JPH03275708A - Modified phenolic resin - Google Patents
Modified phenolic resinInfo
- Publication number
- JPH03275708A JPH03275708A JP7557990A JP7557990A JPH03275708A JP H03275708 A JPH03275708 A JP H03275708A JP 7557990 A JP7557990 A JP 7557990A JP 7557990 A JP7557990 A JP 7557990A JP H03275708 A JPH03275708 A JP H03275708A
- Authority
- JP
- Japan
- Prior art keywords
- phenols
- reaction
- parts
- formaldehyde
- temperature
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000002989 phenols Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 125000005462 imide group Chemical group 0.000 claims abstract description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 formaldehyde, aromatic amine Chemical class 0.000 claims abstract description 6
- 239000005011 phenolic resin Substances 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 44
- 150000004982 aromatic amines Chemical class 0.000 abstract description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 238000010992 reflux Methods 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001743 benzylic group Chemical group 0.000 description 2
- 239000011230 binding agent 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- LVNDUJYMLJDECN-UHFFFAOYSA-N 5-methylbenzene-1,3-diamine Chemical compound CC1=CC(N)=CC(N)=C1 LVNDUJYMLJDECN-UHFFFAOYSA-N 0.000 description 1
- ABAPNKBSVNXXPG-UHFFFAOYSA-N 5-phenylbenzene-1,3-diamine Chemical group NC1=CC(N)=CC(C=2C=CC=CC=2)=C1 ABAPNKBSVNXXPG-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 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
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性、実用特性、硬化性、及び経済性に優れ
た変性フェノール樹脂に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a modified phenolic resin that is excellent in heat resistance, practical properties, curability, and economical efficiency.
を触媒の存在下で反応して得られるフェノール樹脂は、
各種の熱硬化性樹脂のうち、比較的良好な耐熱性、硬化
性、各種基材との結合力、機械的特性、作業性、及び経
済性なとを有するため、有機質及び無機質の各種基材の
バインダーまたは接着剤として産業界に広く使用されて
いる。しかしなから、近年、フェノール樹脂を熱硬化さ
せたフェノール樹脂硬化物の耐熱性を従来の水準に比べ
大幅に向上させることか求められている。The phenolic resin obtained by reacting in the presence of a catalyst is
Among various thermosetting resins, it has relatively good heat resistance, curability, bonding strength with various substrates, mechanical properties, workability, and economic efficiency, so it is suitable for various organic and inorganic substrates. Widely used in industry as a binder or adhesive. However, in recent years, there has been a need to significantly improve the heat resistance of cured phenol resin products, which are obtained by thermosetting phenol resins, compared to conventional levels.
耐熱性か高水準を有する熱硬化性樹脂として、シリコー
ン樹脂、マレイミド樹脂なとがあるが、これらは各種基
材との結合力、機械的特性、硬化性なとの特性が低く、
かつ経済性に劣るという欠点がある。Silicone resins and maleimide resins are thermosetting resins that have a high level of heat resistance, but these have low bonding strength with various base materials, mechanical properties, and curability.
It also has the disadvantage of being less economical.
本発明は従来のフェノール樹脂が有する硬化性、各種基
材との結合力、機械的特性、作業性、及び経済性を損わ
ず、かつ耐熱性が著しく向上した変性フェノール樹脂を
提供するにある。The present invention provides a modified phenolic resin that does not impair the curability, bonding strength with various base materials, mechanical properties, workability, and economic efficiency of conventional phenolic resins, and has significantly improved heat resistance. .
従来、一般にフェノール類とホルムアルデヒド〔課題を
解決するための手段〕
本発明はフェノール類、ホルムアルデヒド、芳香族アミ
ン及び芳香族カルボン酸無水物との反応によるイミド基
を分子中に含有する変性フェノール樹脂において、フェ
ノール類に対してイミド基が１０〜８０モル％てあり、
かつ数平均分子量が２１０〜７００である変性フェノー
ル樹脂である。Conventionally, phenols and formaldehyde have generally been used. [Means for solving the problem] The present invention relates to modified phenol resins containing imide groups in the molecule by reaction with phenols, formaldehyde, aromatic amines, and aromatic carboxylic acid anhydrides. , the imide group is 10 to 80 mol% relative to the phenols,
It is a modified phenol resin having a number average molecular weight of 210 to 700.
本発明における芳香族アミンとしては、アニリン、２−
メチルアニリン、２−クロルアニリン、２−エチルアニ
リン、メタフェニレンジアミン、バラフェニレンジアミ
ン、２．６−ジアミノトルエン、３．５−ジアミノトル
エン、３，５−ジアミノビフェニル、４．４′ −ジア
ミノジフェニルメタン、１．３．５〜トリアミノベンゼ
ン、メタキシリレンジアミン、パラキシリレンジアミン
、４．４′ −ジアミノジフェニルスルホンなどが挙げ
られる。Aromatic amines used in the present invention include aniline, 2-
Methylaniline, 2-chloroaniline, 2-ethylaniline, metaphenylenediamine, paraphenylenediamine, 2,6-diaminotoluene, 3,5-diaminotoluene, 3,5-diaminobiphenyl, 4,4'-diaminodiphenylmethane, Examples include 1.3.5-triaminobenzene, meta-xylylene diamine, para-xylylene diamine, and 4,4'-diaminodiphenylsulfone.
芳香族カルボン酸無水物としては、無水フタル酸、無水
トリメリット酸、無水ピロメリット酸、無水トリメリッ
ト酸クロライド、３．３ ’ 、４．４’ビフエニルテ
トラカルボン酸無水物、２，３．３’ 、４’−ビフェ
ニルテトラカルボン酸無水物、３．３’、４゜４′−ベ
ンゾフェノンテトラカルボン酸無水物、３、４．９．１
０−ペリレンテトラカルボン酸無水物、２゜３．６−ナ
フタリントリカルボン酸無水物、２．３．５−ナフタリ
ントリカルボン酸無水物、１．２．４−ナフタリントリ
カルボン酸無水物などが挙げられる。Examples of the aromatic carboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, trimellitic anhydride chloride, 3.3', 4.4' biphenyltetracarboxylic anhydride, 2,3. 3',4'-biphenyltetracarboxylic anhydride, 3.3',4゜4'-benzophenonetetracarboxylic anhydride, 3,4.9.1
Examples include 0-perylenetetracarboxylic anhydride, 2°3.6-naphthalenetricarboxylic anhydride, 2.3.5-naphthalenetricarboxylic anhydride, and 1.2.4-naphthalenetricarboxylic anhydride.
フェノール類としては、フェノール、クレゾール、キシ
レノール、パラターシャリ−ブチルフェノール、パラオ
クチルフェノール、バラノニルフェノール、バラクミル
フェノール、レゾルシン、カテコール、ハイドロキノン
なとが挙げられる。Examples of phenols include phenol, cresol, xylenol, paratertiary butylphenol, paraoctylphenol, balanonylphenol, baramylphenol, resorcinol, catechol, and hydroquinone.
ホルムアルデヒドとしては通常、ホルマリンが使用され
るが、バラホルムアルデヒドも使用できる。Formaldehyde is usually formalin, but paraformaldehyde can also be used.
本発明の変性フェノール樹脂の製法例を示す。An example of the method for producing the modified phenol resin of the present invention will be shown.
フェノール類と芳香族アミンとホルムアルデヒドを水溶
液もしくはアルコールなとの有機溶媒中で、酸性触媒ま
たはアルカリ性触媒の存在下で、もしくは無触媒下で加
熱反応して、フェノール類と芳香族アミンとホルムアル
デヒドの反応生成物を得、次いて、芳香族カルボン酸無
水物とイミド化反応を行う。Reaction of phenols, aromatic amines, and formaldehyde by heating and reacting phenols, aromatic amines, and formaldehyde in an aqueous solution or an organic solvent such as alcohol in the presence of an acidic or alkaline catalyst or in the absence of a catalyst. The product is obtained and then subjected to an imidization reaction with an aromatic carboxylic acid anhydride.
好適な反応方法の１つはフェノール類と芳香族アミンと
ホルムアルデヒドを９０〜１００℃にて１〜２時間反応
させ、ついで系内を真空下にして脱水操作を行なった後
、 １７０〜１９０“Ｃにて０．５〜２時間加熱して、
フェノール類と芳香族アミンがメチレン基またはベンジ
リックエーテル基により結合し、かつ芳香族アミンのア
ミノ基が未置換の反応生成物を得る。ついで系内を１５
０〜１７０℃として、芳香族カルボン酸無水物を添加後
、０．５〜１．５時間同温度に保持してイミド化反応を
行なわせる。One of the preferred reaction methods is to react phenols, aromatic amines, and formaldehyde at 90 to 100°C for 1 to 2 hours, then dehydrate the system under vacuum, and then react at 170 to 190°C. Heat for 0.5 to 2 hours at
A reaction product is obtained in which a phenol and an aromatic amine are bonded via a methylene group or a benzylic ether group, and the amino group of the aromatic amine is unsubstituted. Then 15 within the system
After adding the aromatic carboxylic acid anhydride to 0 to 170°C, the temperature is maintained at the same temperature for 0.5 to 1.5 hours to carry out the imidization reaction.
ついて系内を１６０〜１９０ ’Ｃでかつ真空下として
、未反応のフェノール類、芳香族アミン、芳香族カルボ
ン酸無水物などを除去した後、冷却して本発明の変性フ
ェノール樹脂を得る。Then, the system is heated to 160 to 190'C under vacuum to remove unreacted phenols, aromatic amines, aromatic carboxylic acid anhydrides, etc., and then cooled to obtain the modified phenol resin of the present invention.
他の製法例として、芳香族アミンとホルムアルデヒドを
水溶液、またはアルコールなとの有機溶媒中でアルカリ
性触媒の存在下で、もしくは無触媒下で加熱反応後、フ
ェノール類を添加してさらに加熱してフェノール類と芳
香族アミンとホルムアルデヒドの反応性生成物を得、次
いて、前記方法てイミド化反応を行う。As another example of a production method, aromatic amine and formaldehyde are heated in an aqueous solution or an organic solvent such as alcohol in the presence of an alkaline catalyst or in the absence of a catalyst, and then phenols are added and further heated to produce phenol. A reactive product of aromatic amine and formaldehyde is obtained, and then an imidization reaction is carried out using the method described above.
好適な反応方法の１つは芳香族アミンとホルムアルデヒ
ドを４０〜８０℃にて０．５〜１．５時間反応させた後
、フェノール類を添加して９５〜１００℃にて２〜４時
間反応させ、ついて系内を真空下にして脱水操作を行な
った後、１７０〜１９０℃にて０．５〜２時間加熱して
、フェノール類と芳香族アミンかメチレン基またはベン
ジリックエーテル基により結合し、かつ芳香族アミンの
アミン基が未置換の反応生成物を得る。ついて前記の手
順と同方法により本発明の変性フェノール樹脂を得る。One of the preferred reaction methods is to react aromatic amine and formaldehyde at 40 to 80°C for 0.5 to 1.5 hours, then add phenols and react at 95 to 100°C for 2 to 4 hours. After dehydrating the system under vacuum, it is heated at 170 to 190°C for 0.5 to 2 hours to bond phenols and aromatic amines through methylene groups or benzylic ether groups. , and a reaction product in which the amine group of the aromatic amine is unsubstituted is obtained. Then, the modified phenolic resin of the present invention is obtained by the same method as described above.
本発明の変性フェノール樹脂を製造する場合、フェノー
ル類と芳香族アミンに対するホルムアルデヒドのモル比
は通常３０〜９０／ １００であり、好ましくは４０〜
８０／ １００である。この割合で反応させることによ
り数平均分子量２１０〜７００のイミド化した最終生成
物を首尾よく得ることができる。When producing the modified phenolic resin of the present invention, the molar ratio of formaldehyde to phenols and aromatic amines is usually 30 to 90/100, preferably 40 to 100.
It is 80/100. By reacting at this ratio, an imidized final product having a number average molecular weight of 210 to 700 can be successfully obtained.
フェノール類と芳香族アミンとのモル比は、通常フェノ
ール類１モルに対して３〜８０モル％であり、これによ
り最終生成物のイミド基含有率がフェノール類１モルに
対して１０〜８０モル％のものか得られる。好ましくは
５〜５０モル％であモル比は通常芳香族アミン１モルに
対して芳香族カルボン酸無水物は１．０〜１．５モル、
好ましくは１．０〜１．３モルである。かかる割合とな
るようフェノール−芳香族アミン−ホルムアルデヒド反
応生成物と芳香族カルボン酸無水物とを反応させること
によりアミノ基をほぼ完全にイミド化することができる
。The molar ratio of phenols and aromatic amines is usually 3 to 80 mol % per 1 mol of phenols, so that the imide group content of the final product is 10 to 80 mol % per 1 mol of phenols. % can be obtained. Preferably 5 to 50 mol%, and the molar ratio is usually 1.0 to 1.5 mol of aromatic carboxylic acid anhydride to 1 mol of aromatic amine.
Preferably it is 1.0 to 1.3 mol. By reacting the phenol-aromatic amine-formaldehyde reaction product with the aromatic carboxylic acid anhydride in such a ratio, the amino group can be almost completely imidized.
本発明の変性フェノール樹脂において、フェノール類と
生成イミド基との組成比は目的に応じてフェノール類と
芳香族アミンとのモル比によって任意に選択することが
てきるか、フェノール類１モルに対して生成イミド基が
１０〜８０モル％である。生成イミド基の含有量が１０
モル％未満の場合、本発明の変性フェノール樹脂の硬化
物の耐熱性か低下し、また８０モル％を越える場合、機
械的特性か低下する。In the modified phenolic resin of the present invention, the composition ratio of phenols to imide groups can be arbitrarily selected depending on the purpose, depending on the molar ratio of phenols to aromatic amines, or The amount of imide groups produced is 10 to 80 mol%. The content of generated imide groups is 10
When the amount is less than mol %, the heat resistance of the cured product of the modified phenol resin of the present invention decreases, and when it exceeds 80 mol %, the mechanical properties decrease.
本発明の変性フェノール樹脂は数平均分子量か２１０〜
７００である。数平均分子量か２１０未満の場合、本発
明の変性フェノール樹脂の硬化物の架橋密度か低下し、
機械的特性か主に低下する。The modified phenolic resin of the present invention has a number average molecular weight of 210~
It is 700. When the number average molecular weight is less than 210, the crosslinking density of the cured product of the modified phenolic resin of the present invention decreases,
Mechanical properties mainly deteriorate.
また、数平均分子量が７００を越える場合、本発明の変
性フェノール樹脂は、硬化時の流れか乏しくなり、機械
的特性が低下する。Further, when the number average molecular weight exceeds 700, the modified phenol resin of the present invention has poor flow during curing, and mechanical properties deteriorate.
本発明の変性フェノール樹脂の融点は毛細管法て通常７
０〜１００℃である。The melting point of the modified phenolic resin of the present invention is usually 7.
The temperature is 0 to 100°C.
本発明の変性フェノール樹脂は熱硬化させるため、通常
へキサメチレンテトラミンを架橋剤（硬％が望ましい。Since the modified phenolic resin of the present invention is thermally cured, hexamethylenetetramine is usually used as a crosslinking agent (hardness % is desirable).
本発明の変性フェノール樹脂にヘキサメチレンテトラミ
ンを１５重量％配合した場合のゲル化時間（１５０″Ｃ
）は通常４０−１５０秒である。Gelation time when 15% by weight of hexamethylenetetramine is added to the modified phenolic resin of the present invention (150"C
) is usually 40-150 seconds.
本発明の変性フェノール樹脂は従来のフェノール樹脂オ
リゴマー分子内に、芳香族アミンと芳香族カルボン酸無
水物とを樹脂合成時に反応させ生成したイミド基を含有
したものである。イミド基は一般に熱分解性か低く、耐
熱性が優れている長所を有する。従来のフェノール樹脂
の硬化物はフェノール類か主にメチレン基により結合さ
れているが、イミド基はメチレン基に比へ、さらに熱分
解性が小さく、耐熱性の水準が高い。さらに本発明の変
性フェノール樹脂におけるイミド基は単に混合物として
存在しているのてはなく、フェノール樹脂オリゴマー分
子に結合して存在する故に、従来のフェノール樹脂に比
べ、耐熱性か著しく高い特長を有する。The modified phenol resin of the present invention contains an imide group produced by reacting an aromatic amine and an aromatic carboxylic acid anhydride during resin synthesis in a conventional phenol resin oligomer molecule. Imide groups generally have the advantage of low thermal decomposition and excellent heat resistance. Conventional cured products of phenolic resins are bonded by phenols or mainly by methylene groups, but imide groups are even less thermally decomposable and have a higher level of heat resistance than methylene groups. Furthermore, since the imide groups in the modified phenolic resin of the present invention are not simply present as a mixture, but are present bonded to phenolic resin oligomer molecules, it has a feature of significantly higher heat resistance than conventional phenolic resins. .
以下、本発明を実施例により説明する。しかし、本発明
はこれら実施例によって限定されるものてはない。The present invention will be explained below using examples. However, the present invention is not limited to these examples.
また、各実施例、比較例に記載されている「部」および
「％」はすべて「重量部」および「重量％」を示す。In addition, "parts" and "%" described in each example and comparative example all indicate "parts by weight" and "% by weight."
実施例１
冷却器と撹拌器付き反応釜にフェノール１０００部、ア
ニリン４００部、および３７％ホルマリン７４０部を仕
込み後、徐々に昇温し温度が９５°Ｃに達してから１２
０分間還流反応を行なった。ついて系内を６００ｍｍＨ
ｇの真空下で脱水を行なった後、常圧にして１８０°Ｃ
にて４０分間反応した。ついて系内を＋５０°Ｃにして
、無水フタル酸２６０部を添加して同温度で６０分間加
熱反応を行なった。その後系内を１７０℃にて６５０＋
ａｍ）Ｉｇの真空下で６０分間保持後釜出しして固形の
変性フェノール樹脂１４４０部を得た。Example 1 After charging 1,000 parts of phenol, 400 parts of aniline, and 740 parts of 37% formalin into a reaction vessel equipped with a condenser and a stirrer, the temperature was gradually raised and after the temperature reached 95°C,
The reflux reaction was carried out for 0 minutes. 600mmH inside the system
After dehydration under a vacuum of
The reaction was carried out for 40 minutes. Then, the temperature inside the system was raised to +50°C, 260 parts of phthalic anhydride was added, and a heating reaction was carried out at the same temperature for 60 minutes. After that, the system was heated to 170℃ for 650+
am) Ig vacuum for 60 minutes and then taken out from the pot to obtain 1440 parts of a solid modified phenol resin.
実施例２
冷却器と撹拌器付き反応釜にフェノール５００部、ビス
フェノールＡ ５００部、４，４′ −ジアミノジフェ
ニルメタン１５０部および３７％ホルマリン５８０部を
仕込み後、徐々に昇温し温度が９５°Ｃに達してから１
５０分間還流反応を行なった。っいて系内を６００ｍＨ
ｇの真空下で脱水を行なった後、常圧にして１８０℃に
て６０分間反応した。ついて系内を１６０°Ｃにして無
水ピロメリット酸１１０部を添加して、同温度て９０分
間加熱反応を行なった。その後系内を１７０℃にて６５
０ｍｍＨＨの真空下で６０分間保持後釜出しして固形の
変性フェノール樹脂１０３０部を得た。Example 2 After charging 500 parts of phenol, 500 parts of bisphenol A, 150 parts of 4,4'-diaminodiphenylmethane, and 580 parts of 37% formalin into a reaction vessel equipped with a cooler and a stirrer, the temperature was gradually raised to 95°C. 1 after reaching
A reflux reaction was carried out for 50 minutes. 600mH inside the system
After dehydration under a vacuum of 1.5 g, the mixture was brought to normal pressure and reacted at 180° C. for 60 minutes. Then, the inside of the system was heated to 160°C, 110 parts of pyromellitic anhydride was added, and a heating reaction was carried out at the same temperature for 90 minutes. After that, the inside of the system was heated to 170℃ for 65 minutes.
After being held under a vacuum of 0 mmHH for 60 minutes, the mixture was taken out of the pot to obtain 1030 parts of a solid modified phenol resin.
実施例３
冷却器と撹拌器付き反応釜にアニリン３００部および３
７％ホルマリン６７０部を仕込後、徐々に昇温し温度が
４０〜４５℃にて６０分間反応させた。Example 3 300 parts of aniline and 3
After charging 670 parts of 7% formalin, the temperature was gradually raised to 40 to 45°C, and the reaction was carried out for 60 minutes.
次いでフェノール１０００部を添加して昇温し、９５〜
１００℃にて１８０分間反応させた後、系内を６００ｍ
１（Ｈの真空下で脱水を行なった。その後常圧にして、
１８０℃にて６０分間反応した。次いて系内を１６０
℃にして無水トリメリット酸２７０部を添加して同温度
で８０分間加熱反応を行なった。Next, 1000 parts of phenol was added and the temperature was raised to 95~
After reacting at 100°C for 180 minutes, the inside of the system was
1 (Dehydration was performed under a vacuum of H. After that, the pressure was changed to normal pressure,
The reaction was carried out at 180°C for 60 minutes. Next, the inside of the system is 160
℃, 270 parts of trimellitic anhydride was added, and a heating reaction was carried out at the same temperature for 80 minutes.
その後系内を１７０℃にて６５０閣Ｈｇの真空下で９０
分間保持後釜出しして固形の変性フェノール樹脂１３２
０部を得た。After that, the inside of the system was heated to 170°C and 90°C under a vacuum of 650 Hg.
After holding for a minute, it is taken out of the pot and becomes a solid modified phenol resin 132.
I got 0 copies.
比較例１
冷却器と撹拌器付き反応釜にフェノール１０００部、３
７％ホルマリン６３０部および蓚酸２０部を仕込み後、
徐々に昇温し温度か９５℃に達してから１２０分間還流
反応を行なった。ついて系内を６５０℃ｌｍＨｇの真空
下て脱水を行ない系内の温度か１９０℃に到達した時釜
出しして固形の変性フェノール樹脂１０８０部を得た。Comparative Example 1 1000 parts of phenol, 3
After preparing 630 parts of 7% formalin and 20 parts of oxalic acid,
The temperature was gradually raised and after reaching 95°C, a reflux reaction was carried out for 120 minutes. The system was then dehydrated under a vacuum of 650° C./lmHg, and when the temperature in the system reached 190° C., it was taken out of the kettle to obtain 1080 parts of a solid modified phenol resin.
比較例２
冷却器と撹拌器付き反応釜にフェノール１０００部、ア
ニリン８０部、および３７％ホルマリン５８０部を仕込
後、徐々に昇温し温度か９５℃に達してから１２０分間
還流反応を行なった。ついて系内を６００ｍｎＨｇの真
空下で脱水を行なった後、常圧にして１８０°Ｃにて４
０分間反応した。ついて系内を１５０℃にして無水フタ
ル酸７０部を添加して同温度で６０分間加熱反応を行な
った。その後系内を１７０°Ｃにて６５０ｍｍＨｇの真
空下て６０分間保持後釜出しして固形の変性フェノール
樹脂９３０部を得た。Comparative Example 2 After charging 1000 parts of phenol, 80 parts of aniline, and 580 parts of 37% formalin into a reaction vessel equipped with a cooler and a stirrer, the temperature was gradually raised and the temperature reached 95°C, after which a reflux reaction was performed for 120 minutes. . After dehydrating the system under a vacuum of 600 mnHg, the system was brought to normal pressure and heated at 180°C for 4 hours.
Reacted for 0 minutes. Then, the inside of the system was heated to 150°C, 70 parts of phthalic anhydride was added, and a heating reaction was carried out at the same temperature for 60 minutes. Thereafter, the system was kept at 170° C. under a vacuum of 650 mmHg for 60 minutes, and then taken out from the pot to obtain 930 parts of a solid modified phenol resin.
比較例３
冷却器と撹拌器付き反応釜にフェノール１０００部、ア
ニリン１０００部、および３７％ホルマリン１２００部
を仕込み後、徐々に昇温し温度が９５°Ｃに達してから
１２０分間還流反応を行なった。ついて系内を６００℃
ｍ）Ｉｇの真空下で脱水を行なった後、常圧にして１８
０℃にて４０分間反応した。ついて系内を１５０℃にし
て無水フタル酸８００部を添加して同温度で９０分間加
熱反応を行なった。その後系内を１７０℃にて６５０ｍ
）（ｇの真空下で９０分間保持後釜出しして固形の変性
フェノール樹脂２３６０部を得た。Comparative Example 3 After charging 1,000 parts of phenol, 1,000 parts of aniline, and 1,200 parts of 37% formalin to a reaction vessel equipped with a condenser and a stirrer, the temperature was gradually raised and the temperature reached 95°C, after which a reflux reaction was performed for 120 minutes. Ta. The inside of the system was heated to 600℃.
m) After dehydration under Ig vacuum, bring to normal pressure to 18
The reaction was carried out at 0°C for 40 minutes. Then, the inside of the system was heated to 150°C, 800 parts of phthalic anhydride was added, and a heating reaction was carried out at the same temperature for 90 minutes. After that, the inside of the system was heated to 170℃ for 650m.
) (g) was maintained under vacuum for 90 minutes and then taken out of the pot to obtain 2,360 parts of a solid modified phenol resin.
実施例１．２．３および比較例１．２．３において得ら
れた各樹脂の一般特性および実用特性を表１に示す。Table 1 shows the general characteristics and practical characteristics of each resin obtained in Example 1.2.3 and Comparative Example 1.2.3.
尚実用特性の試験方法は次の通りである。The test method for practical properties is as follows.
実施例１，２．３および比較例１．２．３において得ら
れた各樹脂１００重量部にヘキサメチレンテトラミンを
各々１５部配合して混合粉末化する。各々の粉末樹脂３
０部にアルミナ７０部を配合して混合する。各々の配合
物を金型に充填し、 １６０°Ｃ１１００ｋｇ／ａｔに
て１０分間成形する。成形体を取り出し後、長さＩＯａ
ｍ、幅Ｊａｎ厚み１０のテストピースを作製する。常態
および熱処理後の曲げ強度を測定する。15 parts of hexamethylenetetramine was added to 100 parts by weight of each resin obtained in Examples 1, 2.3 and Comparative Example 1.2.3, and the mixture was powdered. each powder resin 3
0 parts and 70 parts of alumina are added and mixed. Each compound was filled into a mold and molded at 160° C. and 1100 kg/at for 10 minutes. After taking out the molded body, the length IOa
A test piece with width Jan and thickness 10 is prepared. Measure the bending strength in normal state and after heat treatment.
本発明の新規な熱硬化性樹脂を各種基材のバインダーま
たは接着剤として用いると、高水準の耐熱性、優れた硬
化性、各種基材との結合力、機械的特性、作業性、経済
性が得られ、工業用耐熱性熱硬化性樹脂として極めて有
用である。When the novel thermosetting resin of the present invention is used as a binder or adhesive for various base materials, it has a high level of heat resistance, excellent curability, bonding strength with various base materials, mechanical properties, workability, and economic efficiency. is obtained, and is extremely useful as an industrial heat-resistant thermosetting resin.
Claims (1)
及び芳香族カルボン酸無水物の反応により得られるイミ
ド基を分子中に含有する変性フェノール樹脂において、
フェノール類に対してイミド基が１０〜８０モル％であ
り、かつ数平均分子量が２１０〜７００である変性フェ
ノール樹脂。(1) In a modified phenolic resin containing imide groups in the molecule obtained by the reaction of phenols, formaldehyde, aromatic amines, and aromatic carboxylic acid anhydrides,
A modified phenol resin containing 10 to 80 mol% of imide groups based on phenols and having a number average molecular weight of 210 to 700.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7557990A JPH03275708A (en) | 1990-03-27 | 1990-03-27 | Modified phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7557990A JPH03275708A (en) | 1990-03-27 | 1990-03-27 | Modified phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03275708A true JPH03275708A (en) | 1991-12-06 |
Family
ID=13580244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7557990A Pending JPH03275708A (en) | 1990-03-27 | 1990-03-27 | Modified phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03275708A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010159335A (en) * | 2009-01-07 | 2010-07-22 | Hitachi Chem Co Ltd | Adhesive composition, film-like adhesive, adhesion sheet, and semiconductor device |
| JP2012097207A (en) * | 2010-11-02 | 2012-05-24 | Yokohama National Univ | Polybenzoxazine-modified bismaleimide resin and polybenzoxazine-modified bismaleimide resin composition |
-
1990
- 1990-03-27 JP JP7557990A patent/JPH03275708A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010159335A (en) * | 2009-01-07 | 2010-07-22 | Hitachi Chem Co Ltd | Adhesive composition, film-like adhesive, adhesion sheet, and semiconductor device |
| JP2012097207A (en) * | 2010-11-02 | 2012-05-24 | Yokohama National Univ | Polybenzoxazine-modified bismaleimide resin and polybenzoxazine-modified bismaleimide resin composition |
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