JPH0554847B2 - - Google Patents
Info
- Publication number
- JPH0554847B2 JPH0554847B2 JP24100586A JP24100586A JPH0554847B2 JP H0554847 B2 JPH0554847 B2 JP H0554847B2 JP 24100586 A JP24100586 A JP 24100586A JP 24100586 A JP24100586 A JP 24100586A JP H0554847 B2 JPH0554847 B2 JP H0554847B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- epoxy resin
- phosphine oxide
- curing agent
- acid
- 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 - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000001723 curing Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SZTDSGCADFWGKM-UHFFFAOYSA-N 3-[bis(3-hydroxypropyl)phosphoryl]propan-1-ol Chemical compound OCCCP(=O)(CCCO)CCCO SZTDSGCADFWGKM-UHFFFAOYSA-N 0.000 description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000000034 method Methods 0.000 description 4
- -1 phosphate ester Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005691 triesters Chemical group 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Epoxy Resins (AREA)
Description
〔産業上の利用分野〕
本発明は含りんエポキシ樹脂の製造方法に関す
るものである。詳しくは、エポシキ樹脂の諸物
性、特に耐燃性の改良法に関するものである。
〔従来の技術および問題点〕
従来のエポキシ樹脂の耐燃性はハロゲン化合
物、たとえばテトラブロムビスフエトールＡ、ヘ
ツト酸およびこれらの誘導体を使用することによ
り行われてきたが、電気特性、耐熱性、強度の低
下につながり、エポキシ樹脂本来の優れた物性を
維持できないものであつた。
特にこれまでのりん系難燃剤の多くは、非反応
型の化合物であり、また、りん酸エステル型のた
め、耐水、耐熱性が低く、ほとんどのものは実使
用に至つていない。
上述した問題点を解決するものとして、特開昭
57−195141号があげられる。これは、りん化合物
としてトリス（ヒドロキシプロピル）ホスフイン
オキシドを使用するものであるが、この化合物は
融点が高く、一般の有機化合物との相溶性が低
く、限られた方法でしか使用できない。たとえば
酸無水物と反応させ、次いで他の架橋剤などの共
存下でポリエポキシ化合物を反応させ、エポキシ
樹脂を得る方法があるが、この方法では充分な耐
燃効果を得るまでりん含量を上げることはできな
かつた。
〔問題点を解決するための手段〕
本発明者等は上記の欠点を改良するために鋭意
検討を結果、本発明に到達した。
即ち、本発明の含りんエポシキ樹脂組成物はポ
リエポキシ化合物及び硬化剤を主成分とするエポ
キシ樹脂組成物において、硬化剤の少なくとも一
部分として、下式で示されるホスフインオキシド
誘導体を使用することを特徴とする。
（式中、Ｘ＝０〜２、Ｙ＝１〜３であり、かつＸ
＋Ｙ＝３、Ｒは−CH2−又は−CH2−CH2−であ
る。）
従来、使用されているトリス（ヒドロキシプロ
ピル）ホスフインオキシドはリん酸エステル結合
がなく、耐加水分解性、耐熱性があるが、前述し
たように融点が高く、一般の有機化合物との相溶
性が低い。
本発明の第１の特徴はトリス（ヒドロキシプロ
ピル）ホスフインオキシドとチオグリコール酸お
よび／またはメルカプトプロピオン酸を反応させ
ることにより、液状化させ、ポリエポキシ化合物
等との相溶性を上げたことにあり、これを硬化剤
成分として使用することにある。
第２の特徴はりんおよび硫黄を含有する化合物
を硬化剤成分として使用するため、エポキシ樹脂
中のこれらの含量を所望の量とすることができ、
さらにりんと硫黄の相乗効果により、充分な耐燃
効果を与えることが出来る。
第３の特徴なホスフインオキシド誘導体硬化剤
の反応基が−SH基であるため、エポキシ化合物
との反応性が高く、触媒量の削減、低温硬化等が
可能となることである。
本発明で使用する硬化剤成分の原料であるトリ
ス（ヒドロキシプロピル）ホスフインオキシドの
製造法は公知であり、アリルアルコールとホスフ
インを反応させ次いで酸化することによつて得ら
れる。
ホスフインオキシド誘導体硬化剤の製造はトリ
ス（ヒドロキシプロピル）ホスフインオキシドと
チオグリコール酸および／またはメルカプトプロ
ピオン酸の反応を一般のポリエステルの製造条件
に準じて行えば良い。
使用するエステル化触媒は例えばパラトルエン
スルホン酸、メタンスルホン酸等である。反応温
度は90℃〜150℃が良く、−SH基を保護するため、
好ましくは90℃〜140℃が良い。また、反応は常
圧または減圧で行い、場合によつては溶剤を使用
しても良い。例えば反応装置に分水器を取付け、
トルエン還流下で行うことができる。
トリス（ヒドロキシプロピル）ホスフインオキ
シドとチオグリコール酸および／またはメルカプ
トプロピオン酸のモル比は目的とするエステルに
より適宜かえるのが良い。トリエステルを目的物
とする場合はチオグリコール酸および／またはメ
ルカプトプロピオン酸の使用量を3.3〜4.0モル／
モルとする好収率となる。
本発明の含りんエポキシ樹脂組成物の硬化は一
般に行われているエポキシ樹脂の硬化方法で良
い。ポリエポキシ化合物は市販の例えばビスフエ
ノールＡ型、フエノールノボラツク型のポリエポ
キシ化合物が使用できる。硬化触媒としては３級
アミンの使用が良い。硬化条件はポリエポキシ化
合物、触媒の種類やその使用量によつて異なるが
０℃〜150℃で数分〜数十時間である。また、他
の硬化剤、難燃剤、充填剤、他の樹脂等の混合使
用も可能である。
本発明におけるホスフインオキシド誘導体の使
用量は耐燃効果からみて、硬化剤の10〜100重量
％とするのが好ましく、さらに好ましくは20〜
100重量％である。
〔実施例〕
以下に本発明で使用する、含りんポリチオール
化合物であるホシフインオキシド誘導体の製造
例、エポキシ樹脂組成物の実施例、比較例を示
す。なお、例中の部、％は重量基準である。
含りんポリチオール化合物の製造
製造例 １
ガラス製容器にトリス（ヒドロキシプロピル）
ホスフインオキシド244部、チオクリコール酸304
部、パラトルエンスルホン酸5.3部をとり、窒素
気流下、130〜140℃で6.0時間撹拌した。次いで、
同温度50mmHgで撹拌を6.0時間行つた。この間の
生成水の量は52部であつた。トルエン200部、水
200部を加え、水酸化ナトリウムで中和後、水洗、
脱トルエンを行つた。
得られた生成物は無色の粘ちような液体で、そ
の収量は460部であつた。この生成物の分析結果
を下に示す。
SH価：6.3meq／ｇ 元素分析：6.8％、S20.4％
製造例 ２
分水器の付いたガラス製容器に、トリス（ヒド
ロキシプロピル）ホスフインオキシド244部、メ
ルカプトプロピオン酸424部、メタンスルホン酸
3.2部、トルエン200部をとり、トルエン還流下で
10.0時間撹拌した。この間の生成水は54部であつ
た。製造例１と同様な処理で精製を行つた。
得られた生成物は無色の粘ちような液体で収量
は485部であつた。分析結果を下に示す。
SH価：6.0meq／ｇ 元素分析：P6.4％、S19.5
％
また、この生成物のゲルパーメーシヨンクロマ
トグラムを第１図に、IRスペクトルを第２図に
示す。
製造例 ３
ガラス製容器にトリス（ヒドロキシプロピル）
ホスフインオキシド244部、メルカプトプロピオ
ン酸212部、パラトルエンスルホン酸4.4部をと
り、窒素気流下、常圧、130〜140℃で6.0時間、
次いで50〜20mmHgで6.0時間撹拌した。この間の
生成水は34部であつた。アルミニウムシリケート
系の吸着剤で処理し、次いで濾過を行い、無色の
粘ちような液体を得た。収量は388部であつた。
分析値を下に示す。
SH価：5.0meq／ｇ 元素分析：P7.9％、S15.9
％
エポキシ樹脂の製造
実施例１〜３、比較例１〜３
市販のビスフエノールＡ系の液状エポキシ樹脂
（エポキシ当量190）、製造例１〜３で得た硬化剤、
その他の硬化剤、触媒等を表−１に示した配合で
とり、混合した。これをポリフツ化ビニル樹脂の
容器に注ぎ室温で硬化し試験片を得た。試験結果
を表−１に記載した。
[Industrial Field of Application] The present invention relates to a method for producing a phosphorus-containing epoxy resin. More specifically, it relates to methods for improving the physical properties of epoxy resins, particularly flame resistance. [Prior Art and Problems] The flame resistance of conventional epoxy resins has been achieved by using halogen compounds such as tetrabromobisphetol A, Hett's acid, and derivatives thereof, but the electrical properties, heat resistance, This led to a decrease in strength, and the excellent physical properties inherent to the epoxy resin could not be maintained. In particular, most of the phosphorus-based flame retardants to date are non-reactive compounds, and because they are phosphate ester type, they have low water resistance and heat resistance, and most of them have not been put into practical use. To solve the above-mentioned problems, JP-A-Sho
No. 57-195141 is mentioned. This uses tris(hydroxypropyl)phosphine oxide as a phosphorus compound, but this compound has a high melting point and low compatibility with general organic compounds, so it can only be used in limited ways. For example, there is a method to obtain an epoxy resin by reacting with an acid anhydride and then reacting with a polyepoxy compound in the coexistence of other crosslinking agents, but with this method, it is not possible to increase the phosphorus content until sufficient flame resistance is obtained. I couldn't do it. [Means for Solving the Problems] The present inventors have conducted intensive studies to improve the above-mentioned drawbacks, and have arrived at the present invention. That is, the phosphorus-containing epoxy resin composition of the present invention is an epoxy resin composition containing a polyepoxy compound and a curing agent as main components, in which a phosphine oxide derivative represented by the following formula is used as at least a part of the curing agent. Features. (In the formula, X = 0 to 2, Y = 1 to 3, and
+Y=3, R is -CH2- or -CH2 - CH2- . ) Conventionally used tris(hydroxypropyl)phosphine oxide does not have a phosphate ester bond and is resistant to hydrolysis and heat, but as mentioned above, it has a high melting point and is not compatible with general organic compounds. Low solubility. The first feature of the present invention is that tris(hydroxypropyl)phosphine oxide is liquefied by reacting with thioglycolic acid and/or mercaptopropionic acid, thereby increasing its compatibility with polyepoxy compounds and the like. , to use this as a curing agent component. The second feature is that compounds containing phosphorus and sulfur are used as curing agent components, so the content of these in the epoxy resin can be adjusted to the desired amount.
Furthermore, the synergistic effect of phosphorus and sulfur can provide sufficient flame resistance. The third characteristic is that the reactive group of the phosphine oxide derivative curing agent is a -SH group, so it has high reactivity with an epoxy compound, making it possible to reduce the amount of catalyst and perform low-temperature curing. The method for producing tris(hydroxypropyl)phosphine oxide, which is a raw material for the curing agent component used in the present invention, is known, and is obtained by reacting allyl alcohol with phosphine and then oxidizing it. The phosphine oxide derivative curing agent may be produced by reacting tris(hydroxypropyl)phosphine oxide with thioglycolic acid and/or mercaptopropionic acid according to the conditions for producing general polyesters. The esterification catalyst used is, for example, para-toluenesulfonic acid or methanesulfonic acid. The reaction temperature is preferably 90°C to 150°C to protect the -SH group.
Preferably the temperature is 90°C to 140°C. Further, the reaction may be carried out at normal pressure or reduced pressure, and a solvent may be used depending on the case. For example, attaching a water separator to the reactor,
This can be carried out under toluene reflux. The molar ratio of tris(hydroxypropyl)phosphine oxide to thioglycolic acid and/or mercaptopropionic acid may be changed as appropriate depending on the desired ester. When the target product is triester, the amount of thioglycolic acid and/or mercaptopropionic acid used is 3.3 to 4.0 mol/
Good yield in terms of moles. The phosphorus-containing epoxy resin composition of the present invention may be cured by a commonly used epoxy resin curing method. Commercially available polyepoxy compounds such as bisphenol A type and phenol novolac type can be used as the polyepoxy compound. Tertiary amines are preferably used as curing catalysts. Curing conditions vary depending on the polyepoxy compound, the type of catalyst, and the amount used, but are at 0°C to 150°C and for several minutes to several tens of hours. It is also possible to use a mixture of other curing agents, flame retardants, fillers, other resins, etc. The amount of phosphine oxide derivative used in the present invention is preferably 10 to 100% by weight of the curing agent, more preferably 20 to 100% by weight from the viewpoint of flame resistance.
It is 100% by weight. [Example] Below, examples of manufacturing a phosiphin oxide derivative, which is a phosphorus-containing polythiol compound, and examples and comparative examples of an epoxy resin composition used in the present invention are shown. Note that parts and percentages in the examples are based on weight. Production example of phosphorus-containing polythiol compound 1 Tris (hydroxypropyl) in a glass container
244 parts of phosphine oxide, 304 parts of thiocricholic acid
and 5.3 parts of para-toluenesulfonic acid, and stirred at 130 to 140°C for 6.0 hours under a nitrogen stream. Then,
Stirring was performed for 6.0 hours at the same temperature of 50 mmHg. The amount of water produced during this period was 52 parts. 200 parts toluene, water
Add 200 parts, neutralize with sodium hydroxide, wash with water,
I removed toluene. The product obtained was a colorless viscous liquid, and the yield was 460 parts. The analysis results of this product are shown below. SH value: 6.3meq/g Elemental analysis: 6.8%, S20.4% Production example 2 In a glass container with a water separator, 244 parts of tris(hydroxypropyl)phosphine oxide, 424 parts of mercaptopropionic acid, methanesulfone acid
Take 3.2 parts and 200 parts of toluene, and add toluene under reflux.
Stirred for 10.0 hours. The amount of water produced during this period was 54 parts. Purification was carried out in the same manner as in Production Example 1. The product obtained was a colorless viscous liquid with a yield of 485 parts. The analysis results are shown below. SH value: 6.0meq/g Elemental analysis: P6.4%, S19.5
% A gel permeation chromatogram of this product is shown in FIG. 1, and an IR spectrum is shown in FIG. 2. Production example 3 Tris (hydroxypropyl) in a glass container
244 parts of phosphine oxide, 212 parts of mercaptopropionic acid, and 4.4 parts of para-toluenesulfonic acid were taken, and the mixture was heated at 130 to 140°C under a nitrogen stream at normal pressure for 6.0 hours.
The mixture was then stirred at 50-20 mmHg for 6.0 hours. The amount of water produced during this period was 34 parts. Treatment with an aluminum silicate adsorbent followed by filtration yielded a colorless viscous liquid. The yield was 388 copies.
The analytical values are shown below. SH value: 5.0meq/g Elemental analysis: P7.9%, S15.9
% Epoxy resin production Examples 1 to 3, Comparative Examples 1 to 3 Commercially available bisphenol A-based liquid epoxy resin (epoxy equivalent: 190), curing agent obtained in Production Examples 1 to 3,
Other curing agents, catalysts, etc. were prepared and mixed as shown in Table 1. This was poured into a polyvinyl fluoride resin container and cured at room temperature to obtain a test piece. The test results are listed in Table-1.
【表】【table】
【表】
発明の効果〕
本発明の方法によれば、反応性の高い硬化剤型
の難燃剤を使用するための、他の諸物性を犠牲に
することなく、しかも従来にない有利な条件で、
耐燃性の高い良質なエポキシ樹脂を製造できる。[Table] Effects of the Invention] According to the method of the present invention, a highly reactive curing agent type flame retardant can be used without sacrificing other physical properties and under advantageous conditions not previously available. ,
It is possible to produce high-quality epoxy resin with high flame resistance.
第１図は、製造例２で得られた生成物のゲルパ
ーメーシヨンクロマトグラムであり、第２図は製
造例２で得られた生成物の赤外線吸収スペクトル
である。
FIG. 1 is a gel permeation chromatogram of the product obtained in Production Example 2, and FIG. 2 is an infrared absorption spectrum of the product obtained in Production Example 2.
Claims (1)
るエポキシ樹脂組成物において、硬化剤の少なく
とも一部分として、下式で示されるホスフインオ
キシド誘導体を使用することを特徴とする含りん
エポキシ樹脂組成物。 （式中、Ｘ＝０〜２、Ｙ＝１〜３であり、かつＸ
＋Ｙ＝３、Ｒは−CH2−又は−CH2−CH2−であ
る。）[Scope of Claims] 1. An epoxy resin composition containing a polyepoxy compound and a curing agent as main components, characterized in that a phosphine oxide derivative represented by the following formula is used as at least a portion of the curing agent. Epoxy resin composition. (In the formula, X = 0 to 2, Y = 1 to 3, and
+Y=3, R is -CH2- or -CH2 - CH2- . )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24100586A JPS6395223A (en) | 1986-10-09 | 1986-10-09 | Phosphorus-containing epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24100586A JPS6395223A (en) | 1986-10-09 | 1986-10-09 | Phosphorus-containing epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6395223A JPS6395223A (en) | 1988-04-26 |
| JPH0554847B2 true JPH0554847B2 (en) | 1993-08-13 |
Family
ID=17067913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24100586A Granted JPS6395223A (en) | 1986-10-09 | 1986-10-09 | Phosphorus-containing epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6395223A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023222573A1 (en) | 2022-05-16 | 2023-11-23 | Kuhn Sas | Method and facility for working a plot of land with at least two agricultural robots |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4568937B2 (en) * | 2000-01-17 | 2010-10-27 | 住友ベークライト株式会社 | Flame retardant resin composition, prepreg and laminate using the same |
| EP1508583B1 (en) | 2002-05-29 | 2006-10-11 | Nippon Chemical Industrial Company Limited | Phosphorus-containing epoxy resin, phosphorus-containing epoxy resin composition, process for producing the same, and sealing material and laminate each comprising or made with the same |
-
1986
- 1986-10-09 JP JP24100586A patent/JPS6395223A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023222573A1 (en) | 2022-05-16 | 2023-11-23 | Kuhn Sas | Method and facility for working a plot of land with at least two agricultural robots |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6395223A (en) | 1988-04-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |