JPH01108218A - Purification of epoxy resin - Google Patents
Purification of epoxy resinInfo
- Publication number
- JPH01108218A JPH01108218A JP26367387A JP26367387A JPH01108218A JP H01108218 A JPH01108218 A JP H01108218A JP 26367387 A JP26367387 A JP 26367387A JP 26367387 A JP26367387 A JP 26367387A JP H01108218 A JPH01108218 A JP H01108218A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- organic chlorine
- resin
- organochlorine
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 238000000746 purification Methods 0.000 title description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 150000004292 cyclic ethers Chemical class 0.000 claims abstract description 15
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 15
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims description 48
- 229910052801 chlorine Inorganic materials 0.000 claims description 48
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 235000017168 chlorine Nutrition 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 150000003839 salts Chemical class 0.000 description 6
- -1 alkali metal alkoxide Chemical class 0.000 description 5
- 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 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004448 titration Methods 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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エポキシ樹脂の精製方法に関し、とくに樹脂
中の有機塩素を除去するとともに、無色透明な樹脂を得
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for purifying an epoxy resin, and particularly to a method for removing organic chlorine from the resin and obtaining a colorless and transparent resin.
（従来の技術）
一般に、エポキシ樹脂は、フェノール性水酸基のような
活性水素を有する化合物とエピクロルヒドリンとを反応
させて製造する。この方法で得られるエポキシ樹脂中に
は、不純物として下式のような有機塩素化合物が微量存
在することが避けられない。代表的なエポキシ樹脂であ
るビスフェノールＡ型エポキシ樹脂は、約０，１５重量
％の有機塩素を含有することが知られている。(Prior Art) Epoxy resins are generally produced by reacting a compound having active hydrogen, such as a phenolic hydroxyl group, with epichlorohydrin. In the epoxy resin obtained by this method, it is inevitable that a trace amount of an organic chlorine compound as shown in the following formula is present as an impurity. It is known that bisphenol A type epoxy resin, which is a typical epoxy resin, contains about 0.15% by weight of organic chlorine.
この有機塩素は、一般に下記式で表わされる様な形でエ
ポキシ樹脂中に含有されている。This organic chlorine is generally contained in the epoxy resin in the form represented by the following formula.
Ａｒ−０−ＣＨ２ＣＨＣＨ２Ｃ１（Ｉ）ＯＨ
Ａ ｒ −ＯＣＨＣＨ２Ｃｌ （ＩＩ ）Ｃ
Ｈ，ＯＨ
Ａ ｒ Ｏ−ＣＨ２ＣＨＣＨ２Ｃｌ （ＩＩＩ
）〔式中、Ａｒは多価フェノール類（Ａｒ −０Ｈ）の
芳香族残基をあられす。）
有機塩素を含有するエポキシ樹脂を電子材料として使用
すると、リード線の腐食や絶縁低下の原因となるため、
有機塩素含有量がなるべく少ないエポキシ樹脂が求めら
れている。とくに集積回路の封入用原料とする場合、こ
れは不可欠の条件である。また発光素子の材料として使
用する場合は、これに加え、樹脂が無色透明であること
が要求される。Ar-0-CH2CHCH2C1(I)OH Ar-OCHCH2Cl (II)C
H,OH A r O-CH2CHCH2Cl (III
) [In the formula, Ar represents an aromatic residue of polyhydric phenols (Ar -0H). ) If epoxy resin containing organic chlorine is used as an electronic material, it may lead to corrosion of lead wires or a decrease in insulation.
There is a demand for epoxy resins with as little organic chlorine content as possible. This is an essential condition, especially when used as a raw material for encapsulating integrated circuits. In addition, when used as a material for a light emitting element, the resin is required to be colorless and transparent.
上記の有機塩素のうち（Ｉ）の構造をもつものは、エポ
キシ樹脂製造反応における反応中間体であり、アルカリ
金属水酸化物の水溶液で処理することにより、容易に閉
環してエポキシ化合物となる。従フて、この構造をもつ
有機塩素のエポキシ樹脂中の残存量は、０．０１重量％
以下まで低減することが可能である（以下これを「易加
水分解性塩素」と呼ぶ）。Among the above organic chlorines, those having the structure (I) are reaction intermediates in the epoxy resin production reaction, and when treated with an aqueous solution of an alkali metal hydroxide, they easily undergo ring closure to form an epoxy compound. Therefore, the residual amount of organic chlorine having this structure in the epoxy resin is 0.01% by weight.
(hereinafter referred to as "easily hydrolyzable chlorine").
一方、（Ｉりおよび（■りの構造をもつ有機塩素は、ア
ルカリ金属水酸化物水溶液の処理条件をかなりきびしく
しても、エポキシ樹脂中の残存量を低減するのは困難で
ある（以下これらを「難船水分解性塩素」とよぶ）。On the other hand, it is difficult to reduce the amount of organic chlorine having the structure (I and is called "shipwreck water-decomposable chlorine").
エポキシ樹脂中の有機塩素の低減策として、これまでに
次のような方法が提案されている。The following methods have been proposed to date to reduce organic chlorine in epoxy resins.
特開昭５８−１３４１１２号および同５９−２０６４３
０号には、有機塩素含有エポキシ樹脂をメチルエチルケ
トンとメチルイソブチルケトン（またはトルエン）との
混合溶媒中で、過剰のアルカリ性物質で処理する方法が
開示されている。JP 58-134112 and JP 59-20643
No. 0 discloses a method of treating an organic chlorine-containing epoxy resin with an excess of an alkaline substance in a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone (or toluene).
ところがこの方法は、反応溶媒として使用するケトン類
がアルカリを触媒としてアルドール型縮合反応を起して
エポキシ樹脂中に高沸点締金物として残留し、溶媒の原
単位が低下する、などの欠点がある。また、アルカリ処
理は、エポキシ樹脂中の塩素を減少させるには効果的で
あるが、樹脂の色を濃くする傾向がある。However, this method has drawbacks such as the fact that the ketones used as reaction solvents undergo an aldol-type condensation reaction using an alkali as a catalyst and remain in the epoxy resin as a high-boiling point condensate, reducing the solvent consumption rate. . Also, although alkaline treatment is effective in reducing chlorine in the epoxy resin, it tends to darken the color of the resin.
特開昭６０−１１２８１２号に開示の方法は、有機塩素
含有エポキシ樹脂を実質的に無水の条件下で、アルカリ
金属アルコキシドと処理するものである。反応系を無水
条件に保つことと、アルカリ金属アルコキシドといった
比較的高価な薬剤を使用することから、この方法は工業
的に有利とはいえない。The method disclosed in JP-A-60-112812 involves treating an organic chlorine-containing epoxy resin with an alkali metal alkoxide under substantially anhydrous conditions. This method is not industrially advantageous because the reaction system must be kept under anhydrous conditions and relatively expensive chemicals such as alkali metal alkoxides are used.
（発明が解決しようとする問題点）
本発明の目的は、こうした従来技術の水準から一歩前進
し、工業的に有利な方法でエポキシ樹脂中の有機塩素を
低減させると同時に、樹脂の色を一層うすく、はとんど
無色透明なものにするエポキシ樹脂の精製方法を提供す
ることにある。(Problems to be Solved by the Invention) The purpose of the present invention is to go one step further than the level of the prior art, to reduce organic chlorine in epoxy resin by an industrially advantageous method, and at the same time to further improve the color of the resin. The object of the present invention is to provide a method for purifying an epoxy resin to make it almost colorless and transparent.
（発明の構成）
本発明のエポキシ樹脂の精製方法は、環状エーテルを主
体とする溶媒中で、有機塩素を含有するエポキシ樹脂に
、アルカリ金属水酸化物及び金属水素化物を作用させる
ことから成る。(Structure of the Invention) The method for purifying an epoxy resin of the present invention comprises reacting an epoxy resin containing organic chlorine with an alkali metal hydroxide and a metal hydride in a solvent mainly composed of a cyclic ether.
（作用）
本発明において用いる環状エーテル溶媒は、エポキシ樹
脂、アルカリ金属水酸化物及び金属水素化物を均一に分
散させ、これによってエポキシ樹脂中に含まれる有機塩
素の捕捉反応を均−且つ有効に行なわせるものである。(Function) The cyclic ether solvent used in the present invention uniformly disperses the epoxy resin, alkali metal hydroxide, and metal hydride, thereby uniformly and effectively performing the scavenging reaction of organic chlorine contained in the epoxy resin. It is something that can be done.
しかもこの環状エーテルはアルカリ等に対して極めて安
定な化合物であり、ケトン系の溶媒の様にアルカリ存在
下で縮合反応等の副反応を生ずるおそれは全くない。Furthermore, this cyclic ether is a compound that is extremely stable against alkalis and the like, and unlike ketone solvents, there is no risk of side reactions such as condensation reactions occurring in the presence of alkali.
またアルカリ金属水酸化物は、エポキシ樹脂中に含まれ
る有機塩素と反応して水溶性の塩を形成する。即ち水溶
性塩の形で有機塩素を捕捉する。Further, the alkali metal hydroxide reacts with organic chlorine contained in the epoxy resin to form a water-soluble salt. That is, it captures organic chlorine in the form of water-soluble salts.
金属水素化物は、有機塩素から塩素イオンを遊離させる
際にエポキシ樹脂が着色する傾向を抑制し、無色透明の
樹脂を得る作用をする。またエポキシ樹脂の精製処理に
際してゲル状物質の副生を抑制する作用を有する。The metal hydride suppresses the tendency of the epoxy resin to become colored when liberating chlorine ions from organic chlorine, and functions to obtain a colorless and transparent resin. It also has the effect of suppressing the production of gel-like substances as a by-product during the purification process of epoxy resins.
（発明の効果）
かくして本発明によれば、エポキシ樹脂中に含まれる有
機塩素の量を大きく低減するとともに、樹脂を実買上無
色透明にすることができる。しかもこの方法は、高価な
薬剤を使用したり、特殊な条件下で反応させたりするこ
ともなく、経済的であるうえに、副生物をエポキシ樹脂
中に残すこともない。従って本発明は、工業的なエポキ
シ樹脂の精製方法として有利であって、この方法で精製
されたエポキシ樹脂が電子部品の分野において信頼性の
高い製品を提供できること、とくに、発光素子の材料と
して好適なことは明らかである。(Effects of the Invention) Thus, according to the present invention, the amount of organic chlorine contained in the epoxy resin can be greatly reduced, and the resin can be made colorless and transparent when purchased. Furthermore, this method does not use expensive chemicals or require reactions under special conditions, is economical, and does not leave any by-products in the epoxy resin. Therefore, the present invention is advantageous as an industrial epoxy resin purification method, and the epoxy resin purified by this method can provide highly reliable products in the field of electronic components, and is particularly suitable as a material for light emitting devices. That is clear.
（発明の好適な憇ｍ＞
二二ヱ之旦１
本発明の精製方法の対象とするエポキシ樹脂は、レゾル
シノール、ハイドロキノンなどの！＃環多価フェノール
または２．２−ビス（４−ヒドロキシフェニル）プロパ
ン〔ビスフェノールＡ〕、１．１−ビス（４−ヒドロキ
シフェニル）エタン〔ビスフェノールＡＤ）、２．２−
ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プ
ロパン、フェノールノボラック、クレゾールノボラック
などの多環多価フェノールをエピクロルヒドリンと反応
させて得られる、有機塩素含有量が０．１〜１．５重量
％の程度のエポキシ樹脂である。(Preferred embodiments of the invention> 22ヱノdan 1) The epoxy resin targeted for the purification method of the present invention is !# ring polyhydric phenol such as resorcinol and hydroquinone, or 2,2-bis(4-hydroxyphenyl). Propane [bisphenol A], 1.1-bis(4-hydroxyphenyl)ethane [bisphenol AD), 2.2-
Organic chlorine content of 0.1 to 1.5% by weight, obtained by reacting polycyclic polyhydric phenols such as bis(3,5-dibromo-4-hydroxyphenyl)propane, phenol novolac, and cresol novolak with epichlorohydrin. It is a grade of epoxy resin.
直重
本発明において溶媒として使用する環状エーテルとして
は、１．４−ジオキサン、テトラヒドロフラン及びテト
ラヒドロピラン等が使用される。As the cyclic ether used as a solvent in the present invention, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, etc. are used.
かかる溶媒は、処理すべきエポキシ樹脂の１００重量部
当たり１０乃至２００重量部の割合で使用され、この溶
媒量が少ないとエポキシ樹脂を十分に希釈できず、有機
塩素化合物とアルカリ金属水酸化物及び金属水素化物と
の反応が不完全となり、また多い場合には反応後におけ
る溶媒回収に要する労力が大となり、経済的にも不利と
なる。Such a solvent is used in a proportion of 10 to 200 parts by weight per 100 parts by weight of the epoxy resin to be treated. If the amount of solvent is small, the epoxy resin cannot be diluted sufficiently, and organic chlorine compounds, alkali metal hydroxides and The reaction with the metal hydride will be incomplete, and if there is a large amount, the labor required to recover the solvent after the reaction will be large, which will be economically disadvantageous.
また前述した環状エーテル溶媒は単独で使用してもよい
し、ベンゼン、トルエン等の芳香族炭化水素、或いはメ
チルエチルケトン、メチルイソブチルケトン等のケトン
類と混合して使用することもできる。ただし、後者の使
用量は混合溶媒中の％以下とすべきである。Further, the above-mentioned cyclic ether solvent may be used alone or in combination with aromatic hydrocarbons such as benzene and toluene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone. However, the amount of the latter used should be less than % of the mixed solvent.
アルカリ金属 化
本発明において、エポキシ樹脂中に含まれる有機塩素を
水溶性塩の形で捕捉するために使用するアルカリ金属水
酸化物としては、ＮａＯＨ，ＫＯ）１．Ｌｉ０１ｌが使
用されるが、経済性の見地からＮａＯＨが好適に使用さ
れる。Alkali metalization In the present invention, the alkali metal hydroxides used to capture organic chlorine contained in the epoxy resin in the form of water-soluble salts include NaOH, KO)1. Although Li01l is used, NaOH is preferably used from an economical point of view.
このアルカリ金属水酸化物は、エポキシ樹脂中に含まれ
る有機塩素１当量当たり０．５乃至１０当量、特に１乃
至５当量の割合で使用される。The alkali metal hydroxide is used in an amount of 0.5 to 10 equivalents, particularly 1 to 5 equivalents, per equivalent of organic chlorine contained in the epoxy resin.
アルカリ金属水酸化物の量が、エポキシ樹脂中の有機塩
素に対して０．５当量を下回る少量では、塩素含有量を
十分に低減することができず、１０当量より過剰に加え
ても効果が飽和し無意味である。If the amount of alkali metal hydroxide is less than 0.5 equivalent to the organic chlorine in the epoxy resin, the chlorine content cannot be sufficiently reduced, and even if it is added in excess of 10 equivalents, there is no effect. It is saturated and meaningless.
このアルカリ金属水酸化物は、それ単独で、即ち固体の
まま使用してもよいが、−船釣には水溶液の形で使用す
ることもできる。但し水溶液の形で使用する場合には、
水溶液濃度は５０重量％以上とすることが望ましく、こ
の濃度が希薄であると多量のゲル状物質が副生ずる傾向
がある。The alkali metal hydroxide may be used alone, ie in solid form, but for boat fishing it can also be used in the form of an aqueous solution. However, when used in the form of an aqueous solution,
The concentration of the aqueous solution is desirably 50% by weight or more; if this concentration is too dilute, a large amount of gel-like material tends to be produced as a by-product.
１星水工上句
本発明においては、エポキシ樹脂の着色を防止するため
に金属水素化物を使用するが、かかる金属水素化物とし
ては例えばＮａＢ）１． 、 ＬｉＢＨ４，ＬｉＡ３
Ｎ４等が好適に使用される。In the present invention, a metal hydride is used to prevent coloring of the epoxy resin, and such metal hydrides include, for example, NaB)1. , LiBH4, LiA3
N4 etc. are preferably used.
この様な金属水素化物は、エポキシ樹脂中に含有される
有機塩素１当量当たり０．０５乃至２当量、特に０．１
乃至１．５当量の割合で使用される。０．０５当量より
も少ない場合には、所望の着色防止効果が十分でなく、
また２当量よりも多く使用したとしてもそれ以上の効果
は得られず、却って経済的に不利となる。Such metal hydride is used in an amount of 0.05 to 2 equivalents, particularly 0.1 equivalent per equivalent of organic chlorine contained in the epoxy resin.
It is used in a proportion of 1 to 1.5 equivalents. If it is less than 0.05 equivalent, the desired coloration prevention effect will not be sufficient,
Moreover, even if more than 2 equivalents are used, no further effect can be obtained, and this becomes economically disadvantageous.
この金属水素化物も単独で使用することができるが、５
０重量％以上の濃度の水溶液の形で用いることもできる
。水溶液濃度が５０重量％よりも低い場合には、ゲル状
物質を副生ずる傾向がある。This metal hydride can also be used alone, but
It can also be used in the form of an aqueous solution with a concentration of 0% by weight or more. When the concentration of the aqueous solution is lower than 50% by weight, gel-like substances tend to be produced as by-products.
五翌蓋１
本発明においては、処理すべきエポキシ樹脂を、前述し
た環状エーテル溶媒、アルカリ金属水酸化物及び金属水
素化物と混合し、５０乃至１５０℃、特に６０乃至１０
０℃の温度に加熱し、０．５乃至３時間攪拌することに
よって有機塩素を水溶性の無機塩として捕捉する。Lid 1 In the present invention, the epoxy resin to be treated is mixed with the above-mentioned cyclic ether solvent, alkali metal hydroxide and metal hydride.
The organic chlorine is captured as a water-soluble inorganic salt by heating to a temperature of 0° C. and stirring for 0.5 to 3 hours.
この反応温度が５０℃よりも低い場合には、反応時間が
極めて長くなって工業的に不利となり、また１５０℃を
超える場合には副反応等を生じるおそれがある。If the reaction temperature is lower than 50°C, the reaction time becomes extremely long, which is industrially disadvantageous, and if it exceeds 150°C, side reactions may occur.
エポキシ樹 の 離回収
アルカリ処理後の反応混合物からのエポキシ樹脂の分離
回収は、下記の様な常法に従えばよい。Separation and recovery of epoxy resin The separation and recovery of the epoxy resin from the reaction mixture after the alkali treatment may be carried out in accordance with the following conventional method.
例えば反応終了後に、減圧下で環状エーテルを蒸留回収
し、ベンゼン、トルエンまたはキシレン等の芳香族炭化
水素或いはメチルイソブチルケトン、シクロヘキサノン
等のケトン類等の他の溶媒を残留物に加えてエポキシ樹
脂を抽出する。For example, after the reaction is complete, the cyclic ether is distilled and recovered under reduced pressure, and other solvents such as aromatic hydrocarbons such as benzene, toluene, or xylene, or ketones such as methyl isobutyl ketone and cyclohexanone are added to the residue to form an epoxy resin. Extract.
更にこの混合物を水洗して、捕捉された有機塩素の水溶
性塩及び余剰のアルカリ金属水酸化物及び金属水酸化物
を水層とともに分離除去する。この際、必要によりリン
酸、第１リン酸ナトリウム等を用いてアルカリ金属水酸
化物の中和処理を行なっておく。Furthermore, this mixture is washed with water to separate and remove the captured water-soluble salt of organic chlorine and excess alkali metal hydroxide and metal hydroxide together with the aqueous layer. At this time, if necessary, the alkali metal hydroxide is neutralized using phosphoric acid, dibasic sodium phosphate, or the like.
次いで有機層中に残存する水分を有機溶媒との共沸蒸留
によって除去し、更に溶媒を除去した後、必要によりか
過を行ない、精製エポキシ樹脂を得る。Next, water remaining in the organic layer is removed by azeotropic distillation with an organic solvent, and after further removing the solvent, filtration is performed if necessary to obtain a purified epoxy resin.
かくして得られた精製エポキシ樹脂は、有機塩素含量が
極めて低減され、また透明性も良好である。The purified epoxy resin thus obtained has extremely reduced organic chlorine content and good transparency.
（実施例）
第１表に示す６種類のエポキシ樹脂（Ｎｏ１〜６）２０
０ｇをそれぞれ各種環状エーテル、アルカリ金属水酸化
物（エポキシ樹脂中の有機塩素１当量当たり４．０当量
）及びＮａＢＨ４（全有機塩素１当量当たり１．０当量
）を、温度計、攪拌翼及び窒素導入管を備えた容量１１
！、の四つロフラスコに入れ、窒素置換して所定温度に
加熱し、２時間攪拌した。(Example) Six types of epoxy resins (Nos. 1 to 6) shown in Table 1 20
0 g of various cyclic ethers, alkali metal hydroxides (4.0 equivalents per equivalent of organic chlorine in the epoxy resin), and NaBH4 (1.0 equivalents per equivalent of total organic chlorine) were added to a thermometer, stirring blade, and nitrogen. Capacity 11 with inlet tube
! The mixture was placed in a four-hole flask, the atmosphere was replaced with nitrogen, the mixture was heated to a predetermined temperature, and the mixture was stirred for 2 hours.
用いた環状エーテル、アルカリ金属水酸化物の種類、使
用量等、並びに反応温度は第１表に併せて表示する。The type and amount of the cyclic ether and alkali metal hydroxide used, as well as the reaction temperature, are also shown in Table 1.
尚、Ｎｏ６のエポキシ樹脂の処理にあたっては、比較の
ためＮａＢＨ，を全く使用しなかった。For comparison, no NaBH was used in the treatment of No. 6 epoxy resin.
反応終了後、フラスコ内を減圧して１００℃以下の温度
で環状エーテルを蒸留回収した。Ｎｏ５の残漬にはメチ
ルイソブチルケトンを、その他の歯の残漬にはキシレン
を加えて水層を除去した。有機層に過剰の第一リン酸ナ
トリウム水溶液を加えて中和し、水洗により副生塩を取
り除いた。有機層に残った微量の水分をメチルイソブチ
ルケトンまたはキシレンとの共沸蒸留によって除き、残
存する塩をチ過し、さらにメチルイソブチルケトンまた
はキシレンを蒸留除去してエポキシ樹脂を得た。After the reaction was completed, the pressure inside the flask was reduced and the cyclic ether was distilled and recovered at a temperature of 100° C. or lower. Methyl isobutyl ketone was added to the remaining teeth of No. 5, and xylene was added to the remaining teeth of the other teeth to remove the aqueous layer. The organic layer was neutralized by adding an excess aqueous monobasic sodium phosphate solution, and by-product salts were removed by washing with water. A trace amount of water remaining in the organic layer was removed by azeotropic distillation with methyl isobutyl ketone or xylene, the remaining salt was filtered, and methyl isobutyl ketone or xylene was further removed by distillation to obtain an epoxy resin.
得られたエポキシ樹脂の、エポキシ当量、有機塩素量、
易加水分解性塩素量、難船水分解性塩素量および色相を
、第２表に示す。Epoxy equivalent and organic chlorine content of the obtained epoxy resin,
Table 2 shows the amount of easily hydrolyzable chlorine, the amount of water decomposable chlorine, and the hue.
エポキシ樹脂中の有機塩素量は、全塩素量から塩素イオ
ン量を差引いて求めた。全塩素量は、エポキシ樹脂を酸
素オーブン中で完全に燃焼させ、硝酸銀によって滴定す
ることにより定量した。易加水分解性塩素量は、エポキ
シ樹脂をトルエンに溶解し、０．ＩＮのＮａＯＨメタノ
ール溶液を加えて１５分間還流後１．０．ＩＮのＨＣｐ
水溶液で残存するＮａＯＨを逆滴定して求めた。難船水
分解性塩素量は、有機塩素量から易加水分解性□塩素量
を差し引いたものである。The amount of organic chlorine in the epoxy resin was determined by subtracting the amount of chlorine ions from the total amount of chlorine. The total chlorine content was determined by complete combustion of the epoxy resin in an oxygen oven and titration with silver nitrate. The amount of easily hydrolyzable chlorine is determined by dissolving the epoxy resin in toluene and adjusting the amount to 0. After adding a methanol solution of IN NaOH and refluxing for 15 minutes, the temperature was reduced to 1.0. IN HCp
NaOH remaining in the aqueous solution was determined by back titration. The amount of water-decomposable chlorine is the amount of easily hydrolyzable □chlorine subtracted from the amount of organic chlorine.
第２表にみるとおり、エポキシ樹脂中の有機塩素含有量
はいずれも０．０８重量％以下に低減し、加水分解性塩
素の含有量も２０ ｐｐｍ以下であった。As shown in Table 2, the organic chlorine content in the epoxy resins was reduced to 0.08% by weight or less, and the hydrolyzable chlorine content was also 20 ppm or less.
なお、エポキシ樹脂中の塩素イオン含有量はいずれも１
０ｐｐｍ以下であった。エポキシ樹脂の色相は、Ｎｏ６
が３５０であるのに対し、Ｎｏ １〜５は４０〜８０と
約１／９〜１／４であった。In addition, the chlorine ion content in the epoxy resin is 1
It was 0 ppm or less. The hue of the epoxy resin is No6
was 350, whereas Nos. 1 to 5 were 40 to 80, about 1/9 to 1/4.
Claims (8)
ルを主体とする溶媒中で、アルカリ金属水酸化物および
金属水素化物を作用させることからなるエポキシ樹脂の
精製方法。(1) A method for purifying an epoxy resin, which comprises reacting an epoxy resin containing organic chlorine with an alkali metal hydroxide and a metal hydride in a solvent mainly containing a cyclic ether.
乃至２００重量部の割合で使用する特許請求の範囲第１
項記載の方法。(2) Add 10 parts of the solvent per 100 parts by weight of the epoxy resin.
Claim 1 used in a proportion of 200 parts by weight
The method described in section.
ヒドロフラン、またはテトラヒドロピランを使用する特
許請求の範囲第１項記載の方法。(3) The method according to claim 1, wherein 1,4-dioxane, tetrahydrofuran, or tetrahydropyran is used as the cyclic ether.
またはＬｉＯＨを使用する特許請求の範囲第１項記載の
方法。(4) NaOH, KOH as alkali metal hydroxides
Alternatively, the method according to claim 1, which uses LiOH.
れる有機塩素１当量当たり０．５乃至１０当量の割合で
使用する特許請求の範囲第４項記載の方法。(5) The method according to claim 4, wherein the alkali metal hydroxide is used in an amount of 0.5 to 10 equivalents per equivalent of organic chlorine contained in the epoxy resin.
４、ＬｉＡｌＨ＿４を使用する特許請求の範囲第１項記
載の方法。(6) As metal hydrides, NaBH_4, LiBH_
4. The method according to claim 1, which uses LiAlH_4.
有機塩素１当量当たり０．０５乃至２当量の割合で使用
する特許請求の範囲第６項記載の方法。(7) The method according to claim 6, wherein the metal hydride is used in a ratio of 0.05 to 2 equivalents per equivalent of organic chlorine contained in the epoxy resin.
１５０℃の温度で０．５乃至３時間攪拌下に行なう特許
請求の範囲第１項記載の方法。(8) The method according to claim 1, wherein the treatment of the epoxy resin in the solvent is carried out at a temperature of 50 to 150° C. for 0.5 to 3 hours with stirring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26367387A JPH01108218A (en) | 1987-10-21 | 1987-10-21 | Purification of epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26367387A JPH01108218A (en) | 1987-10-21 | 1987-10-21 | Purification of epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01108218A true JPH01108218A (en) | 1989-04-25 |
Family
ID=17392754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26367387A Pending JPH01108218A (en) | 1987-10-21 | 1987-10-21 | Purification of epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01108218A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013183736A1 (en) * | 2012-06-07 | 2013-12-12 | 日本化薬株式会社 | Epoxy resin composition, cured product thereof, and curable resin composition |
| WO2013183735A1 (en) * | 2012-06-07 | 2013-12-12 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product |
| WO2015037584A1 (en) * | 2013-09-10 | 2015-03-19 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
| CN115073649A (en) * | 2022-07-20 | 2022-09-20 | 杜彪 | Dechlorinating agent and preparation method and application thereof |
-
1987
- 1987-10-21 JP JP26367387A patent/JPH01108218A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013183736A1 (en) * | 2012-06-07 | 2013-12-12 | 日本化薬株式会社 | Epoxy resin composition, cured product thereof, and curable resin composition |
| WO2013183735A1 (en) * | 2012-06-07 | 2013-12-12 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product |
| JPWO2013183736A1 (en) * | 2012-06-07 | 2016-02-01 | 日本化薬株式会社 | Epoxy resin composition, cured product thereof, and curable resin composition |
| JPWO2013183735A1 (en) * | 2012-06-07 | 2016-02-01 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product |
| WO2015037584A1 (en) * | 2013-09-10 | 2015-03-19 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, cured product and semiconductor device |
| CN115073649A (en) * | 2022-07-20 | 2022-09-20 | 杜彪 | Dechlorinating agent and preparation method and application thereof |
| CN115073649B (en) * | 2022-07-20 | 2023-10-27 | 智仑超纯环氧树脂(西安)有限公司 | Chlorine removing agent and preparation method and application thereof |
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