JPH0753786B2 - Method for producing heat-resistant phenol resin - Google Patents
Method for producing heat-resistant phenol resinInfo
- Publication number
- JPH0753786B2 JPH0753786B2 JP61306067A JP30606786A JPH0753786B2 JP H0753786 B2 JPH0753786 B2 JP H0753786B2 JP 61306067 A JP61306067 A JP 61306067A JP 30606786 A JP30606786 A JP 30606786A JP H0753786 B2 JPH0753786 B2 JP H0753786B2
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- resin
- parts
- boric acid
- boron
- 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
- 239000005011 phenolic resin Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 15
- 229910052810 boron oxide Inorganic materials 0.000 claims description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 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
- 239000003054 catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical compound OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は耐熱性に優れたフエノール樹脂の製造方法に関
するものであり、本発明により得られた樹脂は成形品
用、積層品用、シェルモールド法結合剤用、レヂノイド
砥石結合剤用、摩擦材結合剤用、塗料等の公知のフエノ
ール樹脂用途に使用する。TECHNICAL FIELD The present invention relates to a method for producing a phenol resin having excellent heat resistance, and the resin obtained by the present invention is used for molded products, laminated products, shell molds. It is used for known phenol resin applications such as method binders, resinoid grindstone binders, friction material binders and paints.
硼素変性フエノール樹脂は優れた耐熱性を有していなが
らその製造方法の煩雑さから実用上に広く供されていな
い。Boron-modified phenolic resins have excellent heat resistance, but have not been widely used in practice due to the complexity of the manufacturing method.
従来硼素変性フエノール樹脂を製造する方法として硼酸
フェニルエステルにアルデヒド類を反応させる方法（例
えば特公昭37−8847号）又はフェノール類と硼酸又は酸
化硼素を脱水下反応させたのちアルデヒド類と反応させ
る方法（例えば特公昭40−13073号、特公昭47−18867
号、特公昭45−40071号）が公知である。しかしながら
硼酸又は酸化硼素とフエノール類から硼酸フェニルエス
テルを合成する際は高温、長時間（例えば280℃にて５
時間）の反応必要である他、硼酸フェニルエステルはフ
エノール性水酸基に基因するオルト、パラ位の活性がな
くなりアルデヒド類との反後性が著しくそこなわれる。Conventionally, as a method for producing a boron-modified phenolic resin, a method of reacting boric acid phenyl ester with aldehydes (for example, JP-B-37-8847) or a method of reacting phenols with boric acid or boron oxide under dehydration and then reacting with aldehydes (For example, Japanese Patent Publication No. 40-13073, Japanese Patent Publication No. 47-18867
And Japanese Examined Patent Publication No. 45-40071). However, when synthesizing boric acid phenyl ester from boric acid or boron oxide and phenols, the reaction is carried out at high temperature for a long time (for example, at 280 ° C for 5 hours).
In addition to the above, the phenyl ester borate loses its activity in the ortho and para positions due to the phenolic hydroxyl group and remarkably loses its reciprocity with aldehydes.
又、フエノール類をアルデヒド類で樹脂化したのち硼酸
等の硼素化合物で変性する方法もある。レゾール型フエ
ノール樹脂（例えば特公昭40−13073号、特開昭61−152
717号）は公知であるが、通常のノボラツク型フエノー
ル樹脂については、硼素を有意義な量で包含させること
は困難であり、実用に供しなかつた。（特開昭50−7569
2号） （発明が解決しようとする問題点） 本発明は従来製造することのできなかった硼素変性ノボ
ラック型フエノール樹脂の製造方法に関するものであ
り、鋭意研究の結果、ノボラック型フエノール樹脂の性
状を限定することにより、耐熱性に優れた硼素変性フエ
ノール樹脂の製造方法を発明したものである。There is also a method in which phenols are resinified with aldehydes and then modified with a boron compound such as boric acid. Resol-type phenol resin (for example, Japanese Patent Publication No. 40-13073, JP-A No. 61-152)
No. 717) is known, but it is difficult to incorporate boron in a significant amount in a normal novolak type phenol resin, and it has not been put to practical use. (Japanese Patent Laid-Open No. 50-7569
(No. 2) (Problems to be solved by the invention) The present invention relates to a method for producing a boron-modified novolac-type phenolic resin which could not be conventionally produced, and as a result of earnest research, the properties of the novolac-type phenolic resin have been investigated. By limiting the present invention, a method for producing a boron-modified phenol resin having excellent heat resistance is invented.
（問題点を解決するための手段） 本発明はフエノール類とアルデヒド類を酸性触媒下にお
いて反応させて得られたノボラック型フエノール樹脂に
硼酸又は酸化硼素を反応させて、硼素変性フエノール樹
脂を得る方法において、ノボラック型フエノール樹脂の
軟化点が50〜110℃であり、かつ未反応のフエノール類
含有量が５％以下であることを必須とし、樹脂100重量
部に対して硼酸の２〜30重量部又は酸化硼素の１〜20重
量部を110℃以上で反応、脱水させることを特徴とする
耐熱性フエノール樹脂の製造方法である。(Means for Solving Problems) The present invention is a method for obtaining a boron-modified phenol resin by reacting a novolac-type phenol resin obtained by reacting a phenol with an aldehyde under an acidic catalyst with boric acid or boron oxide. In the above, it is essential that the softening point of the novolac type phenol resin is 50 to 110 ° C. and the content of unreacted phenols is 5% or less, and 2 to 30 parts by weight of boric acid is added to 100 parts by weight of the resin. Alternatively, it is a method for producing a heat-resistant phenolic resin, which comprises reacting 1 to 20 parts by weight of boron oxide at 110 ° C. or higher and dehydrating it.
本発明によるフエノール類とはフエノールあるいはクレ
ゾール、キシレノール、パラターシャルブチルフエノー
ル、オクチルフエノール、フエニルフエノールのような
アルキルフエノール類やその混合物、ビスフエノール
Ｆ、ビスフエノールＡ、ビスフエノールＳのようなビス
フエノール類やその混合物であり、アルデヒド類とはホ
ルムアルデヒド、アセトアルデヒド等のアルデヒド類の
発生源となる物質あるいはアルデヒド類の水溶液であ
る。The phenols according to the present invention include phenol or alkylphenols such as cresol, xylenol, para-tertiary butylphenol, octylphenol, phenylphenol and mixtures thereof, bisphenol F, bisphenol A, bisphenol S and bisphenol F. It is a phenol or a mixture thereof, and the aldehyde is a substance that is a generation source of aldehyde such as formaldehyde or acetaldehyde, or an aqueous solution of aldehyde.
本発明におけるノボラック型フエノール樹脂とは前記フ
エノール類とアルデヒド類を酸性触媒下において公知の
方法により合成されるもののうち、軟化点が50℃〜110
℃であり、さらに好ましくは70〜90℃である。軟化点が
50℃以下の場合は本法によって得られた硼素変性フエノ
ール樹脂の軟化点が低すぎ取扱いが困難となり、110℃
以上の場合は硼酸又は酸化硼素との反応において軟化点
が高くなりすぎて製造工程に適合しなくなる。The novolac-type phenol resin in the present invention is a compound synthesized by a known method of the phenols and aldehydes under an acidic catalyst, and has a softening point of 50 ° C to 110 ° C.
C., and more preferably 70 to 90.degree. Softening point
If the temperature is below 50 ℃, the softening point of the boron-modified phenolic resin obtained by this method will be too low and handling will be difficult.
In the above case, the softening point becomes too high in the reaction with boric acid or boron oxide, which makes it unsuitable for the manufacturing process.
本発明におけるノボラック型フエノール樹脂の未反応フ
ェノール類含有量は５％以下、さらに好ましくは２％以
下である。The content of unreacted phenols in the novolac type phenol resin in the present invention is 5% or less, more preferably 2% or less.
未反応フエノール類含有量が５％以上の場合は理由は明
らかでないが、硼酸又は酸化硼素との反応において反応
物が高粘度となり、脱水工程でゲル化状態となるため、
所望の樹脂は製造されない。When the content of unreacted phenols is 5% or more, the reason is not clear, but the reaction product becomes highly viscous in the reaction with boric acid or boron oxide and becomes a gel state in the dehydration step,
The desired resin is not manufactured.
硼酸又は酸化硼素とノボラック型フエノール樹脂の反応
はあらかじめ通常の方法により製造された固体物のノボ
ラック型フエノール樹脂を熱溶融して110℃以上とする
か、ノボラック型フエノール樹脂を焚き上げた後の油状
物が110℃以上において硼酸又は酸化硼素の所定量を投
入し２−３時間撹拌しながら反応させる。The reaction between boric acid or boron oxide and the novolac-type phenol resin is performed by melting a solid novolac-type phenol resin prepared by a conventional method in advance to 110 ° C or higher, or an oil after heating the novolac-type phenol resin. At 110 ° C. or higher, a predetermined amount of boric acid or boron oxide is added and the reaction is carried out while stirring for 2-3 hours.
ノボラック型フェノール樹脂100重量部に対して、反応
させる硼酸が２重量部以下又は酸化硼素が１重量部以下
の場合は得られた樹脂の耐熱性が低く変性の効果がな
く、逆に硼酸が30重量部以上又は酸化硼素が20重量部以
上の場合は未反応の硼酸又は酸化硼素が樹脂中に残って
しまう。When the amount of boric acid to be reacted is 2 parts by weight or less or the amount of boron oxide is 1 part by weight or less with respect to 100 parts by weight of the novolac type phenolic resin, the heat resistance of the obtained resin is low and there is no denaturing effect. If the amount is at least 20 parts by weight or more than 20 parts by weight, unreacted boric acid or boron oxide remains in the resin.
フエノール性水酸基と、硼酸又は酸化硼素との反応によ
って生ずる水分を減圧下にて脱水を行い、系外に出した
後冷却して本発明樹脂を得る。この硼素変性フエノール
樹脂はノボラック型フエノール樹脂の硬化剤であるヘキ
サミン等を混合し硬化させることにより耐熱性の優れた
成形物を得ることができる。Moisture generated by the reaction between the phenolic hydroxyl group and boric acid or boron oxide is dehydrated under reduced pressure, discharged from the system, and then cooled to obtain the resin of the present invention. This boron-modified phenol resin can be mixed with a curing agent such as hexamine, which is a novolak-type phenol resin, and cured to obtain a molded article having excellent heat resistance.
本発明により、耐熱性の優れた硼素変性フエノール樹脂
を安定して製造でき、広く種々の分野に供給することが
できる。According to the present invention, a boron-modified phenol resin having excellent heat resistance can be stably produced and can be widely supplied to various fields.
以下本発明を実施例により詳細に説明するが、本発明は
実施例に限定されるものではない。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
ここに記載する「部」および「％」はすべて「重量」を
示す。All "parts" and "%" described herein indicate "weight".
実施例−１ フエノール・ホルマリン・シユウ酸で得られた軟化点90
℃、未反応フエノール含有量２％のノボラック型フエノ
ール樹脂100部を三口フラスコに入れ140℃にて溶融した
所へ硼酸10部を加えて140℃にて２時間反応させた。そ
の后40mmHgにてフラスコ内温が160℃となるまで脱水を
行い、冷却バットに取り出し、黄色の硼素変性フエノー
ル樹脂を得た。この樹脂の軟化点は105℃、ゲルタイム5
5秒/150℃、フロー78mmであった。（ゲルタイム、フロ
ーはヘキサミン10％混合） 実施例−２ 実施例−１において硼酸の代りに酸化硼素10部を使う他
実施例−１に示す方法によって硼素変性フエノール樹脂
を得た。この樹脂の軟化点は108℃、ゲルタイム60秒/15
0℃、フロー73mmであった（ゲルタイム、フローはヘキ
サミン10％混合） 実施例−３ ノボラック型フエノール樹脂の軟化点が90℃、未反応フ
エノール含有量が８％のものを使っている他は実施例−
１に示す方法で行った所、140℃の反応に於いて樹脂粘
度が高くなり、脱水工程の始めでゲル化状態となり所望
の硼素変性フエノール樹脂は得られなかった。Example 1 Softening point 90 obtained with phenol formalin oxalic acid
At 100 ° C., 100 parts of a novolak type phenol resin having an unreacted phenol content of 2% was placed in a three-necked flask, 10 parts of boric acid was added to the molten place at 140 ° C., and the mixture was reacted at 140 ° C. for 2 hours. After that, dehydration was carried out at 40 mmHg until the temperature inside the flask reached 160 ° C, and the product was taken out in a cooling vat to obtain a yellow boron-modified phenol resin. This resin has a softening point of 105 ° C and a gel time of 5
The flow rate was 78 mm at 5 seconds / 150 ° C. (Gel time and flow are mixed with 10% hexamine) Example-2 A boron-modified phenolic resin was obtained by the method shown in Example-1 except that 10 parts of boron oxide was used in place of boric acid in Example-1. The softening point of this resin is 108 ℃, gel time 60 seconds / 15
The temperature was 0 ° C and the flow was 73 mm (gel time and flow were 10% hexamine mixed). Example-3 Other than using a novolac type phenolic resin having a softening point of 90 ° C and an unreacted phenol content of 8%. Example-
When the method shown in 1 was carried out, the resin viscosity became high in the reaction at 140 ° C., and the desired boron-modified phenolic resin could not be obtained because of the gelation state at the beginning of the dehydration step.
以上の実施例1,2で得た硼素変性フエノール樹脂および
通常のフエノール樹脂にヘキサミン10％を加えて粉砕し
たもの25部と炭酸カルシユーム粉末75部を混合し、形に
つめ150℃−25分−100kg/cm2の条件でプレス成形を行っ
た。Boron-modified phenol resin obtained in the above Examples 1 and 2 and normal phenol resin were mixed with 25 parts of crushed 10% of hexamine and 75 parts of calcium carbonate powder, and the mixture was clogged at 150 ° C for 25 minutes- Press molding was performed under the condition of 100 kg / cm 2 .
これを300℃オーブン中に入れ経時的に曲げ強さを測定
した結果を表−１に示す。The results of measuring the bending strength over time in an oven at 300 ° C are shown in Table-1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡本 邦夫 群馬県高崎市大八木町622 群栄化学工業 株式会社内 (72)発明者 長壁 勘二 群馬県高崎市大八木町622 群栄化学工業 株式会社内 (56)参考文献 特開 昭61−152717（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kunio Okamoto 622 Oyagi-cho, Gunma Prefecture Takasaki-shi Gunei Chemical Industry Co., Ltd. (56) References JP-A-61-152717 (JP, A)
Claims (3)
フェノール類が５％以下であるノボラック型フェノール
樹脂と硼酸又は酸化硼素を110℃以上で反応させること
を特徴とする耐熱性フェノール樹脂の製造方法。1. A heat resistance characterized by reacting a novolac type phenolic resin having a softening point of 50 to 110 ° C. and unreacted phenols of 5% or less with boric acid or boron oxide at 110 ° C. or more. Method for producing phenolic resin.
２〜30重量部である特許請求の範囲第１項記載の製造方
法。2. The method according to claim 1, wherein the boric acid is 2 to 30 parts by weight with respect to 100 parts by weight of the phenol resin.
して１〜20重量部である特許請求の範囲第１項記載の製
造方法。3. The method according to claim 1, wherein the amount of boron oxide is 1 to 20 parts by weight with respect to 100 parts by weight of the phenol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61306067A JPH0753786B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing heat-resistant phenol resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61306067A JPH0753786B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing heat-resistant phenol resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63156814A JPS63156814A (en) | 1988-06-29 |
| JPH0753786B2 true JPH0753786B2 (en) | 1995-06-07 |
Family
ID=17952647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61306067A Expired - Lifetime JPH0753786B2 (en) | 1986-12-22 | 1986-12-22 | Method for producing heat-resistant phenol resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753786B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006045546A (en) * | 2004-07-05 | 2006-02-16 | Dainippon Ink & Chem Inc | Thermosetting resin composition, boric acid-modified triazine structure-containing novolak resin, and method for producing the same |
| TW200613399A (en) * | 2004-07-05 | 2006-05-01 | Dainippon Ink & Chemicals | Thermosetting resin composition, boric acid modification triazine structure containing novolac resin and method of producing thereof |
| CN100365036C (en) * | 2006-03-09 | 2008-01-30 | 同济大学 | A kind of preparation method of high boron content boron modified phenolic resin |
| CN112239526B (en) * | 2020-09-22 | 2023-01-17 | 航天特种材料及工艺技术研究所 | A kind of preparation method of RTM type boron phenolic resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152717A (en) * | 1984-12-27 | 1986-07-11 | Sumitomo Deyurezu Kk | Phenolic resin composition modified with boric acid |
-
1986
- 1986-12-22 JP JP61306067A patent/JPH0753786B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63156814A (en) | 1988-06-29 |
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