JPH0759617B2 - Method for producing high molecular weight epoxy resin - Google Patents
Method for producing high molecular weight epoxy resinInfo
- Publication number
- JPH0759617B2 JPH0759617B2 JP2239398A JP23939890A JPH0759617B2 JP H0759617 B2 JPH0759617 B2 JP H0759617B2 JP 2239398 A JP2239398 A JP 2239398A JP 23939890 A JP23939890 A JP 23939890A JP H0759617 B2 JPH0759617 B2 JP H0759617B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- molecular weight
- high molecular
- bifunctional
- film
- 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
- 239000003822 epoxy resin Substances 0.000 title claims description 102
- 229920000647 polyepoxide Polymers 0.000 title claims description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 230000001588 bifunctional effect Effects 0.000 claims description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- -1 alkyl phosphorus Chemical compound 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims 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 26
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000000149 argon plasma sintering Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000006266 etherification reaction Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000013034 phenoxy resin Substances 0.000 description 3
- 229920006287 phenoxy resin Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、接着剤、絶縁材料、塗料、成形品、フィルム
などに用いられる高分子量エポキシ樹脂の製造方法に関
する。TECHNICAL FIELD The present invention relates to a method for producing a high molecular weight epoxy resin used for adhesives, insulating materials, paints, molded products, films and the like.
比較的低分子量の二官能エポキシ樹脂と二官能フェノー
ル類を原料として高分子量エポキシ樹脂を製造する方法
は、一般に二段法と呼ばれ、この方法に関する最初の文
献は特公昭28−4494号公報である。この公報では重合触
媒として水酸化ナトリウムを用い、無溶媒下、150〜200
℃で反応させることにより、エポキシ当量が5,600の高
分子量エポキシ樹脂を得ている。この樹脂の平均分子量
は、約11,000であると推定できる。A method for producing a high molecular weight epoxy resin from a relatively low molecular weight difunctional epoxy resin and a bifunctional phenol as a raw material is generally called a two-step method, and the first document relating to this method is Japanese Patent Publication No. is there. In this publication, sodium hydroxide is used as a polymerization catalyst, and the solvent is 150-200 without solvent.
A high molecular weight epoxy resin having an epoxy equivalent of 5,600 is obtained by reacting at ℃. The average molecular weight of this resin can be estimated to be about 11,000.
重合触媒としてリチウム化合物を用いた文献としては特
公昭37−3394号公報及び特公昭38−334号公報がある。
これらに記載されている製造方法においては、分子量1
0,000以上の樹脂は得られていない。Documents using a lithium compound as a polymerization catalyst include JP-B-37-3394 and JP-B-38-334.
In the production methods described in these, the molecular weight 1
No more than 0,000 resins have been obtained.
重合触媒としてホスホニウム塩を用いた文献としては特
公昭50−5760号公報、特公昭52−19878号公報、特開昭5
0−110499号公報、特開昭54−52200号公報、特開昭58−
185611号公報、特開昭60−118757号公報、特開昭60−14
4323号公報、特開昭60−114324号公報がある。これらに
記載されている製造方法のうち、高分子量エポキシ樹脂
が得られているものとしては、特開昭54−52200号公
報、特開昭60−118757号公報、特開昭60−144323号公
報、特開昭60−114324号公報に記載されている方法があ
る。これらの方法においてはいずれの場合にも、溶媒中
で重合反応を行っている。Documents using a phosphonium salt as a polymerization catalyst include JP-B-50-5760, JP-B-52-19878, and JP-A-5-19878.
0-110499, JP-A-54-52200, JP-A-58-
185611, JP-A-60-118757, JP-A-60-14
There are 4323 and JP-A-60-114324. Among the production methods described in these, those having obtained a high molecular weight epoxy resin include those disclosed in JP-A-54-52200, JP-A-60-118757, and JP-A-60-144323. , JP-A-60-114324. In any of these methods, the polymerization reaction is carried out in a solvent.
しかしながら、これらの公報に記載されている実施例に
よれば、反応溶媒中の樹脂固形分濃度は最も少ないもの
で40重量％である。本発明者らは、反応時の固形分濃度
がこのように多い場合には、副反応による枝分かれが生
じ、直鎖状の高分子量エポキシ樹脂が生成しないことを
確認した。特に特開昭60−144323号公報、特開昭60−11
4324号公報に示されているような重量平均分子量が100,
000程度の超高分子量エポキシ樹脂が直鎖状の場合に
は、フィルム形成能を有することを本発明者らは確認し
ているが、特開昭60−144323号公報、特開昭60−114324
号公報には、フィルム形成能を有するという趣旨の記載
は見当たらない。However, according to the examples described in these publications, the resin solid content concentration in the reaction solvent is 40% by weight at the lowest. The present inventors have confirmed that when the solid content concentration during the reaction is such high, branching occurs due to a side reaction and a linear high molecular weight epoxy resin is not produced. In particular, JP-A-60-144323 and JP-A-60-11
The weight average molecular weight as shown in 4324 publication is 100,
It has been confirmed by the present inventors that the ultra-high molecular weight epoxy resin of about 000 has a film-forming ability when it is linear, but it is disclosed in JP-A-60-144323 and JP-A-60-114324.
In the publication, there is no description to the effect that it has a film forming ability.
すなわち、従来の高分子量エポキシ樹脂の製造方法で
は、フィルム形成能を有するまでに高分子量化した直鎖
状エポキシ樹脂を得ることかできなかったことは明らか
である。That is, it is clear that the conventional method for producing a high molecular weight epoxy resin could not obtain a linear epoxy resin having a high molecular weight until it had a film-forming ability.
本発明は、フィルム形成能を有するまでに高分子量化し
た超高分子量エポキシ樹脂の製造方法を提供することを
目的とする。An object of the present invention is to provide a method for producing an ultra-high molecular weight epoxy resin which has a high molecular weight until it has a film forming ability.
本発明の高分子量エポキシ樹脂の製造方法は、二官能エ
ポキシ樹脂と二官能フェノール類を触媒の存在下、重合
反応溶媒中で加熱して重合させ、高分子量エポキシ樹脂
を製造する方法において、二官能エポキシ樹脂と二官能
フェノール類の配合当量比をエポキシ基／フェノール性
水酸基＝1:0.9〜1.1とし、アミド系溶媒中アルキルりん
系触媒を用いることを特徴とする。The method for producing a high molecular weight epoxy resin of the present invention is a method for producing a high molecular weight epoxy resin by heating a bifunctional epoxy resin and a bifunctional phenol in a polymerization reaction solvent in the presence of a catalyst to polymerize the bifunctional epoxy resin. It is characterized in that the compounding equivalent ratio of the epoxy resin and the bifunctional phenol is set to epoxy group / phenolic hydroxyl group = 1: 0.9 to 1.1 and an alkylphosphorus catalyst in an amide solvent is used.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明における二官能エポキシ樹脂は、分子内に二個の
エポキシ基をもつ化合物であばどのようなものでもよ
く、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフ
ェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキ
シ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹
脂、二官能フェノール類のジグリシジルエーテル化物、
二官能アルコール類のジグリシジルエーテル化物、これ
らのハロゲン化物、これらの水素添加物などがある。こ
れらの化合物の分子量はどのようなものでもよい。これ
らの化合物は何種類かを併用することができる。また二
官能エポキシ樹脂以外の成分が、不純物として含まれて
いても構わない。The bifunctional epoxy resin in the present invention may be any compound having two epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, Alicyclic epoxy resin, aliphatic chain epoxy resin, diglycidyl ether of bifunctional phenols,
There are diglycidyl ether compounds of difunctional alcohols, halides thereof, hydrogenated products thereof, and the like. The molecular weight of these compounds may be any. Several kinds of these compounds can be used in combination. Further, components other than the bifunctional epoxy resin may be included as impurities.
本発明における二官能フェノール類は、２個のフェノー
ル性水酸基をもつ化合物であればどのようなものでもよ
く、例えば、単環二官能フェノールであるヒドロキノ
ン、レゾルシノール、カテコール、多環二官能フェノー
ルであるビスフェノールＡ、ビスフェノールＦ及びこれ
らのハロゲン化物、アルキル基置換体などがある。これ
らの化合物の分子量はどのようなものでもよい。これら
の化合物は何種類かを併用することができる。また二官
能フェノール類以外の成分が、不純物として含まれてい
ても構わない。The bifunctional phenol in the present invention may be any compound as long as it has two phenolic hydroxyl groups, and examples thereof include monocyclic bifunctional phenols such as hydroquinone, resorcinol, catechol, and polycyclic bifunctional phenols. Examples include bisphenol A, bisphenol F, their halides, and alkyl group-substituted products. The molecular weight of these compounds may be any. Several kinds of these compounds can be used in combination. Further, components other than the bifunctional phenols may be included as impurities.
本発明におけるアルキルりん系触媒は、エポキシ基とフ
ェノール性水酸基のエーテル化反応を促進させるような
触媒能をもつ化合物であればどのようなものでもよく、
例えばトリ−ｎ−プロピルホスフィン、トリ−ｎ−ブチ
ルホスフインなどがある。これらの触媒は併用すること
ができる。また、アルカリ金属系、イミダゾール系に代
表されるその他の触媒と併用しても構わない。The alkylphosphorus catalyst in the present invention may be any compound having a catalytic ability to promote the etherification reaction of the epoxy group and the phenolic hydroxyl group,
Examples include tri-n-propylphosphine and tri-n-butylphosphine. These catalysts can be used in combination. Further, it may be used in combination with other catalysts represented by alkali metal type and imidazole type.
本発明における重合反応溶媒は、原料となるエポキシ樹
脂とフェノール類を溶解するアミド系溶媒がよい。アミ
ド系溶媒としては、例えばホルムアミド、Ｎ−メチルホ
ルムアミド、N,N−ジメチルホルムアミド、アセトアミ
ド、Ｎ−メチルアセトアミド、N,N−ジメチルアセトア
ミド、N,N,N′,N′−テトラメチル尿素、２−ピロリド
ン、Ｎ−メチルピロリドンなどがある。これらの溶媒は
併用することができる。また、エーテル系などのほかの
溶媒と併用しても構わない。The polymerization reaction solvent in the present invention is preferably an amide-based solvent that dissolves the raw material epoxy resin and phenols. Examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N, N ′, N′-tetramethylurea, 2 -Pyrrolidone, N-methylpyrrolidone and the like. These solvents can be used in combination. Further, it may be used in combination with other solvent such as ether type.
本発明における製造条件としては二官能エポキシ樹脂と
二官能フェノール類の配合当量比は、エポキシ基／フェ
ノール性水酸基＝1:0.9〜1.1とする。0.9当量より少な
いと、直鎖状に高分子量化せずに、副反応が起きて架橋
し、樹脂が溶媒に不溶になる。1.1当量より多いと樹脂
の高分子量化が進まない。As the production conditions in the present invention, the compounding equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol is set to epoxy group / phenolic hydroxyl group = 1: 0.9 to 1.1. If the amount is less than 0.9 equivalent, the polymer does not linearly increase in molecular weight, a side reaction occurs and crosslinks, and the resin becomes insoluble in the solvent. If the amount is more than 1.1 equivalents, the high molecular weight resin will not proceed.
触媒の配合量は特に制限はないが、一般には二官能エポ
キシ樹脂１モルに対して触媒は0.0001〜0.2モル程度で
ある。この範囲より少ないと高分子量化反応が著しく遅
く、この範囲より多いと副反応が多くなり直鎖状に高分
子量化しないことがある。The amount of the catalyst to be blended is not particularly limited, but generally 0.0001 to 0.2 mol of the catalyst is used with respect to 1 mol of the bifunctional epoxy resin. If the amount is less than this range, the high molecular weight reaction is remarkably slow, and if it is more than this range, side reactions increase and the molecular weight may not linearly increase.
製造時の合成反応温度は、60〜150℃であることが望ま
しい。60℃より低いと高分子量化反応が著しく遅く、15
0℃より高いと副反応が多くなり直鎖状に高分子量化し
ないことがある。The synthesis reaction temperature during production is preferably 60 to 150 ° C. If the temperature is lower than 60 ° C, the high molecular weight reaction is extremely slow, and
If the temperature is higher than 0 ° C, side reactions may increase and the molecular weight may not linearly increase.
製造時の合成反応における固形分濃度は、50％（重量
％、以下同じ）以下であればよいが、好ましくは30％以
下がよい。この範囲より高濃度の場合には、副反応が多
くなり直鎖状に高分子量化しにくくなる。したがって、
比較的高濃度で重合反応を行い、しかも直鎖状の高分子
量エポキシ樹脂を得ようとする場合には、反応温度を低
くし、触媒量を少なくすればよい。The solid content concentration in the synthetic reaction at the time of production may be 50% (% by weight, the same applies hereinafter) or less, but preferably 30% or less. When the concentration is higher than this range, side reactions increase and it becomes difficult to form a linear high molecular weight compound. Therefore,
When the polymerization reaction is carried out at a relatively high concentration and a linear high molecular weight epoxy resin is to be obtained, the reaction temperature may be lowered and the catalyst amount may be reduced.
本発明により得られた高分子量エポキシ樹脂はフィルム
形成能を有する超高分子量エポキシ樹脂であり、従来の
高分子量エポキシ樹脂に比較して、枝分かれが少なく、
更に高分子量化が進んでいると考えられ、十分な強度の
フィルム形成能を有する。得られたフィルムは、従来の
高分子量エポキシ樹脂を使用して成形したフィルムでは
実現が不可能な特性を有する。すなわち、強度が著しく
大きく、伸びが著しく大きい。The high molecular weight epoxy resin obtained by the present invention is an ultra high molecular weight epoxy resin having film forming ability, and has less branching as compared with the conventional high molecular weight epoxy resin,
It is considered that the polymer has a higher molecular weight and has a film forming ability with sufficient strength. The obtained film has properties that cannot be realized by a film formed using a conventional high molecular weight epoxy resin. That is, the strength is remarkably large and the elongation is remarkably large.
また、本発明のもう一つの特徴として、重合反応触媒と
してアルキルりん系化合物を用いることによって、溶媒
を用いた重合反応が速く進行することが挙げられる。Another feature of the present invention is that by using an alkyl phosphorus compound as a polymerization reaction catalyst, the polymerization reaction using a solvent proceeds rapidly.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
実施例１ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:177.5）177.5g、二官能フェノール
類としてビスフェノールＡ（水酸基当量:115.5）115.5
g、エーテル化触媒としてトリ−ｎ−プロピルホスフィ
ン4.81gをN,N−メチルアセトアミド694.9gに溶解させ、
反応系中の固形分濃度を30％とした．これを機械的に攪
拌しながら、110℃のオイルバス中で反応系中の温度を1
00℃に保ち、そのまま24時間保持した。その結果、粘度
が1,331mPa・ｓの高分子量エポキシ樹脂溶液が得られ
た。このエポキシ樹脂の重量平均分子量はゲル透過クロ
マトグラフィーによって測定した結果では72,000、光散
乱法によって測定した結果では55,000であった。又この
高分子量エポキシ樹脂の稀薄溶液（N,N−ジメチルアセ
トアミド、30℃、以下同じ）の還元粘度は0.750（dl/
g）であった。この高分子量エポキシ樹脂溶液をガラス
板に塗布し、200℃で１時間乾燥して、厚さ30μｍのエ
ポキシ樹脂フィルムを得た。このフィルムの引っ張り強
度は34.3MPa、伸びは43.3％、引っ張り弾性率は415MPa
であった。またガラス転移温度は100℃、熱分解温度は3
47℃であった。Example 1 177.5 g of bisphenol A type epoxy resin (epoxy equivalent: 177.5) as a bifunctional epoxy resin and bisphenol A (hydroxyl equivalent: 115.5) as a bifunctional phenol 115.5
g, 4.81 g of tri-n-propylphosphine as an etherification catalyst was dissolved in 694.9 g of N, N-methylacetamide,
The solid content concentration in the reaction system was 30%. While mechanically stirring this, keep the temperature in the reaction system at 1 ° C in an oil bath at 110 ° C.
It was kept at 00 ° C and kept as it was for 24 hours. As a result, a high molecular weight epoxy resin solution having a viscosity of 1,331 mPa · s was obtained. The weight average molecular weight of this epoxy resin was 72,000 as measured by gel permeation chromatography and 55,000 as measured by light scattering method. The reduced viscosity of this dilute solution of high molecular weight epoxy resin (N, N-dimethylacetamide, 30 ° C, the same below) is 0.750 (dl /
g). This high molecular weight epoxy resin solution was applied to a glass plate and dried at 200 ° C. for 1 hour to obtain an epoxy resin film having a thickness of 30 μm. This film has a tensile strength of 34.3MPa, an elongation of 43.3% and a tensile modulus of 415MPa.
Met. The glass transition temperature is 100 ° C and the thermal decomposition temperature is 3.
It was 47 ° C.
実施例２ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:177.5）177.5g、二官能フェノール
類としてビスフェノールＡ（水酸基当量:115.5）115.5
g、エーテル化触媒としてトリ−ｎ−ブチルホスフィン
6.07gをN,N−ジメチルアセトアミド697.8gに溶解させ、
反応系中の固形分濃度を30％とした。これを機械的に攪
拌しながら、110℃のオイルバス中で反応系中の温度を1
00℃に保ち、そのまま24時間保持した。その結果、粘度
が1,152mPa・ｓの高分子量エポキシ樹脂溶液が得られ
た。このエポキシ樹脂の重量平均分子量は、ゲル透過ク
ロマトグラフィーによって測定した結果では89,000、光
散乱法によって測定した結果では65,000であった。ま
た、この高分子量エポキシ樹脂の稀薄溶液の還元粘度
は、0.842（dl/g）であった。この高分子量エポキシ樹
脂溶液をガラス板に塗布し、200℃で１時間乾燥して、
厚さ35μｍのエポキシ樹脂フィルムを得た。このフィル
ムの引っ張り粘度は26.5MPa、伸びは44.3％、引っ張り
弾性率は400MPaであった。またガラス転移温度は102
℃、熱分解温度は350℃であった。Example 2 177.5 g of bisphenol A type epoxy resin (epoxy equivalent: 177.5) as a bifunctional epoxy resin and bisphenol A (hydroxyl equivalent: 115.5) as a bifunctional phenol 115.5
g, tri-n-butylphosphine as an etherification catalyst
6.07 g was dissolved in N, N-dimethylacetamide 697.8 g,
The solid content concentration in the reaction system was 30%. While mechanically stirring this, keep the temperature in the reaction system at 1 ° C in an oil bath at 110 ° C.
It was kept at 00 ° C and kept as it was for 24 hours. As a result, a high molecular weight epoxy resin solution having a viscosity of 1,152 mPa · s was obtained. The weight average molecular weight of this epoxy resin was 89,000 as a result of measurement by gel permeation chromatography, and 65,000 as a result of measurement by a light scattering method. The reduced viscosity of the dilute solution of the high molecular weight epoxy resin was 0.842 (dl / g). This high molecular weight epoxy resin solution is applied to a glass plate and dried at 200 ° C for 1 hour,
An epoxy resin film having a thickness of 35 μm was obtained. The tensile viscosity of this film was 26.5 MPa, the elongation was 44.3%, and the tensile elastic modulus was 400 MPa. The glass transition temperature is 102.
℃, the thermal decomposition temperature was 350 ℃.
実施例３ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:173.2）173.2g、二官能フェノール
類としてヒドロキノン（水酸基当量:55.3）55.3g、エー
テル化触媒としてトリ−ｎ−プロピルホスフィン4.81g
をN,N−ジメチルアセトアミド933.2gに溶解させ、反応
系中の固形分濃度を20％とした。これを機械的に攪拌し
ながら、125℃のオイルバス中で反応系中の温度を120℃
に保ち、そのまま12時間保持した。その結果、粘度が1,
920mPa・ｓの高分子量エポキシ樹脂溶液が得られた。こ
のエポキシ樹脂の重量平均分子量は、ゲル透過クロマト
グラフィーによって測定した結果では108,000、光散乱
法によって測定した結果では87,500であった．また、こ
の高分子量エポキシ樹脂の稀薄溶液の還元粘度は0.890
（dl/g）であった。この高分子量エポキシ樹脂溶液をガ
ラス板に塗布し、200℃で１時間乾燥して、厚さ28μｍ
のエポキシ樹脂フィルムを得た。このフィルムの引っ張
り強度は36.7MPa、伸びは43.2％、引っ張り弾性率は392
MPaであった。またガラス転移温度は78℃、熱分解温度
は348℃であった。Example 3 173.2 g of a bisphenol A type epoxy resin (epoxy equivalent: 173.2) as a bifunctional epoxy resin, 55.3 g of hydroquinone (hydroxyl group equivalent: 55.3) as a bifunctional phenol, and tri-n-propylphosphine 4.81 g as an etherification catalyst.
Was dissolved in 933.2 g of N, N-dimethylacetamide to adjust the solid content concentration in the reaction system to 20%. While mechanically stirring this, keep the temperature in the reaction system at 120 ° C in an oil bath at 125 ° C.
And kept for 12 hours. As a result, the viscosity is 1.
A high molecular weight epoxy resin solution of 920 mPa · s was obtained. The weight average molecular weight of this epoxy resin was 108,000 as measured by gel permeation chromatography and 87,500 as measured by light scattering method. The reduced viscosity of a dilute solution of this high molecular weight epoxy resin is 0.890.
(Dl / g). This high molecular weight epoxy resin solution is applied to a glass plate and dried at 200 ° C for 1 hour to give a thickness of 28 μm.
The epoxy resin film of was obtained. This film has a tensile strength of 36.7 MPa, an elongation of 43.2% and a tensile modulus of 392.
It was MPa. The glass transition temperature was 78 ° C and the thermal decomposition temperature was 348 ° C.
実施例４ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:173.2）173.2g、二官能フェノール
類としてヒドロキノン（水酸基当量:55.3）55.3g、エー
テル化触媒としてトリ−ｎ−ブチルホスフィン6.07gを
N,N−ジメチルホルムアミド938.3gに溶解させ、反応系
中の固形分濃度を20％とした。これを機械的に攪拌しな
がら、125℃のオイルバス中で反応系中の温度を120℃に
保ち、そのまま12時間保持した。その結果、粘度が2,17
6mPa.sの高分子量エポキシ樹脂溶液が得られた。このエ
ポキシ樹脂の重量平均分子量は、ゲル透過クロマトグラ
フィーによって測定した結果では112,000、光散乱法に
よって測定した結果では89,500であった。また、この高
分子量エポキシ樹脂の稀薄溶液の還元粘度は0.925（dl/
g）であった。この高分子量エポキシ樹脂溶液をガラス
板に塗布し、200℃で１時間乾燥して、厚さ33μｍのエ
ポキシ樹脂フィルムを得た。このフィルムの引っ張り強
度は42.2MPa、伸びは49.0％、引っ張り弾性率は375MPa
であった。またガラス転移温度は79℃、熱分解温度は35
0℃であった。Example 4 173.2 g of bisphenol A type epoxy resin (epoxy equivalent: 173.2) as a bifunctional epoxy resin, 55.3 g of hydroquinone (hydroxyl equivalent: 55.3) as a bifunctional phenol, and tri-n-butylphosphine 6.07 g as an etherification catalyst.
It was dissolved in 938.3 g of N, N-dimethylformamide, and the solid content concentration in the reaction system was set to 20%. While mechanically stirring this, the temperature in the reaction system was kept at 120 ° C. in an oil bath at 125 ° C. and kept as it was for 12 hours. As a result, the viscosity is 2,17
A high molecular weight epoxy resin solution of 6 mPa.s was obtained. The weight average molecular weight of this epoxy resin was 112,000 as measured by gel permeation chromatography and 89,500 as measured by light scattering method. The reduced viscosity of this dilute solution of high molecular weight epoxy resin is 0.925 (dl /
g). This high molecular weight epoxy resin solution was applied to a glass plate and dried at 200 ° C. for 1 hour to obtain an epoxy resin film having a thickness of 33 μm. This film has a tensile strength of 42.2MPa, an elongation of 49.0% and a tensile modulus of 375MPa.
Met. The glass transition temperature is 79 ° C and the thermal decomposition temperature is 35.
It was 0 ° C.
実施例５ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:173.2）173.2g、二官能フェノール
類としてレゾルシノール（水酸基当量:55.4）55.4g、エ
ーテル化触媒としてトリ−ｎ−プロピルホスフィン4.81
gをN,N−ジメチルアセトアミド544.6gに溶解させ、反応
系中の固形分濃度を30％とした。これを機械的に攪拌し
ながら、115℃のオイルバス中で反応系中の温度を110℃
に保ち、そのまま20時間保持した。その結果、粘度が1,
306mPa・ｓの高分子量エポキシ樹脂溶液が得られた。こ
のエポキシ樹脂の重量平均分子量は、ゲル透過クロマト
グラフィーによって測定した結果では92,000、光散乱法
によって測定した結果では79,000であった。また、この
高分子量エポキシ樹脂の稀薄溶液の還元粘度は0.812（d
l/g）であった。この高分子量エポキシ樹脂溶液をガラ
ス板に塗布し、200℃で１時間乾燥して、厚さ30μｍの
エポキシ樹脂フィルムを得た。このフィルムの引っ張り
強度は38.2MPa、伸びは52.0％、引っ張り弾性率は435MP
aであった。またガラス転移温度は80℃、熱分解温度は3
45℃であった。Example 5 173.2 g of a bisphenol A type epoxy resin (epoxy equivalent: 173.2) as a bifunctional epoxy resin, 55.4 g of resorcinol (hydroxyl equivalent: 55.4) as a bifunctional phenol, and tri-n-propylphosphine 4.81 as an etherification catalyst.
g was dissolved in 544.6 g of N, N-dimethylacetamide to adjust the solid content concentration in the reaction system to 30%. While mechanically stirring this, keep the temperature in the reaction system at 110 ° C in an oil bath at 115 ° C.
And kept for 20 hours. As a result, the viscosity is 1.
A high molecular weight epoxy resin solution of 306 mPa · s was obtained. The weight average molecular weight of this epoxy resin was 92,000 as a result of measurement by gel permeation chromatography and 79,000 as a result of measurement by a light scattering method. The reduced viscosity of a dilute solution of this high molecular weight epoxy resin is 0.812 (d
l / g). This high molecular weight epoxy resin solution was applied to a glass plate and dried at 200 ° C. for 1 hour to obtain an epoxy resin film having a thickness of 30 μm. The tensile strength of this film is 38.2MPa, the elongation is 52.0%, the tensile modulus is 435MP.
It was a. The glass transition temperature is 80 ° C and the thermal decomposition temperature is 3.
It was 45 ° C.
実施例６ 二官能エポキシ樹脂としてビスフェノールＡ型エポキシ
樹脂（エポキシ当量:173.2）173.2g、二官能フェノール
類としてレゾルシノール（水酸基当量:55.4）55.4g、エ
ーテル化触媒としてトリ−ｎ−ブチルホスフイン6.07g
をN,N−ジメチルホルムアミド547.6gに溶解させ、反応
系中の固形分濃度を30％とした。これを機械的に攪拌し
ながら、115℃のオイルバス中で反応系中の温度を110℃
に保ち、そのまま20時間保持した。その結果、粘度が1,
740mPa・ｓの高分子量エポキシ樹脂溶液が得られた。こ
のエポキシ樹脂の重量平均分子量は、ゲル透過クロマト
グラフィーによって測定した結果では92,000、光散乱法
によって測定した結果では83,000であった。また、この
高分子量エポキシ樹脂の稀薄溶液の還元粘度は、0.785
（dl/g）であった。この高分子量エポキシ樹脂溶液をガ
ラス板に塗布し、200℃で１時間乾燥して、厚さ30μｍ
のエポキシ樹脂フィルムを得た。このフィルムの引っ張
り強度は32.2Mpa、伸びは46.0％、引っ張り弾性率は395
MPaであった。またガラス転移温度は78℃、熱分解温度
は340℃であった。Example 6 173.2 g of bisphenol A type epoxy resin (epoxy equivalent: 173.2) as a bifunctional epoxy resin, 55.4 g of resorcinol (hydroxyl equivalent: 55.4) as a bifunctional phenol, and tri-n-butylphosphine 6.07 g as an etherification catalyst.
Was dissolved in 547.6 g of N, N-dimethylformamide to adjust the solid content concentration in the reaction system to 30%. While mechanically stirring this, keep the temperature in the reaction system at 110 ° C in an oil bath at 115 ° C.
And kept for 20 hours. As a result, the viscosity is 1.
A high molecular weight epoxy resin solution of 740 mPa · s was obtained. The weight average molecular weight of this epoxy resin was 92,000 as a result of measurement by gel permeation chromatography and 83,000 as a result of measurement by a light scattering method. The reduced viscosity of this dilute solution of high molecular weight epoxy resin is 0.785.
(Dl / g). This high molecular weight epoxy resin solution is applied to a glass plate and dried at 200 ° C for 1 hour to give a thickness of 30 μm.
The epoxy resin film of was obtained. This film has a tensile strength of 32.2 Mpa, an elongation of 46.0% and a tensile modulus of 395.
It was MPa. The glass transition temperature was 78 ° C and the thermal decomposition temperature was 340 ° C.
比較例１ 実施例１におけるビスフェノールＡの配合量115.5g（エ
ポキシ樹脂に対して1.00当量）を80.9g（エポキシ樹脂
に対して0.70当量）に変え、N,N−ジメチルアセトアミ
ドの配合量694.9gを614.2gに変えた以外は、実施例１と
同様にして行った。その結果、１時間後にゲル化し、溶
媒に不溶になった。Comparative Example 1 The compounding amount of bisphenol A in Example 1 was changed from 115.5 g (1.00 equivalent to the epoxy resin) to 80.9 g (0.70 equivalent to the epoxy resin), and the compounding amount of N, N-dimethylacetamide was 694.9 g. Example 1 was repeated except that the amount was changed to 614.2 g. As a result, it gelated after 1 hour and became insoluble in the solvent.
比較例２ 実施例１におけるビスフェノールＡの配合量115.5g（エ
ポキシ樹脂に対して1.00当量）を80.9g（エポキシ樹脂
に対して0.70当量）に変え、N,N−ジメチルアセトアミ
ドの配合量694.9gを614.2gに変えた以外は、実施例１と
同様にして行ったが、ゲル化する前に加熱を中止し、粘
度が620mPa・ｓの高分子量エポキシ樹脂溶液を得た。得
られた樹脂の重量平均分子量は、ゲル透過クロマトグラ
フィーによって測定した結果では72,000、光散乱法によ
って測定した結果では58,000であった。また、この高分
子量エポキシ樹脂の稀薄溶液の還元粘度は0.495（dl/
g）であった。この高分子量エポキシ樹脂をガラス板に
塗布し、200℃で１時間乾燥したが、取り扱い上十分な
強度の100μｍ以下のエポキシ樹脂フィルムは得られな
かった。Comparative Example 2 The compounding amount of bisphenol A in Example 1 was changed from 115.5 g (1.00 equivalent to the epoxy resin) to 80.9 g (0.70 equivalent to the epoxy resin), and the compounding amount of N, N-dimethylacetamide was 694.9 g. The procedure of Example 1 was repeated except that the amount was changed to 614.2 g, but heating was stopped before gelation to obtain a high molecular weight epoxy resin solution having a viscosity of 620 mPa · s. The weight average molecular weight of the obtained resin was 72,000 as a result of measurement by gel permeation chromatography and 58,000 as a result of measurement by a light scattering method. The reduced viscosity of a dilute solution of this high molecular weight epoxy resin is 0.495 (dl /
g). This high molecular weight epoxy resin was applied to a glass plate and dried at 200 ° C. for 1 hour, but an epoxy resin film of 100 μm or less having sufficient strength for handling was not obtained.
比較例３ 実施例１におけるN,N−ジメチルアセトアミドをメチル
エチルケトンに変えた以外は、実施例１と同様にして行
ったが、加熱開始後24時間後の粘度は1.9mPa・ｓであっ
た。得られた樹脂の重量平均分子量は、ゲル透過クロマ
トグラフィーによって測定した結果では1,800であり、
光散乱法では測定できなかった。この高分子量エポキシ
樹脂をガラス板に塗布し、200℃で１時間乾燥したが、
エポキシ樹脂フィルムは得られなかった。Comparative Example 3 The procedure of Example 1 was repeated, except that N, N-dimethylacetamide in Example 1 was changed to methyl ethyl ketone, but the viscosity after 24 hours from the start of heating was 1.9 mPa · s. The weight average molecular weight of the obtained resin is 1,800 in the result measured by gel permeation chromatography,
It could not be measured by the light scattering method. This high molecular weight epoxy resin was applied to a glass plate and dried at 200 ° C for 1 hour.
No epoxy resin film was obtained.
比較例４ 実施例２におけるトリ−ｎ−ブチルホスフィンを三ふっ
化ほう素−メタノール錯塩に変えた以外は、実施例２と
同様にして行ったが、加熱開始後24時間後の粘度は3.8m
Pa・ｓであった。得られた樹脂の重量平均分子量は、ゲ
ル透過クロマトグラフィーによって測定した結果では4,
800であり、光散乱法では測定できなかった。この高分
子量エポキシ樹脂をガラス板に塗布し、200℃で１時間
乾燥したが、取り扱い上十分な強度を示す100μｍ以下
のエポキシ樹脂フィルムは得られなかった。Comparative Example 4 The procedure of Example 2 was repeated, except that the tri-n-butylphosphine in Example 2 was changed to boron trifluoride-methanol complex salt, but the viscosity after 24 hours from the start of heating was 3.8 m.
It was Pa · s. The weight average molecular weight of the obtained resin was 4, in the result measured by gel permeation chromatography.
It was 800 and could not be measured by the light scattering method. This high molecular weight epoxy resin was applied to a glass plate and dried at 200 ° C. for 1 hour, but an epoxy resin film of 100 μm or less showing sufficient strength in handling was not obtained.
比較例５ 実施例２におけるトリ−ｎ−ブチルホスフィンをベンズ
イミダゾールに変えた以外は、実施例２と同様にして行
ったが、加熱開始後24時間後の粘度は10.2mPa・ｓであ
った。得られた樹脂の重量平均分子量は、ゲル透過クロ
マトグラフィーによって測定した結果では7,800であ
り、光散乱法では測定できなかった。この高分子量エポ
キシ樹脂をガラス板に塗布し、200℃で１時間乾燥した
が、取り扱い上十分な強度を示す100μｍ以下のエポキ
シ樹脂フィルムは得られなかった。Comparative Example 5 The procedure of Example 2 was repeated except that benzimidazole was used instead of tri-n-butylphosphine in Example 2, but the viscosity after heating for 24 hours was 10.2 mPa · s. The weight average molecular weight of the obtained resin was 7,800 as measured by gel permeation chromatography, and could not be measured by the light scattering method. This high molecular weight epoxy resin was applied to a glass plate and dried at 200 ° C. for 1 hour, but an epoxy resin film of 100 μm or less showing sufficient strength in handling was not obtained.
比較例６ 高分子量エポキシ樹脂であるフェノキシ樹脂YP50P（東
都化成）の平均分子量を測定した。ゲル浸透クロマトグ
ラフィーによるスチレン換算重量平均分子量は77,000で
あった。また、このフェノキシ樹脂の稀薄溶液の還元粘
度は0.488（dl/g）であった。この樹脂はメチルエチル
ケトンに容易に溶解した。また、シクロヘキサノン20％
溶液粘度は205mPa・ｓであった。この高分子量エポキシ
樹脂溶液をガラス板上に塗布し、乾燥器中で加熱乾燥し
てエポキシ樹脂フィルムを作製することを試みたが、10
0μｍ以下の厚さのフィルムは得られなかった。Comparative Example 6 The average molecular weight of phenoxy resin YP50P (Toto Kasei), which is a high molecular weight epoxy resin, was measured. The weight average molecular weight calculated as styrene by gel permeation chromatography was 77,000. The reduced viscosity of this dilute solution of phenoxy resin was 0.488 (dl / g). The resin dissolved readily in methyl ethyl ketone. Also, cyclohexanone 20%
The solution viscosity was 205 mPa · s. This high molecular weight epoxy resin solution was coated on a glass plate and heated and dried in a dryer to try to prepare an epoxy resin film.
A film having a thickness of 0 μm or less was not obtained.
以上の実施例及び比較例における実験方法の詳細を以下
に示す。Details of the experimental methods in the above Examples and Comparative Examples are shown below.
粘度はEMD型粘度計（東京計器）を用いて測定した。ゲ
ル浸透クロマトグラフィー（GPC）に使用したカラム
は、TSKgelG6000＋G5000＋G4000＋G3000＋G2000であ
る。溶離液には、N,N−ジメチルアセトアミドを使用
し、試料濃度は２％とした。様々な分子量のスチレンを
用いて分子量と溶出時間との関係を求めた後、溶出時間
から分子量を算出し、スチレン換算重量平均分子量とし
た。光散乱光度計は、大塚電子（株）製DLS−700を用い
た。引っ張り強度、伸び、引っ張り弾性率は、東洋ボー
ルドウィン製テンシロンを用いた。フィルム試料サイズ
は50×10mm、引っ張り速度は5mm/minとした。ガラス転
移温度（Tg）はデュポン製910型示差走査熱量計（DSC）
を用いて測定した。熱分解温度は、真空理工製の示差熱
天秤TGD−3000を用いて空気中での減量開始温度を熱分
解温度とした。The viscosity was measured using an EMD viscometer (Tokyo Keiki). The column used for gel permeation chromatography (GPC) is TSKgel G6000 + G5000 + G4000 + G3000 + G2000. N, N-dimethylacetamide was used as the eluent, and the sample concentration was 2%. After the relationship between the molecular weight and the elution time was obtained using styrene having various molecular weights, the molecular weight was calculated from the elution time to obtain the styrene-equivalent weight average molecular weight. As the light scattering photometer, DLS-700 manufactured by Otsuka Electronics Co., Ltd. was used. Tensilon manufactured by Toyo Baldwin was used for tensile strength, elongation, and tensile elasticity. The film sample size was 50 × 10 mm, and the pulling speed was 5 mm / min. Glass transition temperature (Tg) is 910 type differential scanning calorimeter (DSC) manufactured by DuPont
Was measured using. The thermal decomposition temperature was determined by using a differential thermal balance TGD-3000 manufactured by Vacuum Riko Co., Ltd. as the temperature at which the weight loss started in the air.
比較例１及び２に示したように、エポキシ樹脂の配合当
量を過剰にした場合には枝分かれが多いと考えられ、分
子量が70,000以上とかなり高分子量化しているにもかか
わらず、100μｍ以下のフィルムは成形できなかった。As shown in Comparative Examples 1 and 2, when the compounding equivalent of the epoxy resin is excessive, it is considered that there is a large amount of branching, and although the molecular weight is considerably higher than 70,000, it is a film of 100 μm or less. Could not be molded.
また、比較例６に示したように、市販の、ビスフェノー
ルＡ型超高分子量エポキシ樹脂であるフェノキシ樹脂
も、かなり高分子量化しているにもかかわらず、メチル
エチルケトンに溶解し、シクロヘキサノン20％溶液の粘
度は、本発明の超高分子量エポキシ樹脂溶液の粘度に比
べて著しく低かった。これらの樹脂についても、100μ
ｍ以下のフィルムは成形できなかった。In addition, as shown in Comparative Example 6, a commercially available phenoxy resin, which is a bisphenol A type ultra high molecular weight epoxy resin, was dissolved in methyl ethyl ketone even though it had a considerably high molecular weight, and the viscosity of a 20% cyclohexanone solution was increased. Was significantly lower than the viscosity of the ultra high molecular weight epoxy resin solution of the present invention. For these resins, 100μ
A film of m or less could not be formed.
実施例１と同様の配合で、反応を途中で停止し、比較的
低分子量のエポキシ樹脂を用いた場合には、フィルムは
成形できるが強度が著しく低かった。When the reaction was stopped halfway and the epoxy resin having a relatively low molecular weight was used in the same formulation as in Example 1, the film could be molded, but the strength was remarkably low.
比較例に対してすべての実施例では、厚さ100μｍ以下
の十分な強度のエポキシ樹脂フィルムが得られる。In all of the examples, as compared with the comparative example, an epoxy resin film having a thickness of 100 μm or less and having sufficient strength is obtained.
本発明の高分子量エポキシ樹脂の製造方法によれば、従
来は得られなかった100μｍ以下、さらには50μｍ以下
の十分に薄く、十分な強度を有するエポキシ樹脂フィル
ムを形成することができる超高分子量エポキシ樹脂を製
造することが可能となり、またこの超高分子量エポキシ
樹脂を短時間で得ることができる。According to the method for producing a high molecular weight epoxy resin of the present invention, an ultrahigh molecular weight epoxy capable of forming a sufficiently thin epoxy resin film having a sufficient strength of 100 μm or less, further 50 μm or less, which has not been obtained conventionally. It becomes possible to produce a resin, and this ultra high molecular weight epoxy resin can be obtained in a short time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新井 正美 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 (72)発明者 星 郁夫 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 (56)参考文献 特開 昭53−98399（ＪＰ，Ａ) 特開 昭57−179219（ＪＰ，Ａ) 特開 昭58−149914（ＪＰ，Ａ) 特開 昭60−262819（ＪＰ，Ａ) 特開 平１−254733（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masami Arai, 1500 Ogawa, Shimodate, Shimodate, Ibaraki, Shimodate Research Laboratory, Hitachi Chemical Co., Ltd. (72) Ikuo Hoshi, 1500, Ogawa, Shimodate, Ibaraki, Hitachi Chemical Co., Ltd. Shimodate Laboratory (56) Reference JP-A-53-98399 (JP, A) JP-A-57-179219 (JP, A) JP-A-58-149914 (JP, A) JP-A-60-262819 (JP, A) JP-A-1-254733 (JP, A)
Claims (1)
を触媒の存在下、重合反応溶媒中で加熱して重合させ、
高分子量エポキシ樹脂を製造する方法において、二官能
エポキシ樹脂と二官能フェノール類の配合当量比をエポ
キシ基／フェノール性水酸基＝1:0.9〜1.1とし、アミド
系溶媒中、アルキルりん系触媒を用い、重合反応時の固
形分濃度を50重量％以下にして重合することを特徴とす
るメチルエチルケトンに溶解せず、還元粘度が0.6dl/g
（30℃、N,N−ジメチルアセトアミド）以上である高分
子量エポキシ樹脂の製造方法。1. A bifunctional epoxy resin and a bifunctional phenol are polymerized by heating in a polymerization reaction solvent in the presence of a catalyst,
In the method for producing a high molecular weight epoxy resin, the compounding equivalent ratio of the bifunctional epoxy resin and the bifunctional phenols is set to epoxy group / phenolic hydroxyl group = 1: 0.9 to 1.1, in an amide solvent, using an alkyl phosphorus catalyst, The solid content concentration at the time of the polymerization reaction is 50% by weight or less and is polymerized, which does not dissolve in methyl ethyl ketone and has a reduced viscosity of 0.6 dl / g.
(30 ° C., N, N-dimethylacetamide) or higher, a method for producing a high molecular weight epoxy resin.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2239398A JPH0759617B2 (en) | 1990-09-10 | 1990-09-10 | Method for producing high molecular weight epoxy resin |
| DE1991629052 DE69129052T2 (en) | 1990-09-10 | 1991-09-10 | Process for the preparation of high molecular weight epoxy resins |
| EP91115289A EP0475359B1 (en) | 1990-09-10 | 1991-09-10 | Method of producing high molecular weight epoxy resin |
| US08/137,229 US5391687A (en) | 1990-09-10 | 1993-10-18 | Method of producing high molecular weight epoxy resin using an amide solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2239398A JPH0759617B2 (en) | 1990-09-10 | 1990-09-10 | Method for producing high molecular weight epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04120122A JPH04120122A (en) | 1992-04-21 |
| JPH0759617B2 true JPH0759617B2 (en) | 1995-06-28 |
Family
ID=17044185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2239398A Expired - Lifetime JPH0759617B2 (en) | 1990-09-10 | 1990-09-10 | Method for producing high molecular weight epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0759617B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265782B1 (en) | 1996-10-08 | 2001-07-24 | Hitachi Chemical Co., Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| WO2012046814A1 (en) | 2010-10-06 | 2012-04-12 | 日立化成工業株式会社 | Multilayer resin sheet and process for production thereof, resin sheet laminate and process for production thereof, cured multilayer resin sheet, metal-foil-cladded multilayer resin sheet, and semiconductor device |
| WO2020153205A1 (en) | 2019-01-23 | 2020-07-30 | 富士フイルム株式会社 | Composition, thermally-conductive sheet, and device equipped with thermally-conductive layer |
| WO2021010291A1 (en) | 2019-07-17 | 2021-01-21 | 富士フイルム株式会社 | Composition for forming thermally conductive material, thermally conductive material, and surface-modified inorganic substance |
| WO2021131803A1 (en) | 2019-12-26 | 2021-07-01 | 富士フイルム株式会社 | Composition, heat conductive sheet, and device having heat conductive sheet |
| WO2021157246A1 (en) | 2020-02-06 | 2021-08-12 | 富士フイルム株式会社 | Composition, thermally conductive material, thermally conductive sheet, and device with thermally conductive layer |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0768327B2 (en) * | 1990-09-11 | 1995-07-26 | 日立化成工業株式会社 | Method for producing ultra high molecular weight epoxy resin |
| JPH08302161A (en) | 1995-05-10 | 1996-11-19 | Hitachi Chem Co Ltd | Resin composition and method for chemically etching same |
| JP3657720B2 (en) * | 1996-12-11 | 2005-06-08 | ジャパンエポキシレジン株式会社 | Method for producing polymer epoxy resin |
| JP5156233B2 (en) * | 2004-07-20 | 2013-03-06 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product thereof |
| JP6409487B2 (en) * | 2014-10-15 | 2018-10-24 | 三菱ケミカル株式会社 | Epoxy resin and production method thereof, epoxy resin-containing composition and cured product |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5928338B2 (en) * | 1977-02-08 | 1984-07-12 | 旭硝子株式会社 | Manufacturing method of epoxy resin |
| JPS57179219A (en) * | 1981-04-28 | 1982-11-04 | Mitsubishi Gas Chem Co Inc | Preparation of curable resin |
| JPS58149914A (en) * | 1982-03-03 | 1983-09-06 | Sumitomo Chem Co Ltd | Production of polyhydroxy polyether |
| JPS59136357A (en) * | 1983-01-26 | 1984-08-04 | Toyo Seikan Kaisha Ltd | Production of epoxy based coating material |
| JPS60262819A (en) * | 1984-06-11 | 1985-12-26 | Mitsubishi Petrochem Co Ltd | Production of polyepoxy compound |
| DE3518770A1 (en) * | 1985-05-24 | 1986-11-27 | BASF Lacke + Farben AG, 4400 Münster | WATER-DISCOVERABLE BINDING AGENTS FOR CATIONIC ELECTRO-DIP COATINGS AND METHOD FOR THEIR PRODUCTION |
| DE3518732A1 (en) * | 1985-05-24 | 1986-11-27 | BASF Lacke + Farben AG, 4400 Münster | WATER-DISCOVERABLE BINDING AGENTS FOR CATIONIC ELECTRO-DIP COATINGS AND METHOD FOR THEIR PRODUCTION |
| JPH0751693B2 (en) * | 1987-11-06 | 1995-06-05 | 関西ペイント株式会社 | Coating resin composition |
| US4808692A (en) * | 1988-02-18 | 1989-02-28 | The Dow Chemical Company | Preparation of advanced epoxy resins from epoxy resins and dihydric phenols in the presence of phosphonium compounds |
-
1990
- 1990-09-10 JP JP2239398A patent/JPH0759617B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265782B1 (en) | 1996-10-08 | 2001-07-24 | Hitachi Chemical Co., Ltd. | Semiconductor device, semiconductor chip mounting substrate, methods of manufacturing the device and substrate, adhesive, and adhesive double coated film |
| WO2012046814A1 (en) | 2010-10-06 | 2012-04-12 | 日立化成工業株式会社 | Multilayer resin sheet and process for production thereof, resin sheet laminate and process for production thereof, cured multilayer resin sheet, metal-foil-cladded multilayer resin sheet, and semiconductor device |
| WO2020153205A1 (en) | 2019-01-23 | 2020-07-30 | 富士フイルム株式会社 | Composition, thermally-conductive sheet, and device equipped with thermally-conductive layer |
| WO2021010291A1 (en) | 2019-07-17 | 2021-01-21 | 富士フイルム株式会社 | Composition for forming thermally conductive material, thermally conductive material, and surface-modified inorganic substance |
| WO2021131803A1 (en) | 2019-12-26 | 2021-07-01 | 富士フイルム株式会社 | Composition, heat conductive sheet, and device having heat conductive sheet |
| WO2021157246A1 (en) | 2020-02-06 | 2021-08-12 | 富士フイルム株式会社 | Composition, thermally conductive material, thermally conductive sheet, and device with thermally conductive layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04120122A (en) | 1992-04-21 |
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