JP3377110B2 - Epoxy resin composition for mold and resin mold obtained therefrom - Google Patents
Epoxy resin composition for mold and resin mold obtained therefromInfo
- Publication number
- JP3377110B2 JP3377110B2 JP11417193A JP11417193A JP3377110B2 JP 3377110 B2 JP3377110 B2 JP 3377110B2 JP 11417193 A JP11417193 A JP 11417193A JP 11417193 A JP11417193 A JP 11417193A JP 3377110 B2 JP3377110 B2 JP 3377110B2
- Authority
- JP
- Japan
- Prior art keywords
- mold
- epoxy resin
- resin
- resin composition
- curing
- 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 title claims description 44
- 229920000647 polyepoxide Polymers 0.000 title claims description 44
- 229920005989 resin Polymers 0.000 title claims description 43
- 239000011347 resin Substances 0.000 title claims description 43
- 239000000203 mixture Substances 0.000 title claims description 24
- 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 claims description 10
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920006305 unsaturated polyester Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 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
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 aliphatic diamine Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DBIKWHSBKVRPBS-UHFFFAOYSA-N n,3,3,5-tetramethylcyclohexan-1-amine Chemical compound CNC1CC(C)CC(C)(C)C1 DBIKWHSBKVRPBS-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は型用エポキシ樹脂組成物
及び該組成物を硬化して得られる樹脂型に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold epoxy resin composition and a resin mold obtained by curing the composition.
【０００２】[0002]
【従来の技術】不飽和ポリエステル等の熱硬化性樹脂を
母型に流し込み、硬化させて成形物を製造する方法がよ
く行われている。この時使用する母型の種類としては、
金属型、石膏型及び樹脂型がある。このうち金属型は耐
久性に優れ大量の生産に適しているが、製作費が高価で
あるため試作や少量生産には適していない。また石膏型
は安価で製作も容易であるが、脆くて破損し易くまた表
面が荒いため複雑な形状や鏡面を要求される物の製造に
は適していない。このため試作や少量生産を目的とする
場合樹脂型がよく使用され、樹脂型の材料としてエポキ
シ樹脂が使用されていることはよく知られているところ
である。しかしながら従来使用されている、エポキシ樹
脂は硬化収縮が大きく寸法精度がでなかったり反りが発
生する欠点があり、特に大型の成形物を作成する場合反
りの発生は大きな問題となっている。また更にマスター
の材質が木型や軟化点の低いプラスチックの場合、母型
の作成は室温で行う必要があり（加熱すると木型の場合
木型中の水分が析出し好ましくない、また軟化点の低い
プラスチックの場合マスターの変形が起こる）、その場
合充分な強度と耐熱性が得られず、母型を作る工程でマ
スターを母型から外すとき破損したり、熱硬化性樹脂を
硬化させ成形した時、反応熱により変形をおこす等の問
題がありまだ満足すべき樹脂型を得るにいたっていな
い。2. Description of the Related Art A method of casting a thermosetting resin such as unsaturated polyester into a mother mold and curing the resin to produce a molded product is often used. As the type of matrix used at this time,
There are metal type, gypsum type and resin type. Among them, the metal mold is excellent in durability and suitable for mass production, but is not suitable for trial manufacture and small-scale production because the manufacturing cost is high. The gypsum mold is inexpensive and easy to manufacture, but it is not suitable for manufacturing a product that requires a complicated shape or a mirror surface because it is brittle and easily damaged and its surface is rough. Therefore, it is well known that resin molds are often used for the purpose of trial manufacture and small-scale production, and epoxy resins are used as the material of the resin molds. However, conventionally used epoxy resins have the drawbacks of large curing shrinkage, poor dimensional accuracy, and warpage, and warpage is a serious problem especially when a large molded product is produced. If the material of the master is a wooden mold or a plastic with a low softening point, it is necessary to prepare the mother mold at room temperature (when heated, moisture in the wooden mold will precipitate, which is not desirable. If the plastic is low, the master will deform.) In that case, sufficient strength and heat resistance cannot be obtained, and when the master is removed from the master in the process of making the master, it is damaged or the thermosetting resin is cured and molded. At the same time, there are problems such as deformation due to heat of reaction, and a satisfactory resin mold has not yet been obtained.
【０００３】[0003]
【発明が解決しようとする課題】低温で硬化でき硬化収
縮が小さく反りがなく且つ耐熱性や物理的性能に優れる
型用エポキシ樹脂組成物及び樹脂型の開発が望まれてい
る。It is desired to develop a mold epoxy resin composition and a resin mold which can be cured at a low temperature, have a small curing shrinkage, have no warpage, and are excellent in heat resistance and physical performance.
【０００４】[0004]
【課題を解決するための手段】本発明者らは前記した課
題を解決すべく鋭意研究を重ねた結果、本発明を完成さ
せたものである。即ち本発明は
ａ．ビスフェノール型エポキシ樹脂６０〜８０重量％、
ジグリシジルオルトトルイジン型エポキシ樹脂２０〜４
０重量％からなるエポキシ樹脂
ｂ．ビススピロ環ジアミン、３−アミノメチル−３、
５、５−トリメチルシクロヘキシルアミン、メタキシリ
レンジアミン、Ｎ−アミノエチルピペラジン及びポリア
ミノアミドの中から選ばれる一種以上からなる硬化剤か
らなる型用エポキシ樹脂組成物及び該組成物を硬化して
得られる樹脂型を提供する。The present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention comprises a. Bisphenol type epoxy resin 60 to 80% by weight,
Diglycidyl orthotoluidine type epoxy resin 20-4
0% by weight of epoxy resin b. Bisspiro ring diamine, 3-aminomethyl-3,
Epoxy resin composition for mold comprising a curing agent composed of one or more selected from 5,5-trimethylcyclohexylamine, metaxylylenediamine, N-aminoethylpiperazine and polyaminoamide, and obtained by curing the composition Provide a resin mold.
【０００５】本発明で使用するエポキシ樹脂は、ビスフ
ェノール型エポキシ樹脂及びグリシジルアミン型エポキ
シ樹脂の混合物からなる。ビスフェノール型エポキシ樹
脂はビスフェノールＡ及びビスフェノールＦ型エポキシ
樹脂を、またグリシジルアミン型エポキシ樹脂はジグリ
シジルオルトトルイジン及びジグリシジルアニリン型エ
ポキシ樹脂を示す。両者の配合比率は前記した通りであ
るが、より好ましくはビスフェノール型エポキシ樹脂６
５〜７５重量％、グリシジルアミン型エポキシ樹脂３０
〜３５重量％である。本発明の範囲よりビスフェノール
型エポキシ樹脂の使用量が多い場合、粘度が高くなり過
ぎ作業性が著しく悪くなり、硬化物である樹脂型に気泡
を巻き込み好ましくない。また本発明の範囲よりも使用
量が少ない場合耐熱性の低下が認められ、また硬化収縮
が大きくなり寸法精度が悪くなりまた反りが発生し好ま
しくない。The epoxy resin used in the present invention comprises a mixture of a bisphenol type epoxy resin and a glycidyl amine type epoxy resin. The bisphenol type epoxy resin is bisphenol A and bisphenol F type epoxy resin, and the glycidyl amine type epoxy resin is diglycidyl orthotoluidine and diglycidyl aniline type epoxy resin. The mixing ratio of both is as described above, but more preferably bisphenol type epoxy resin 6
5 to 75% by weight, glycidyl amine type epoxy resin 30
~ 35% by weight. When the amount of the bisphenol type epoxy resin used is larger than the range of the present invention, the viscosity becomes too high and the workability is remarkably deteriorated, and air bubbles are entrained in the resin type which is a cured product, which is not preferable. Further, when the amount used is less than the range of the present invention, the heat resistance is decreased, the curing shrinkage is increased, the dimensional accuracy is deteriorated, and warpage occurs, which is not preferable.
【０００６】次ぎに本発明で使用する硬化剤はビススピ
ロ環ジアミン、３−アミノメチル−３、５、５−トリメ
チルシクロヘキシルアミン、メタキシリレンジアミン、
Ｎ−アミノエチルピペラジン及びポリアミノアミドの中
から選ばれる一種以上からなる。ビススピロ環ジアミン
は３、９−ビス（３−アミノプロピル）−２、４、８、
１０−テトラスピロ［５、５］ウンデカンを基本骨格と
するジアミンでエポメートの商品名で、３−アミノメチ
ル−３、５、５トリメチルシクロヘキシルアミンはイソ
ホロンジアミンの商品名で、メタキシリレンジアミンは
ＭＸＤＡの商品名で、Ｎ−アミノエチルピペラジンはＡ
ＥＰの商品名でまたポリアミノアミドは例えばアンカマ
イドの商品名でそれぞれ市販されている。これらのアミ
ン類は一種であるいは一種以上混合して用いてもよく混
合する場合の比率は任意である。硬化剤の使用量はエポ
キシ樹脂に対し０．８〜１．２化学当量好ましくは０．
９〜１．０化学当量使用する。Next, the curing agent used in the present invention is bisspirocyclic diamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, metaxylylenediamine,
One or more selected from N-aminoethylpiperazine and polyaminoamide. Bisspiro ring diamine is 3,9-bis (3-aminopropyl) -2,4,8,
Diamine having 10-tetraspiro [5,5] undecane as a basic skeleton is a trade name of Epomate, 3-aminomethyl-3,5,5 trimethylcyclohexylamine is a trade name of isophoronediamine, and metaxylylenediamine is MXDA. In the trade name, N-aminoethylpiperazine is A
Polyaminoamides are commercially available under the trade name of EP, and polyaminoamides under the trade name of, for example, ancamide. These amines may be used alone or in admixture of one or more, and when they are mixed, the ratio is arbitrary. The amount of the curing agent used is 0.8 to 1.2 chemical equivalents to the epoxy resin, preferably 0.1.
Use 9-1.0 chemical equivalents.
【０００７】本発明の型用エポキシ樹脂組成物は、樹脂
型の転写面が鏡面を必要とする場合は充填材を添加しな
いで用いるが、通常充填材を添加して用いる。使用しう
る充填材としては例えば、アルミ粉末、銅粉末、シリカ
粉末、アルミナ粉末等が挙げられ、その添加量は樹脂組
成物全重量の５０〜８０重量％、好ましくは６０〜７０
重量％になる量必要により添加する。本発明の樹脂組成
物には充填剤の他カップリング剤、硬化促進剤、着色剤
等常用の添加剤を添加してもよい。本発明の型用エポキ
シ樹脂組成物は前記したエポキシ樹脂、脂肪族ジアミン
硬化剤及び必要であれば充填材、カップリング剤、硬化
を促進するための例えば３級アミン、サリチル酸、多価
フェノール等の硬化促進剤及び着色剤の所定量を真空ニ
ーダを用い均一に撹拌する事によって容易に得られる。
樹脂型の作成は得られたエポキシ樹脂組成物を、マスタ
ーがセットされた型枠の中に流し込み脱泡した後、室温
で５時間〜１日硬化させた後マスターを外す事により得
られる。得られた樹脂型はそのままで使用する事もでき
るが、６０〜１５０℃で３〜２０時間アフターキュアす
る事により更に優れた特性を有する樹脂型が得られる。The epoxy resin composition for a mold of the present invention is used without adding a filler when the transfer surface of the resin mold requires a mirror surface, but it is usually used after adding a filler. Examples of the filler that can be used include aluminum powder, copper powder, silica powder, alumina powder and the like, and the addition amount thereof is 50 to 80% by weight, preferably 60 to 70% by weight based on the total weight of the resin composition.
Amount to be added by weight Add if necessary. In addition to the filler, the resin composition of the present invention may contain conventional additives such as a coupling agent, a curing accelerator, and a coloring agent. The mold epoxy resin composition of the present invention comprises the above-mentioned epoxy resin, an aliphatic diamine curing agent and, if necessary, a filler, a coupling agent, a tertiary amine for promoting curing, salicylic acid, polyhydric phenol and the like. It can be easily obtained by uniformly stirring a predetermined amount of the curing accelerator and the colorant using a vacuum kneader.
The resin mold is prepared by pouring the obtained epoxy resin composition into a mold in which a master is set, defoaming, curing at room temperature for 5 hours to 1 day, and then removing the master. Although the obtained resin mold can be used as it is, after-curing at 60 to 150 ° C. for 3 to 20 hours gives a resin mold having more excellent properties.
【０００８】[0008]
【実施例】以下に実施例で本発明を更に詳しく説明す
る。
実施例１
ビスフェノールＡ型エポキシ樹脂（ＲＥ−３１０Ｓ、日
本化薬社製、エポキシ当量１８０）７００ｇ，ジグリシ
ジルオルトトルイジン型エポキシ樹脂（ＧＯＴ、日本化
薬社製、エポキシ当量１３５）３００ｇ、３−アミノメ
チル−３、５、５−トリメチルシクロヘキシルアミン
（イソホロンジアミン、フィルス社製）２５０ｇ及びア
ルミ粉末１９００ｇ（ＶＡ−３００、山石金属社製、平
均粒径３５ミクロン）を真空ニーダで均一に撹拌して型
用エポキシ樹脂組成物３１５０ｇを得た（２５℃の粘度
３００ポイズ）。得られた型用エポキシ樹脂組成物を、
試験用マスター（ＡＢＳ製、２５０ミリ×２５０ミリ×
２０ミリ）をセットした型枠（３００ミリ×３００ミリ
×５０ミリ）の中に流し込み脱泡を行った後室温で２４
時間硬化した。次いで型枠とマスターを外し樹脂型を得
た。得られた樹脂型の収縮はほとんどなく、反りは認め
られなかった。またこの樹脂型を用いて不飽和ポリエス
テルの重合成形を行ったが反応熱による樹脂型の変形
（反り）は認められなかった。The present invention will be described in more detail with reference to the following examples. Example 1 700 g of bisphenol A type epoxy resin (RE-310S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 180), 300 g of diglycidyl orthotoluidine type epoxy resin (GOT, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 135), 3-amino 250 g of methyl-3,5,5-trimethylcyclohexylamine (isophorone diamine, manufactured by Fils) and 1900 g of aluminum powder (VA-300, manufactured by Yamaishi Metal Co., Ltd., average particle size: 35 microns) are uniformly stirred with a vacuum kneader. 3150 g of an epoxy resin composition for use was obtained (viscosity at 25 ° C .: 300 poise). The obtained mold epoxy resin composition,
Test master (ABS, 250 mm x 250 mm x
20 mm) and cast into a mold (300 mm x 300 mm x 50 mm) to defoam, then at room temperature 24
Hardened for hours. Then, the mold and the master were removed to obtain a resin mold. The resin mold thus obtained showed almost no shrinkage and no warpage was observed. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【０００９】実施例２
実施例１で使用した３−アミノメチル−３、５、５−ト
リメチルシクロヘキシルアミン（イソホロンジアミン、
フィルス社製）２５０ｇの代わりに、ビススピロ環ジア
ミン（エポメートＢ−００２、油化シェル社製）４２０
ｇを用いた他は実施例１と同様にして型用エポキシ樹脂
組成物３３２０ｇを得た（２５℃の粘度２８０ポイ
ズ）。得られた型用エポキシ樹脂組成物を用い、実施例
１と同様にして樹脂型を得た。得られた樹脂型の収縮は
ほとんどなく、反りは認められなかった。またこの樹脂
型を用いて不飽和ポリエステルの重合成形を行ったが反
応熱による樹脂型の変形（反り）は認められなかった。Example 2 3-Aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, used in Example 1)
Bisspiro ring diamine (Epomate B-002, manufactured by Yuka Shell Co., Ltd.) 420 instead of 250 g of Fils.
3320 g of a mold epoxy resin composition was obtained in the same manner as in Example 1 except that g was used (viscosity of 280 poise at 25 ° C.). Using the obtained epoxy resin composition for molds, a resin mold was obtained in the same manner as in Example 1. The resin mold thus obtained showed almost no shrinkage and no warpage was observed. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【００１０】実施例３
実施例１で使用したアルミ粉末を用いないでエポキシ樹
脂と硬化剤だけを用いて他は実施例１と同様にして型用
エポキシ樹脂組成物１２５０ｇを得た（２５℃の粘度１
２ポイズ）。得られた型用エポキシ樹脂組成物を用い、
実施例１と同様にして樹脂型を得さらに１００℃で３時
間アフターキュアを行った。得られた樹脂型はマスター
表面の転写性に優れたもので収縮率０．１５％で、反り
は認められなかった。またこの樹脂型を用いて不飽和ポ
リエステルの重合成形を行ったが反応熱による樹脂型の
変形（反り）は認められなかった。Example 3 1250 g of a mold epoxy resin composition was prepared in the same manner as in Example 1 except that the aluminum powder used in Example 1 was not used and only the epoxy resin and the curing agent were used. Viscosity 1
2 poise). Using the obtained mold epoxy resin composition,
A resin mold was obtained in the same manner as in Example 1, and after-cured at 100 ° C. for 3 hours. The resin mold thus obtained had excellent transferability on the master surface, had a shrinkage of 0.15%, and showed no warpage. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【００１１】実施例４
実施例１で使用した３−アミノメチル−３、５、５−ト
リメチルシクロヘキシルアミン（イソホロンジアミン、
フィルス社製）２５０ｇの代わりに、ビススピロ環ジア
ミン（エポメートＢ−００２、油化シェル社製）３００
ｇ、ポリアミノアミド（アンカマイド５０６、ＡＣＩジ
ャパン社製）１５０ｇを用いた他は実施例１と同様にし
て型用エポキシ樹脂組成物３３５０ｇを得た（２５℃の
粘度３８０ポイズ）。得られた型用エポキシ樹脂組成物
を用い、実施例１と同様にして樹脂型を得た。得られた
樹脂型の収縮はほとんどなく、反りは認められなかっ
た。またこの樹脂型を用いて不飽和ポリエステルの重合
成形を行ったが反応熱による樹脂型の変形（反り）は認
められなかった。Example 4 3-Aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, used in Example 1)
250 g instead of 250 g of Fils) 300 bisspiro-ring diamine (Epomate B-002, manufactured by Yuka Shell Co., Ltd.)
g, polyaminoamide (Ankamide 506, manufactured by ACI Japan), and 3350 g of an epoxy resin composition for mold (viscosity of 380 poise at 25 ° C.) was obtained in the same manner as in Example 1. Using the obtained epoxy resin composition for molds, a resin mold was obtained in the same manner as in Example 1. The resin mold thus obtained showed almost no shrinkage and no warpage was observed. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【００１２】実施例５
実施例１で使用した３−アミノメチル−３、５、５−ト
リメチルシクロヘキシルアミン（イソホロンジアミン、
フィルス社製）２５０ｇの代わりに、メタキシリレンジ
アミン（ＭＸＤＡ，三菱ガス化学社製）３５０ｇを用い
た他は実施例１と同様にして型用エポキシ樹脂組成物３
４５０ｇを得た（２５℃の粘度３５０ポイズ）。得られ
た型用エポキシ樹脂組成物を用い、実施例１と同様にし
て樹脂型を得た。得られた樹脂型の収縮はほとんどな
く、反りは認められなかった。またこの樹脂型を用いて
不飽和ポリエステルの重合成形を行ったが反応熱による
樹脂型の変形（反り）は認められなかった。Example 5 3-Aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, used in Example 1)
Epoxy resin composition 3 for mold in the same manner as in Example 1 except that 350 g of metaxylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Inc.) was used instead of 250 g of Fils.
450 g were obtained (viscosity at 25 ° C. 350 poise). Using the obtained epoxy resin composition for molds, a resin mold was obtained in the same manner as in Example 1. The resin mold thus obtained showed almost no shrinkage and no warpage was observed. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【００１３】実施例６
実施例１で使用した３−アミノメチル−３、５、５−ト
リメチルシクロヘキシルアミン（イソホロンジアミン、
フィルス社製）２５０ｇの代わりに、Ｎ−アミノエチル
ピペラジン（ＡＥＰ、広栄化学社製）２２５及び硬化促
進剤としてビスフェノールＦ（試薬）２５ｇを用いた他
は実施例１と同様にして型用エポキシ樹脂組成物３１５
０ｇを得た（２５℃の粘度３６０ポイズ）。得られた型
用エポキシ樹脂組成物を用い、実施例１と同様にして樹
脂型を得た。得られた樹脂型の収縮はほとんどなく、反
りは認められなかった。またこの樹脂型を用いて不飽和
ポリエステルの重合成形を行ったが反応熱による樹脂型
の変形（反り）は認められなかった。Example 6 3-Aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine, used in Example 1)
Epoxy resin for mold in the same manner as in Example 1 except that N-aminoethylpiperazine (AEP, manufactured by Koei Chemical Co., Ltd.) 225 and bisphenol F (reagent) 25 g as a curing accelerator were used instead of 250 g of Fils. Composition 315
0 g was obtained (viscosity at 25 ° C. 360 poise). Using the obtained epoxy resin composition for molds, a resin mold was obtained in the same manner as in Example 1. The resin mold thus obtained showed almost no shrinkage and no warpage was observed. Further, the unsaturated polyester was polymerized and molded using this resin mold, but no deformation (warping) of the resin mold due to reaction heat was observed.
【００１４】[0014]
【発明の効果】室温硬化で硬化収縮が小さく寸法精度に
優れ、反りのない樹脂型の製造が可能となり、経済性、
信頼性に優れた樹脂成形が可能になった。EFFECTS OF THE INVENTION When cured at room temperature, curing shrinkage is small, dimensional accuracy is excellent, and it is possible to manufacture a resin mold without warping, which is economical and
Resin molding with excellent reliability has become possible.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−56965（ＪＰ，Ａ) 特開 平６−271646（ＪＰ，Ａ) 特開 平５−78554（ＪＰ，Ａ) 特開 平４−185630（ＪＰ，Ａ) 特開 平６−263840（ＪＰ，Ａ) 特開 平４−178421（ＪＰ，Ａ) 特開 平５−20919（ＪＰ，Ａ) 特開 昭60−137623（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 59/20 - 59/72 B29C 33/40 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-56965 (JP, A) JP-A-6-271646 (JP, A) JP-A-5-78554 (JP, A) JP-A-4- 185630 (JP, A) JP 6-263840 (JP, A) JP 4-178421 (JP, A) JP 5-20919 (JP, A) JP 60-137623 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 59/20-59/72 B29C 33/40
Claims (2)
８０重量％、ジグリシジルオルトトルイジン型エポキシ
樹脂２０〜４０重量％からなるエポキシ樹脂 ｂ．ビススピロ環ジアミン、３−アミノメチル−３、
５、５−トリメチルシクロヘキシルアミン、メタキシリ
レンジアミン、Ｎ−アミノエチルピペラジン及びポリア
ミノアミドの中から選ばれる一種以上からなる硬化剤か
らなる型用エポキシ樹脂組成物。1. A. Bisphenol type epoxy resin 60 ~
Epoxy resin consisting of 80% by weight and 20 to 40% by weight of diglycidyl orthotoluidine type epoxy resin b. Bisspiro ring diamine, 3-aminomethyl-3,
A mold epoxy resin composition comprising a curing agent composed of one or more selected from 5,5-trimethylcyclohexylamine, metaxylylenediamine, N-aminoethylpiperazine and polyaminoamide.
硬化して得られる樹脂型。2. A resin mold obtained by curing the epoxy resin composition for mold according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11417193A JP3377110B2 (en) | 1993-04-19 | 1993-04-19 | Epoxy resin composition for mold and resin mold obtained therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11417193A JP3377110B2 (en) | 1993-04-19 | 1993-04-19 | Epoxy resin composition for mold and resin mold obtained therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06298909A JPH06298909A (en) | 1994-10-25 |
| JP3377110B2 true JP3377110B2 (en) | 2003-02-17 |
Family
ID=14630959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11417193A Expired - Fee Related JP3377110B2 (en) | 1993-04-19 | 1993-04-19 | Epoxy resin composition for mold and resin mold obtained therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3377110B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010121853A1 (en) * | 2009-04-24 | 2010-10-28 | Huntsman Advanced Materials (Switzerland) Gmbh | Method of making chemically resistant moulds and tools |
| CN112795138B (en) * | 2020-12-31 | 2023-02-03 | 道生天合材料科技(上海)股份有限公司 | Mold perfusion resin composition |
| CN113549302A (en) * | 2021-08-14 | 2021-10-26 | 东莞市德鸿家居用品有限公司 | Forming mold for bathroom product and preparation method thereof |
-
1993
- 1993-04-19 JP JP11417193A patent/JP3377110B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06298909A (en) | 1994-10-25 |
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