-が好ましい。また、X
が一般式（９）で表わされる基であることも好ましい。
また、Ar1はフェニレン基を含む基で、全体として３〜
５環となった４価の芳香族基であることも望ましい。In the above general formula (1), Ar1Is a monocycle
Or a tetravalent aromatic group having 2 or more rings, which is bonded to -O-
Water that can be substituted at either ortho position with respect to the carbon
There is no limitation as long as it has an element
It may also have a substituent such as an alkyl group or an alkyl group. Replacement
As the group, hydrogen or an organic group having 1 to 6 carbon atoms is preferable.
Yes. Preferably, a tetravalent fragrance represented by the general formula (2)
It is a group group. In the above general formula (2), R1Are each
Independently represent an organic group having 1 to 6 carbon atoms and have an organic group having 1 to 6 carbon atoms.
As the functional group, an alkyl group, a phenyl group, an alkenyl group
Or, a group in which a halogen or the like is substituted is mentioned,
A lower alkyl group having 1 to 3 carbon atoms is preferable. These placements
When the substituent is present in one or more benzene rings,
In this case, they may be the same or different. m is independent
An integer of 0 to 3 is shown, and 0 or 1 is preferable. General formula
In (2), X does not exist, -O-, -SO2-, -S-,
-CH2-, -C (CH3) 2-Or- C (CF3)2-Indicates, but does not exist
Or -O-, -S-, -CH2-Or-C (CH3)2-Is preferred. Also, X
Is also preferably a group represented by the general formula (9).
Also, Ar1Is a group containing a phenylene group, and is 3 to
A tetravalent aromatic group having 5 rings is also desirable.
【００１１】上記一般式（１）において、Ar2は単環又
は２環以上の２価の芳香族基を示すが、この芳香族基に
は格別制限はなく、芳香族環にハロゲン、アルキル基等
の置換基を有することもできる。好ましくは２環以上の
２価の芳香族基であり、置換基としては、上記Ar1で説
明したR1に相当するものが挙げられ、炭素数１〜６の炭
化水素基が好ましく、より好ましくはメチル基又はエチ
ル基であり、その数は０〜４が好ましい。また、下記一
般式（６）に示されるような２価の芳香族ジアミンの残
基である場合であって、芳香族環の間に２価の結合基Ｙ
を有する場合は、Ｙとしては上記Ｘと同様な基が好まし
く挙げられる。また、Ar2はフェニレン基を含む基で、
全体として３〜５環となった２価の芳香族基であること
も望ましい。In the above general formula (1), Ar 2 represents a monocyclic or bicyclic or more divalent aromatic group. The aromatic group is not particularly limited, and the aromatic ring has a halogen or alkyl group. It is also possible to have a substituent such as It is preferably a divalent aromatic group having 2 or more rings, and examples of the substituent include those corresponding to R 1 described in Ar 1 above, preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably Is a methyl group or an ethyl group, and the number thereof is preferably 0-4. Further, in the case of a residue of a divalent aromatic diamine as represented by the following general formula (6), a divalent bonding group Y is present between aromatic rings.
In the case of having Y, a group similar to X above is preferably mentioned as Y. Ar 2 is a group containing a phenylene group,
A divalent aromatic group having 3 to 5 rings as a whole is also desirable.
【化７】 [Chemical 7]
【００１２】上記一般式（１）の内、好ましい構造を示
せば式（７）で示される構造が挙げられる。Among the above-mentioned general formula (1), the structure represented by the formula (7) can be given as a preferable structure.
【化８】
（R1は水素又は炭素数１〜６の炭化水素基を示し、R1〜
R5は、独立に水素又は炭素数１〜６の有機基を示し、X
及びYは存在しないか、２価の基を示し、ｎは２〜５０
の数を示す）[Chemical 8] (R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R 1
R 5 independently represents hydrogen or an organic group having 1 to 6 carbon atoms, X 5
And Y are absent or represent a divalent group, and n is 2 to 50
The number of)
【００１３】また、上記一般式（１）において、ｎは平
均の繰返し数であり、２〜５０の数を示す。本発明の硬
化性樹脂は、上記一般式（１）で示される構造のみから
なるものであってもよいが、構造単位の３０モル％以
上、好ましくは５０モル％以上、更に好ましくは７０モ
ル％以上有することが好ましい。その他の構造単位とし
ては、後記する反応で副生するフェノール樹脂単位等が
含まれ得る。なお、本発明の硬化性樹脂は、上記一般式
（１）で構造単位のみからなる場合、ｎは２〜５０の数
であり、他の構造単位を分子中に平均ｐ個有する場合、
ｎ+ｐは２〜５０の数であることがよい。上記一般式
（１）において、Rは水素又は炭素数１〜６の炭化水素
基を示すが、水素が好ましい。In the above general formula (1), n is the average number of repetitions and is a number of 2 to 50. The curable resin of the present invention may consist of only the structure represented by the above general formula (1), but is 30 mol% or more, preferably 50 mol% or more, and more preferably 70 mol% of the structural unit. It is preferable to have the above. The other structural unit may include a phenol resin unit produced as a by-product in the reaction described below. In addition, when the curable resin of the present invention is composed of only structural units in the general formula (1), n is a number of 2 to 50, and when other structural units have an average of p in the molecule,
n + p is preferably a number of 2 to 50. In the general formula (1), R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen.
【００１４】[0014]
【発明の実施の形態】上記の耐熱性樹脂の製造方法には
制限はないが、上記本発明の製造方法を採用することが
有利である。本発明の耐熱性樹脂の製造方法は、オルト
位に少なくとも１つの水素を有する上記一般式（３）で
表されるフェノール化合物、上記一般式（４）で表され
るジアミン化合物と上記一般式（５）アルデヒド化合物
を、フェノール化合物１モルに対しジアミン化合物０．
８〜１．２モル、好ましくは０．９〜１．１モル使用
し、フェノール化合物とジアミン化合物の合計２モルに
対しアルデヒド化合物を６〜１０モル使用し、７０〜１
２０℃で反応させる方法である。上記一般式（５）にお
いて、Rは上記一般式（１）で説明したＲと対応する。The method for producing the heat-resistant resin is not limited, but it is advantageous to employ the method for producing the present invention. The method for producing a heat-resistant resin of the present invention includes a phenol compound represented by the above general formula (3) having at least one hydrogen at the ortho position, a diamine compound represented by the above general formula (4) and the above general formula ( 5) The aldehyde compound was added to the diamine compound 0.
8 to 1.2 moles, preferably 0.9 to 1.1 moles, 6 to 10 moles of aldehyde compound to 70 moles to total 2 moles of phenol compound and diamine compound,
This is a method of reacting at 20 ° C. In the general formula (5), R corresponds to R described in the general formula (1).
【００１５】上記ジアミン化合物とフェノール化合物
は、nを十分大きくする場合はほぼ１：１のモル比とす
ることがよいが、末端を変性したりする場合は、いずれ
かを過剰に使用することができる。アルデヒド化合物の
使用量は、上記ジアミン化合物及びフェノール化合物の
合計２モルに対し６〜１０モルであるが、理論量である
８モル以下、好ましくは６〜８モルとすることがよい。
アルデヒド化合物の使用量が多いと、ノボラック樹脂構
造等が副生する。The above diamine compound and phenol compound are preferably used in a molar ratio of about 1: 1 when n is made sufficiently large, but when modifying the terminals, one of them may be used in excess. it can. The amount of the aldehyde compound used is 6 to 10 moles based on the total 2 moles of the diamine compound and the phenol compound, and is 8 moles or less, which is a theoretical amount, and preferably 6 to 8 moles.
When the amount of the aldehyde compound used is large, a novolac resin structure or the like is by-produced.
【００１６】一例として、ジアミン化合物をＮＨ2−Ar2
−ＮＨ2で表し、アルデヒド化合物をＨＣＨＯで表し、
フェノール化合物をビスフェノールＡで表すと、ヒドロ
ベンゾキサジン化合物と同様の方法で、下記反応式に示
されるように、ベンゾキサジン環構造単位からなる繰り
返しを有する重合物が得られる。As an example, the diamine compound is NH 2 --Ar 2
Represented by —NH 2 , an aldehyde compound represented by HCHO,
When the phenol compound is represented by bisphenol A, a polymer having a repeating unit of a benzoxazine ring structural unit is obtained in the same manner as in the hydrobenzoxazine compound, as shown in the following reaction formula.
【化９】
（式中、Ar3は上記一般式（２）のXに対応し、Ar2及び
ｎは一般式（１）のAr2及びｎに対応する）[Chemical 9] (Wherein, Ar 3 corresponds to X in the general formula (2), Ar 2 and n corresponds to Ar 2 and n in the general formula (1))
【００１７】上記一般式（３）で表されるフェノール化
合物としては、下記に構造式で示すようなフェノール化
合物が挙げられる。また、下記に構造式で示すフェノー
ル化合物の他に、カテコール、レゾルシノール、ヒドロ
キノン等の単環のフェノール化合物、ビスフェノール
S、ビスフェノールF、ビスフェノールA、ヘキサフルオ
ロビスフェノールA等のビスフェノール類が挙げられ
る。また、ＯＨ基を２個有するフェノール樹脂も使用可
能であり、フェノールノボラック樹脂、レゾール樹脂、
フェノール変性キシレン樹脂、アルキルフェノール樹
脂、メラミンフェノール樹脂、ポリブタジエン変性フェ
ノール樹脂等が挙げられる。これらは、１種類あるいは
２種類以上を組み合わせて用いることもできる。具体的
には次に示すようなフェノール化合物が好ましく挙げら
れる。Examples of the phenol compound represented by the above general formula (3) include phenol compounds represented by the structural formulas below. In addition to the phenol compounds represented by the structural formulas below, catechol, resorcinol, monocyclic phenol compounds such as hydroquinone, and bisphenol.
Examples thereof include bisphenols such as S, bisphenol F, bisphenol A, and hexafluorobisphenol A. Further, a phenol resin having two OH groups can also be used, such as phenol novolac resin, resol resin,
Examples thereof include phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, polybutadiene-modified phenol resin and the like. These may be used alone or in combination of two or more. Specifically, the following phenol compounds are preferable.
【００１８】[0018]
【化１０】 [Chemical 10]
【００１９】[0019]
【化１１】 [Chemical 11]
【００２０】[0020]
【化１２】 [Chemical 12]
【００２１】また、上記一般式（４）で表されるジアミ
ン化合物としては、耐熱性向上の観点から、芳香族ジア
ミン化合物が使用される。更に、熱分解温度の低下を抑
制し、可とう性を付与するために、一般式（４）に示す
ような、置換基を有しない２環のジアミン化合物をジア
ミン化合物の一部又は全部として使用することが有利で
ある。その他の、ジアミン化合物の好ましい具体例を構
造式で次に示す。これらは、１種類あるいは２種類以上
を組み合わせて用いることもできる。一般式（６）にお
いて、Ｙは上記Ｘと同じものが好ましく挙げられる。As the diamine compound represented by the general formula (4), an aromatic diamine compound is used from the viewpoint of improving heat resistance. Further, in order to suppress the decrease in thermal decomposition temperature and impart flexibility, a bicyclic diamine compound having no substituent as shown in the general formula (4) is used as a part or all of the diamine compound. It is advantageous to do Other preferable specific examples of the diamine compound are shown below by structural formulas. These may be used alone or in combination of two or more. In the general formula (6), Y is preferably the same as the above X.
【００２２】[0022]
【化１３】 [Chemical 13]
【００２３】[0023]
【化１４】 [Chemical 14]
【００２４】[0024]
【化１５】 [Chemical 15]
【００２５】[0025]
【化１６】 [Chemical 16]
【００２６】[0026]
【化１７】 [Chemical 17]
【００２７】[0027]
【化１８】 [Chemical 18]
【００２８】これらジアミン化合物は、上記具体例に限
定されない。また、これらジアミン化合物は１種又は２
種以上を組み合わせて用いることができる。より良好な
可とう性を付与するためには、（ｇ）〜（ｊ）のような
３つのフェニレン環を有するジアミン化合物、更には、
（ｋ）〜（ｔ）のような４つのフェニレン環を有するジ
アミン化合物を用いることが好ましい。また、化学的及
び物理的耐熱性の観点からは、（a）〜（e）のような２
つのフェニレン環を有するジアミン化合物を用いること
が好ましく、更に耐熱性を向上させる目的で、パラフェ
ニレンジアミン等を併用することができる。さらに、分
子量、軟化点温度をコントロールするため、アミンとジ
アミンを組み合わせることもできる。この目的に、用い
られるアミンとしては、メチルアミン、エチルアミン等
の脂肪族アミン、フェニルアミン（アニリン）、置換フ
ェニルアミン等の芳香族アミン、あるいはアリルアミ
ン、プロパルギルアミン等の不飽和結合を有するアミン
等を用いることができるが、第一級アミノ基を有する化
合物であればこれらに限定することなく用いることがで
きる。These diamine compounds are not limited to the above specific examples. Also, these diamine compounds may be used alone or in combination.
A combination of two or more species can be used. In order to impart better flexibility, a diamine compound having three phenylene rings such as (g) to (j), and further,
It is preferable to use a diamine compound having four phenylene rings such as (k) to (t). In addition, from the viewpoint of chemical and physical heat resistance, 2 like (a) to (e)
It is preferable to use a diamine compound having two phenylene rings, and paraphenylenediamine and the like can be used in combination for the purpose of further improving heat resistance. Further, in order to control the molecular weight and the softening point temperature, amine and diamine can be combined. As the amine used for this purpose, aliphatic amines such as methylamine and ethylamine, aromatic amines such as phenylamine (aniline) and substituted phenylamine, and amines having unsaturated bonds such as allylamine and propargylamine, etc. Although they can be used, any compound having a primary amino group can be used without limitation.
【００２９】また、アルデヒド化合物としては、RCHOで
表されるアルデヒド化合物が使用でき、Rは水素又は炭
素数１〜６の炭化水素基である。具体的には、ホルムア
デヒド、アセトアルデヒド、ベンズアルデヒド等が挙げ
られるが、ホルムアデヒドが好ましい。ホルムアルデヒ
ドは、ホルマリン溶液として、またパラホルムアルデヒ
ドとして、いずれの形態でも用いることができる。本発
明の製造方法では、上記原料を使用するが本発明の効果
を阻害しない範囲内で少量の他の成分、例えばモノアミ
ン化合物、トリアミン化合物、モノフェノール化合物、
トリフェノール化合物等を加えることも可能である。As the aldehyde compound, an aldehyde compound represented by RCHO can be used, and R is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof include formaldehyde, acetaldehyde, benzaldehyde and the like, and formaldehyde is preferable. Formaldehyde can be used in any form, as a formalin solution or as paraformaldehyde. In the production method of the present invention, a small amount of other components, such as a monoamine compound, a triamine compound, a monophenol compound, which use the above raw materials but do not impair the effects of the present invention,
It is also possible to add a triphenol compound or the like.
【００３０】ジヒドロベンゾキサジン環を有する硬化性
樹脂の具体的な製造方法の一例を示すと、上記ジアミン
化合物をアルデヒド化合物へ徐々に加えて反応させたの
ち、上記フェノール化合物を加え、７０〜１２０℃に保
ち、２０分〜２４時間反応させる。このとき、必要に応
じて有機溶剤を用いることもできる。反応後、生成物を
メタノール等の生成樹脂に対するの溶解力が低い貧溶媒
中に投入し、再沈殿させる方法や溶剤抽出等の合成化学
的手法で分離・精製し縮合水等の揮発成分を乾燥除去す
ることにより目的とするジヒドロベンゾキサジン環を有
する樹脂が得られる。An example of a specific method for producing a curable resin having a dihydrobenzoxazine ring will be described. After gradually adding the diamine compound to an aldehyde compound to cause a reaction, the phenol compound is added to 70 to 120. Keep at 0 ° C. and react for 20 minutes to 24 hours. At this time, an organic solvent can be used if necessary. After the reaction, the product is placed in a poor solvent that has a low solubility in the resin such as methanol and reprecipitated or separated and purified by synthetic chemical methods such as solvent extraction, and the volatile components such as condensed water are dried. By removing the resin, a resin having a desired dihydrobenzoxazine ring can be obtained.
【００３１】本発明の硬化性樹脂の製造方法において、
反応温度が７０℃未満ではジヒドロベンゾキサジン環の
生成反応が遅くなり、１２０℃を超えると、生成したジ
ヒドロベンゾキサジン環の開環架橋反応が、ジヒドロベ
ンゾキサジン環生成反応と並行して起こりやすく、不溶
性ゲルを生成し易くなる。ジヒドロベンゾキサジン環生
成反応の向上とゲル発生の低減のため、反応温度８０〜
１１０℃の温度範囲で反応させることがより好ましい。
また、反応時間に関しては、２０分以下では、ジヒドロ
ベンゾキサジン環の生成が充分ではなく、２４時間以上
では、並行して徐々に生成したジヒドロベンゾキサジン
環の開環架橋反応が起こる。このため、ジヒドロベンゾ
キサジン環生成反応の向上とゲル発生の低減のため、反
応時間を１〜１０時間で終了させることが、より好まし
い。In the method for producing a curable resin of the present invention,
When the reaction temperature is lower than 70 ° C, the reaction for forming the dihydrobenzoxazine ring becomes slow, and when it exceeds 120 ° C, the ring-opening crosslinking reaction of the formed dihydrobenzoxazine ring occurs in parallel with the reaction for forming the dihydrobenzoxazine ring. It is likely to occur and easily form an insoluble gel. In order to improve the dihydrobenzoxazine ring formation reaction and reduce gel generation, the reaction temperature should be 80-
It is more preferable to react in the temperature range of 110 ° C.
Regarding the reaction time, if the reaction time is 20 minutes or less, the formation of the dihydrobenzoxazine ring is not sufficient, and if it is 24 hours or more, the ring-opening cross-linking reaction of the dihydrobenzoxazine ring that is gradually generated in parallel occurs. Therefore, in order to improve the dihydrobenzoxazine ring formation reaction and reduce gel generation, it is more preferable to complete the reaction time within 1 to 10 hours.
【００３２】このようにして得られた反応混合液中にメ
タノール等の貧溶媒を投入することにより、樹脂成分を
析出させて固体として分離することができる。分離され
た本発明の硬化性樹脂はテトラヒドロフラン、ジオキサ
ン、ジグライム等のエーテル系有機溶剤、あるいは、ジ
メチルホルムアミド、ジメチルアセトアミド、N-メチル
-２-ピロリジノン、ジメチルイミダゾロン等のアミド系
有機溶剤に再度溶解させた後、ガラス基板等に流延し、
溶剤を１５０℃以下の温度で、加熱あるいは真空除去す
ることにより、フィルムあるいはシート状に成型するこ
とができる。By adding a poor solvent such as methanol to the reaction mixture thus obtained, the resin component can be precipitated and separated as a solid. The separated curable resin of the present invention is tetrahydrofuran, dioxane, ether organic solvent such as diglyme, or dimethylformamide, dimethylacetamide, N-methyl.
-After dissolving again in amide-based organic solvent such as 2-pyrrolidinone and dimethylimidazolone, cast on glass substrate etc.,
By heating or vacuum removing the solvent at a temperature of 150 ° C. or less, it is possible to form a film or sheet.
【００３３】本発明の硬化性樹脂は、ジヒドロベンゾキ
サジン環を有するため、加熱することにより、開環反応
が起こり、架橋反応性を有している。本発明の硬化性樹
脂は、ジヒドロベンゾキサジン環を主成分として有する
必要があるが、架橋するに必要なジヒドロベンゾキサジ
ン環を有すればよく、分子中にその他の構成単位が少
量、例えば５０モル％以下、好ましくは２０モル％以
下、より好ましくは１０モル％以下含まれてもよい。Since the curable resin of the present invention has a dihydrobenzoxazine ring, it undergoes a ring-opening reaction by heating and has a cross-linking reactivity. The curable resin of the present invention needs to have a dihydrobenzoxazine ring as a main component, but it may have a dihydrobenzoxazine ring necessary for cross-linking, and a small amount of other structural unit in the molecule, for example, The content may be 50 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.
【００３４】本発明の硬化性樹脂は、１５０〜２５０℃
の温度で加熱することにより、開環架橋反応が起こり、
強固な硬化樹脂を得ることができる。一般に、フェノー
ル性水酸基を有する化合物から合成されるジヒドロベン
ゾキサジン類は加熱あるいはアミン系触媒により下記反
応式で示されるように、開環架橋反応が起こり、フェノ
ール性水酸基と三級アミノ基を有する樹脂硬化物を生成
することが知られている。The curable resin of the present invention has a temperature of 150 to 250 ° C.
By heating at the temperature of, ring-opening crosslinking reaction occurs,
A strong cured resin can be obtained. Generally, dihydrobenzoxazines synthesized from compounds having a phenolic hydroxyl group have a phenolic hydroxyl group and a tertiary amino group by a ring-opening crosslinking reaction as shown in the following reaction formula by heating or an amine catalyst. It is known to produce a resin cured product.
【００３５】[0035]
【化１９】 [Chemical 19]
【００３６】この開環架橋反応の際、フェノール性水酸
基と三級アミノ基を有する構造となるため、種々のエポ
キシ樹脂と組み合わせて用いることもできる。用いられ
るエポキシ樹脂としては、ビスフェノールA型エポキシ
樹脂、ビスフェノールF型エポキシ樹脂、フェノールノ
ボラック型エポキシ樹脂、クレゾールノボラック型エポ
キシ樹脂、あるいは、水素化ビスフェノールA型エポキ
シ樹脂、各種の脂環式エポキシ樹脂、更には、ナフタレ
ン構造を有する各種エポキシ樹脂、臭素化エポキシ樹脂
等が挙げられるが、これらに限定することなく用いるこ
とができる。更に、これらは、１種あるいは２種以上を
組み合わせて用いることができる。During the ring-opening cross-linking reaction, a structure having a phenolic hydroxyl group and a tertiary amino group is formed, and therefore it can be used in combination with various epoxy resins. As the epoxy resin used, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or hydrogenated bisphenol A type epoxy resin, various alicyclic epoxy resins, further Examples of the epoxy resin include various epoxy resins having a naphthalene structure, brominated epoxy resins, and the like, but they can be used without limitation. Furthermore, these can be used alone or in combination of two or more.
【００３７】更に、本発明の硬化性樹脂には、ポリアミ
ド、ポリイミド、ポリエステル、エポキシ樹脂等の耐熱
性樹脂と併用して用いることもできる。本発明の硬化性
樹脂は、以上に記した成分以外に必要に応じ、各種フェ
ノール樹脂、メラミン樹脂等を含有することができる。
更に、本発明の硬化性樹脂は、他のジヒドロベンゾキサ
ジン環を有する化合物を組み合わせて用いることもでき
る。Further, the curable resin of the present invention may be used in combination with a heat resistant resin such as polyamide, polyimide, polyester and epoxy resin. The curable resin of the present invention may contain various phenol resins, melamine resins, and the like, if necessary, in addition to the components described above.
Further, the curable resin of the present invention may be used in combination with another compound having a dihydrobenzoxazine ring.
【００３８】また、本発明の硬化性樹脂には、充填材、
補強材、離型剤、カップリング剤、可塑剤、難燃剤、硬
化助剤、着色剤、カップリング剤、あるいはカーボンブ
ラック等を含有することもできる。更に、必要に応じ
て、ジヒドロナフトキサジン環を開環する効果のあるフ
ェノール性水酸基を有する化合物、例えば、ビスフェノ
ールA、ノボラック樹脂、レゾ−ル樹脂、アミノ基を有
する化合物を用いることもできる。また、エポキシ樹脂
とフェノール性水酸基の反応に効果的な触媒として、例
えば、イミダゾール系化合物、ジシアンジアミド系化合
物、リン系化合物を使用することができる。また、樹脂
の難燃性を更に向上させる目的で、トリフェニルホスフ
ィン等の各種有機リン系化合物を使用することもでき
る。The curable resin of the present invention includes a filler,
It may also contain a reinforcing material, a release agent, a coupling agent, a plasticizer, a flame retardant, a curing aid, a coloring agent, a coupling agent, carbon black, or the like. Further, if necessary, a compound having a phenolic hydroxyl group having an effect of opening a dihydronaphthoxazine ring, such as bisphenol A, a novolak resin, a resole resin, or a compound having an amino group can be used. Further, as an effective catalyst for the reaction between the epoxy resin and the phenolic hydroxyl group, for example, an imidazole compound, a dicyandiamide compound, or a phosphorus compound can be used. Further, various organic phosphorus compounds such as triphenylphosphine can be used for the purpose of further improving the flame retardancy of the resin.
【００３９】[0039]
【実施例】以下、合成例及び実施例により、本発明を具
体的に説明するが、本発明はこれらの実施例に限定され
るものではない。
実施例１
4,4'−ジアミノジフェニルエーテル0.2モル（40.0ｇ）
をジオキサン200ｍｌ中に溶解し、ホルムアルデヒド液
（36〜38％水溶液）67ｇを滴下し、室温下で5時間反応
させた。その後、ビスフェノールA 0.2モル（32.03ｇ）
を加え、撹拌下、100〜120℃で、5時間反応させた。反
応終了後、反応溶液をメタノール中に投入し、析出した
固体をろ取し、ジヒドロベンゾキサジン構造を有する樹
脂（A）72ｇを得た。この樹脂の重量平均分子量は、Ｇ
ＰＣ測定の結果8,500（ポリスチレン換算）であった。
また、この樹脂のDSC測定の結果156.7℃に4.7mJ/mgの発
熱が、267.4℃に120.7mJ/mg吸熱が認められた。更に、
この樹脂の赤外吸収スペクトル（IRスペクトル）を図１
に示した。EXAMPLES The present invention will be described in detail below with reference to synthetic examples and examples, but the present invention is not limited to these examples. Example 1 0.2 mol (40.0 g) of 4,4'-diaminodiphenyl ether
Was dissolved in 200 ml of dioxane, 67 g of formaldehyde solution (36-38% aqueous solution) was added dropwise, and the mixture was reacted at room temperature for 5 hours. After that, 0.2 mol of bisphenol A (32.03 g)
Was added, and the mixture was reacted at 100 to 120 ° C for 5 hours with stirring. After completion of the reaction, the reaction solution was put into methanol, and the precipitated solid was collected by filtration to obtain 72 g of resin (A) having a dihydrobenzoxazine structure. The weight average molecular weight of this resin is G
The result of PC measurement was 8,500 (converted to polystyrene).
As a result of DSC measurement of this resin, an exotherm of 4.7 mJ / mg at 156.7 ° C and an endotherm of 120.7 mJ / mg at 267.4 ° C were observed. Furthermore,
Figure 1 shows the infrared absorption spectrum (IR spectrum) of this resin.
It was shown to.
【００４０】上記の樹脂（A)10ｇをジオキサンに溶解さ
せた後、ガラス基板上にバーコーターでキャストし、イ
ナートオーブン中で100℃-3時間で乾燥させた。イナー
トオーブン中から取り出し、ガラス基板上から引き剥が
すことにより、耐熱性樹脂のシートを得られた。また、
この樹脂（A）10ｇを180℃に維持したホットプレート上
で１時間保持して硬化させた後、物性の測定を行った。
その結果を表２に示した。After dissolving 10 g of the above resin (A) in dioxane, it was cast on a glass substrate with a bar coater and dried in an inert oven at 100 ° C. for 3 hours. The heat-resistant resin sheet was obtained by taking it out from the inert oven and peeling it off from the glass substrate. Also,
After 10 g of this resin (A) was held on a hot plate maintained at 180 ° C. for 1 hour to cure, the physical properties were measured.
The results are shown in Table 2.
【００４１】なお、ガラス転移温度は、動的粘弾性測定
装置（DMA）、熱膨張係数は、熱機械分析装置（TMA）
を、熱分解開始温度（5%重量減少温度）は、熱重量分析
装置（TGA）を用い,曲げ強度及び曲げ弾性率はJIS K 69
11に準じて測定を行った。また、吸水率は、3mm厚の硬
化物を作成した後、硬化物をPCT（121℃、2atm）処理時
間20時間の条件で処理した後、PCT処理前後の重量変化
を測定し、吸水率を求めた。更に、難燃性は、UL規格の
方法に従って、1.6mm厚の硬化物の難燃性を評価した。The glass transition temperature is a dynamic viscoelasticity measuring device (DMA), and the thermal expansion coefficient is a thermomechanical analyzer (TMA).
The thermal decomposition starting temperature (5% weight loss temperature) was measured using a thermogravimetric analyzer (TGA).
The measurement was performed according to 11. In addition, the water absorption rate was measured by measuring the weight change before and after the PCT treatment after preparing a 3 mm thick cured product and treating the cured product under PCT (121 ° C, 2 atm) treatment time of 20 hours. I asked. Furthermore, the flame retardancy was evaluated according to the method of UL standard.
【００４２】実施例２〜６
樹脂の原料組成以外は、実施例１の記載と同様の方法に
より硬化性樹脂を合成し、これを硬化させて硬化樹脂の
特性評価を行った。なお、実施例３の樹脂の赤外吸収ス
ペクトル（IRスペクトル）を図２に示した。Examples 2 to 6 A curable resin was synthesized by the same method as described in Example 1 except for the raw material composition of the resin, which was cured to evaluate the characteristics of the cured resin. The infrared absorption spectrum (IR spectrum) of the resin of Example 3 is shown in FIG.
【００４３】比較例１〜３
合成原料において、ジアミン化合物を用いないこと以外
は、実施例１の記載と同様の方法により硬化性樹脂を合
成し、これを硬化させて硬化樹脂の特性評価を行った。
樹脂の原料組成を表１に、得られた硬化樹脂の物性を表
２にまとめて示す。表中、各種化合物の符合は、本文中
の化学式に付した記号に対応する。各種化合物の数字は
フェノール化合物の使用量を１００モル％とに換算した
ときの使用量（モル％）である。また、フィルム形成能
は硬化前樹脂の形成能であり、○は有りを、×はなしを
示す。Comparative Examples 1 to 3 A curable resin was synthesized by the same method as described in Example 1 except that the diamine compound was not used in the synthetic raw materials, and this was cured to evaluate the characteristics of the cured resin. It was
The raw material composition of the resin is shown in Table 1, and the physical properties of the obtained cured resin are shown in Table 2. In the table, the signs of various compounds correspond to the symbols attached to the chemical formulas in the text. The numbers of various compounds are the amounts (mol%) used when the amount of the phenol compound used is converted to 100 mol%. The film-forming ability is the ability to form the resin before curing, where ◯ means yes and x means no.
【００４４】[0044]
【表1】 【table 1】
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【発明の効果】本発明の硬化性樹脂は、ジヒドロベンゾ
キサジン環構造を含有し、熱硬化性を有し、硬化収縮も
小さいという特性を有する。更に、形状保持のための十
分な分子量を有しているためフィルムやシートあるいは
繊維等として用いることができる。また、硬化後におい
て耐熱性に優れ、難燃性を向上させることができ、電気
特性や機械的特性も良好なため、プリント配線板用積層
板、プリント配線板、半導体封止材、半導体搭載用モジ
ュール、その他各種電子部品周辺部材として、その他各
種電子部品周辺部材として有用である。また、自動車、
航空機部材、建築部材等、更には、炭素繊維や炭素電
極、各種複合材料等のバインダーやマトリックス樹脂と
して用いることができる。EFFECTS OF THE INVENTION The curable resin of the present invention contains a dihydrobenzoxazine ring structure, has thermosetting properties, and has the property of having small curing shrinkage. Further, since it has a sufficient molecular weight for maintaining its shape, it can be used as a film, sheet, fiber or the like. In addition, since it has excellent heat resistance after curing, it can improve flame retardancy, and has good electrical and mechanical properties. Therefore, it can be used as a laminate for printed wiring boards, printed wiring boards, semiconductor encapsulation materials, and semiconductor mounting materials. It is useful as a peripheral member for various electronic components such as modules and other electronic components. Also cars,
It can be used as an aircraft member, a building member, and the like, and also as a binder and a matrix resin for carbon fibers, carbon electrodes, various composite materials, and the like.
【図１】 硬化性樹脂の赤外吸収スペクトルFig. 1 Infrared absorption spectrum of curable resin
【図２】 他の硬化性樹脂の赤外吸収スペクトルFIG. 2 Infrared absorption spectra of other curable resins
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J043 PA02 QB44 QB64 RA51 SA06 SB01 TA03 TB01 UA122 UA131 UA132 UA141 UA151 UB011 UB012 UB021 UB022 UB061 UB121 UB131 UB141 UB281 UB301 UB302 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4J043 PA02 QB44 QB64 RA51 SA06 SB01 TA03 TB01 UA122 UA131 UA132 UA141 UA151 UB011 UB012 UB021 UB022 UB061 UB121 UB131 UB141 UB281 UB301 UB302
Claims (4)
族基を示し、Rは水素又は炭素数１〜６の炭化水素基を
示し、ｎは平均の繰返し数であり、２〜５０の数を示
す）で表される構造を有する硬化性樹脂。1. The following general formula (1): (In the formula, Ar 1 represents a tetravalent aromatic group, Ar 2 represents a divalent aromatic group, R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and n represents an average number of repetitions. And shows the number of 2 to 50).
式（２）で表される4価の芳香族基である請求項１記載
の硬化性樹脂。 【化２】 （式中、R1はそれぞれ独立に炭素数１〜６の有機基を示
し、mは独立に０〜３の整数を示し、Xは存在しないか、
-O-, -SO2-, -S-, -CH2-, -C(CH3)2-、-C(CF3)2-又は下
記一般式（９）で表される4価の芳香族基を示す） 【化３】 （式中、R2は存在しないか炭素数1〜10の有機基を示
し、R3は炭素数1〜6の有機基を示し、kは1〜20の数を示
す）2. The curable resin according to claim 1, wherein Ar 1 in the general formula (1) is a tetravalent aromatic group represented by the following general formula (2). [Chemical 2] (In the formula, each R 1 independently represents an organic group having 1 to 6 carbon atoms, m independently represents an integer of 0 to 3, and X does not exist,
-O-, -SO 2 -, -S-, -CH 2 -, -C (CH 3) 2 -, - C (CF 3) 2 - or tetravalent aromatic represented by the following general formula (9) Indicates a group) (In the formula, R 2 does not exist or represents an organic group having 1 to 10 carbon atoms, R 3 represents an organic group having 1 to 6 carbon atoms, and k represents a number of 1 to 20)
る下記一般式（３）で表されるフェノール化合物、下記
一般式（４）で表される芳香族ジアミン化合物と下記一
般式（５）で表されるアルデヒド化合物を、フェノール
化合物１モルに対し、芳香族ジアミン化合物０．８〜
１．２モルを使用し、フェノール化合物と芳香族ジアミ
ン化合物の合計２モルに対し、アルデヒド化合物６〜１
０モルを使用し、７０〜１２０℃で反応させることを特
徴とするジヒドロベンゾキサジン環を有する硬化性樹脂
の製造方法。 ＨＯ-Ar1-ＯＨ （３） Ｈ2Ｎ-Ar2-ＮＨ2 （４） Ｒ-ＣＨＯ （５） （式中、Ar1は２価の芳香族基を示し、Ar2は２価の芳香
族基を示し、Rは水素又は炭素数１〜６の炭化水素基を
示す）3. A phenol compound represented by the following general formula (3) having at least one hydrogen at the ortho position, an aromatic diamine compound represented by the following general formula (4) and a general formula (5) below. The aldehyde compound to be used is aromatic diamine compound 0.8 to 1 mol per 1 mol of the phenol compound.
Using 1.2 mol, the aldehyde compound 6-1 is added to the total 2 mol of the phenol compound and the aromatic diamine compound.
A method for producing a curable resin having a dihydrobenzoxazine ring, which comprises reacting 0 mol of the compound at 70 to 120 ° C. HO-Ar 1 -OH (3) H 2 N-Ar 2 -NH 2 (4) R-CHO (5) (In the formula, Ar 1 represents a divalent aromatic group and Ar 2 represents a divalent aromatic. Represents a group group, and R represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms)
求項３で得られた熱硬化性樹脂を熱硬化させてなる耐熱
性硬化樹脂。4. A heat-resistant curable resin obtained by thermosetting the curable resin according to claim 1 or 2 or the thermosetting resin obtained in claim 3.
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| JP2002169203A JP2003064180A (en) | 2001-06-11 | 2002-06-10 | Curable resin having dihydrobenzoxazine ring structure and heat-resistant cured resin |
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| JP2001176103 | 2001-06-11 | ||
| JP2001-176103 | 2001-06-11 | ||
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