JPH09194540A - Resin composition for forming optical three-dimensional article - Google Patents
Resin composition for forming optical three-dimensional articleInfo
- Publication number
- JPH09194540A JPH09194540A JP8026218A JP2621896A JPH09194540A JP H09194540 A JPH09194540 A JP H09194540A JP 8026218 A JP8026218 A JP 8026218A JP 2621896 A JP2621896 A JP 2621896A JP H09194540 A JPH09194540 A JP H09194540A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- meth
- weight
- resin composition
- parts
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学的立体造形用
樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a resin composition for optical three-dimensional modeling.
【０００２】[0002]
【従来の技術】光硬化性樹脂を用いて三次元立体物を造
形する方法は、特開昭５６−１４４４７８号公報、特開
昭６０−２４７５１５号公報等においてその基本的な方
法が開示されている。この光学的立体造形法の代表滴な
例の概略を説明すると、光硬化性樹脂の液面にレーザ照
射を選択的に行い液面から一定深さの樹脂層を硬化させ
ることによって、平面状の特定形状の硬化層を形成し、
続いて硬化層を液面下に一層分だけ移動させ或いは硬化
層に光硬化性樹脂を供給して硬化層上の新たな液面にレ
ーザ照射を行い硬化層を形成するという積層操作の繰り
返しにより最終的には三次元立体物を造形するものであ
る。2. Description of the Related Art As a method of forming a three-dimensional solid object using a photocurable resin, the basic method is disclosed in JP-A-56-144478 and JP-A-60-247515. There is. Explaining the outline of a representative example of this optical three-dimensional modeling method, the liquid surface of the photocurable resin is selectively irradiated with laser light to cure a resin layer having a constant depth from the liquid surface, thereby providing a planar shape. Form a hardened layer with a specific shape,
Then, the cured layer is moved below the liquid surface by one layer, or a photocurable resin is supplied to the cured layer to irradiate a new liquid surface on the cured layer with a laser to form a cured layer, thereby repeating the stacking operation. Eventually, it will create a three-dimensional object.
【０００３】かかる光学的立体造形用の光硬化性樹脂と
しては、取扱い性、造形速度、造形精度、造形物の物性
等の点から、樹脂粘度が低い、樹脂の皮膚刺激性が低
い、光感度が高い、硬化収縮が小さい、硬化物の機械的
物性や耐熱性が高い等が求められているが、これら全て
を十分に満足させることは非常に困難であり、特に高耐
熱性、高弾性率で、かつ高衝撃性の立体造形物を得る光
硬化性樹脂については未だ知られていなかった。As a photocurable resin for optical three-dimensional modeling, the resin viscosity is low, the skin irritation of the resin is low, and the photosensitivity is high in terms of handleability, modeling speed, modeling accuracy, physical properties of the molded article, and the like. High hardness, small curing shrinkage, high mechanical properties and high heat resistance of the cured product, etc., but it is very difficult to satisfy all of these, especially high heat resistance and high elastic modulus. However, a photocurable resin for obtaining a three-dimensional molded article having high impact resistance has not yet been known.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、高耐
熱性、高弾性率で、かつ高衝撃性の立体造形物を作業性
良好に得る光学的立体造形用樹脂組成物を提供すること
にある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for optical three-dimensional modeling, which has a high heat resistance, a high elastic modulus and a high impact, and which has good workability. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明は、次の（Ａ）、
（Ｂ）、（Ｃ）及び（Ｄ）成分からなる光学的立体造形
用樹脂組成物にある。 （Ａ）下記一般式（１）で示されるジイソシアネート１
モルに対し下記一般式（２）で示されるヒドロキシル基
含有（メタ）アクリレート１．５〜２．５モルの比で反
応させたウレタンジ（メタ）アクリレート ５０〜９０
重量部The present invention provides the following (A),
It is a resin composition for optical three-dimensional modeling comprising components (B), (C) and (D). (A) Diisocyanate 1 represented by the following general formula (1)
Urethane di (meth) acrylate 50-90 reacted with a hydroxyl group-containing (meth) acrylate represented by the following general formula (2) in a ratio of 1.5 to 2.5 mol per mol.
Parts by weight
【０００６】[0006]
【化３】 Embedded image
【０００７】[0007]
【化４】 Embedded image
【０００８】（Ｂ）単官能希釈モノマー １０〜４０重
量部 （Ｃ）ポリアルキレングリコールジ（メタ）アクリレー
ト ０〜３０重量部 （Ｄ）光重合開始剤 （Ａ）、（Ｂ）及び（Ｃ）成分の
合計量１００重量部に対し０．０１〜１０重量部(B) Monofunctional diluting monomer 10 to 40 parts by weight (C) Polyalkylene glycol di (meth) acrylate 0 to 30 parts by weight (D) Photopolymerization initiator Components (A), (B) and (C) 0.01 to 10 parts by weight per 100 parts by weight
【０００９】[0009]
【発明の実施の形態】本発明の樹脂組成物における
（Ａ）成分のウレタンジ（メタ）アクリレートは、前記
一般式（１）で示されるジイソシアネートと前記一般式
（２）で示されるヒドロキシル基含有（メタ）アクリレ
ートを反応させてなるものであり、低粘度の樹脂液を与
え、また高耐熱性、高弾性率で、かつ高衝撃性の硬化物
を得る上での必須の成分である。なお、本発明におい
て、（メタ）アクリレートとは、アクリレート、メタク
リレートを指す。BEST MODE FOR CARRYING OUT THE INVENTION The urethane di (meth) acrylate of the component (A) in the resin composition of the present invention contains a diisocyanate represented by the general formula (1) and a hydroxyl group-containing compound represented by the general formula (2) ( It is formed by reacting a (meth) acrylate, and is an essential component for providing a low-viscosity resin liquid and for obtaining a cured product having high heat resistance, high elastic modulus and high impact. In addition, in this invention, (meth) acrylate refers to an acrylate and a methacrylate.
【００１０】（Ａ）成分のウレタンジ（メタ）アクリレ
ートにおける一般式（１）で示されるジイソシアネート
としては、例えばオルトキシリレンジイソシアネート、
メタキシリレンジイソシアネート、パラキシリレンジイ
ソシアネート、メタテトラメチルキシリレンジイソシア
ネート等が挙げられ、特にメタキシリレンジイソシアネ
ートまたはテトラメチルキシリレンジイソシアネートが
好ましく用いられる。As the diisocyanate represented by the general formula (1) in the urethane di (meth) acrylate as the component (A), for example, orthoxylylene diisocyanate,
Examples thereof include meta-xylylene diisocyanate, para-xylylene diisocyanate, and meta-tetramethyl xylylene diisocyanate, with meta-xylylene diisocyanate or tetramethyl xylylene diisocyanate being particularly preferred.
【００１１】また、一般式（２）で示されるヒドロキシ
ル基含有（メタ）アクリレートとしては、例えば２−ヒ
ドロキシエチル（メタ）アクリレート、２−ヒドロキシ
プロピル（メタ）アクリレート、２−ヒドロキシブチル
（メタ）アクリレート、４−ヒドロキシブチル（メタ）
アクリレート、フェノキシヒドロキシプロピル（メタ）
アクリレート等が挙げられ、特に２−ヒドロキシエチル
（メタ）アクリレート、２−ヒドロキシプロピル（メ
タ）アクリレートが好ましく用いられる。Examples of the hydroxyl group-containing (meth) acrylate represented by the general formula (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. , 4-hydroxybutyl (meth)
Acrylate, phenoxy hydroxypropyl (meth)
An acrylate etc. are mentioned, Especially 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are used preferably.
【００１２】そして、（Ａ）成分のウレタンジ（メタ）
アクリレートは、前記一般式（１）で示されるジイソシ
アネート１モルに対し、前記一般式（２）で示されるヒ
ドロキシル基含有（メタ）アクリレート１．５〜２．５
モルを反応させてなるものである。The urethane di (meth) component (A)
The acrylate is 1.5 to 2.5 of the hydroxyl group-containing (meth) acrylate represented by the general formula (2) with respect to 1 mol of the diisocyanate represented by the general formula (1).
It is made by reacting moles.
【００１３】（Ａ）成分のウレタンジ（メタ）アクリレ
ートの使用量は、５０〜９０重量部、好ましくは６０〜
８０重量部であり、５０重量部未満では、硬化物の耐熱
性、機械的強度が不十分であり、９０重量部を超える
と、樹脂液の粘度が高くなって取扱い性が悪化し造形作
業性が低下する。The amount of urethane di (meth) acrylate used as the component (A) is 50 to 90 parts by weight, preferably 60 to 90 parts by weight.
If it is less than 50 parts by weight, the heat resistance and mechanical strength of the cured product will be insufficient, and if it exceeds 90 parts by weight, the viscosity of the resin liquid will be high and the handleability will deteriorate, and the molding workability will be poor. Is reduced.
【００１４】（Ｂ）成分の単官能希釈モノマーは、反応
性希釈剤としての役割を果たし、例えばメチル（メタ）
アクリレート、エチル（メタ）アクリレート、ｎ−ブチ
ル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレ
ート、ｔ−ブチル（メタ）アクリレート、２−エチルヘ
キシル（メタ）アクリレート、ラウリル（メタ）アクリ
レート、ステアリル（メタ）アクリレート、２−ヒドロ
キシエチル（メタ）アクリレート、２−ヒドロキシプロ
ピル（メタ）アクリレート、２−ヒドロキシブチル（メ
タ）アクリレート、４−ヒドロキシブチル（メタ）アク
リレート、メトキシエチル（メタ）アクリレート、エト
キシエチル（メタ）アクリレート等の脂肪族（メタ）ア
クリレート、フェニル（メタ）アクリレート、ベンジル
（メタ）アクリレート、フェノキシエチル（メタ）アク
リレート、フェノキシプロピル（メタ）アクリレート、
フェノキシジエチレングリコール（メタ）アクリレー
ト、フェノキシヒドロキシプロピル（メタ）アクリレー
ト等の芳香族（メタ）アクリレート、The monofunctional diluting monomer of the component (B) serves as a reactive diluent, for example, methyl (meth).
Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) Aliphatic (meth) acrylates such as acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate,
Aromatic (meth) acrylates such as phenoxydiethylene glycol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate,
【００１５】シクロヘキシル（メタ）アクリレート、イ
ソボルニル（メタ）アクリレート、ジシクロペンテニル
（メタ）アクリレート、ジシクロペンテニルオキシエチ
ル（メタ）アクリレート、トリシクロ［５・２・１・０
2,6］デカニル（メタ）アクリレート、テトラヒドロフ
ルフリル（メタ）アクリレート等の脂環族（メタ）アク
リレート、（メタ）アクリルアミド、Ｎ−メチル（メ
タ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミ
ド、Ｎ−ブチル（メタ）アクリルアミド、Ｎ−オクチル
（メタ）アクリルアミド、Ｎ、Ｎ−ジメチル（メタ）ア
クリルアミド、Ｎ、Ｎ−ジエチル（メタ）アクリルアミ
ド、（メタ）アクリロイルモルホリン、Ｎ−ビニルピロ
リドン等が挙げられる。Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo [5.2.1.0]
2,6 ] Decanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and other alicyclic (meth) acrylates, (meth) acrylamides, N-methyl (meth) acrylamides, N-ethyl (meth) acrylamides, N- Butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, N-vinylpyrrolidone, etc. are mentioned.
【００１６】そして、より高感度化し、硬化物の耐熱
性、機械的強度をより向上させるためには、（Ｂ）成分
の単官能希釈モノマーとしては、先に例示したうちの特
に芳香族アクリレート、脂環族アクリレート及びアクリ
ルアミドの群から選ばれる少なくとも一つであることが
より好ましい。好ましい芳香族アクリレートとしては、
フェニルアクリレート、ベンジルアクリレート、フェノ
キシエチルアクリレート、フェノキシプロピルアクリレ
ート、フェノキシジエチレングリコールアクリレート、
フェノキシヒドロキシプロピルアクリレート等が、好ま
しい脂環族アクリレートとしては、シクロヘキシルアク
リレート、イソボルニルアクリレート、ジシクロペンテ
ニルアクリレート、ジシクロペンテニルオキシエチルア
クリレート、トリシクロ［５・２・１・０2,6］デカニ
ルアクリレート、テトラヒドロフルフリルアクリレート
等が、また好ましいアクリルアミドとしては、アクリル
アミド、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリ
ルアミド、Ｎ−ブチルアクリルアミド、Ｎ−オクチルア
クリルアミド、Ｎ、Ｎ−ジメチルアクリルアミド、Ｎ、
Ｎ−ジエチルアクリルアミド、アクリロイルモルホリン
等がそれぞれ挙げられる。In order to further increase the sensitivity and to further improve the heat resistance and mechanical strength of the cured product, the monofunctional diluting monomer of the component (B) is preferably an aromatic acrylate among those exemplified above. More preferably, it is at least one selected from the group of alicyclic acrylate and acrylamide. Preferred aromatic acrylates include
Phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, phenoxydiethylene glycol acrylate,
Phenoxyhydroxypropyl acrylate and the like are preferable cycloaliphatic acrylates, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclo [5.2.1.0 2,6 ] decanyl Acrylate, tetrahydrofurfuryl acrylate and the like, and preferable acrylamides are acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-butyl acrylamide, N-octyl acrylamide, N, N-dimethyl acrylamide, N,
Examples thereof include N-diethylacrylamide and acryloylmorpholine.
【００１７】（Ｂ）成分の単官能希釈モノマーの使用量
は、１０〜４０重量部、好ましくは１５〜３０重量部で
あり、１０重量部未満では、樹脂液の粘度が高くなって
取扱い性が悪化し造形作業性が低下し、４０重量部を超
えると、硬化物の耐熱性、機械的強度が不十分となる。The amount of the monofunctional diluting monomer used as the component (B) is 10 to 40 parts by weight, preferably 15 to 30 parts by weight. If the amount is less than 10 parts by weight, the viscosity of the resin liquid will be high and handling will be difficult. When it exceeds 40 parts by weight, the heat resistance and mechanical strength of the cured product become insufficient.
【００１８】（Ｃ）成分のポリアルキレングリコールジ
（メタ）アクリレートは、硬化物の耐衝撃性向上の目的
で用い、例えばトリエチレングリコールジ（メタ）アク
リレート、テトラエチレングリコールジ（メタ）アクリ
レート、ノナエチレングリコールジ（メタ）アクリレー
ト、ポリエチレングリコールジ（メタ）アクリレート、
トリプロピレングリコールジ（メタ）アクリレート、ノ
ナブチレングリコールジ（メタ）アクリレート等が挙げ
られる。The polyalkylene glycol di (meth) acrylate as the component (C) is used for the purpose of improving the impact resistance of the cured product. For example, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nona Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Examples include tripropylene glycol di (meth) acrylate and nonabutylene glycol di (meth) acrylate.
【００１９】（Ｃ）成分のポリアルキレングリコールジ
（メタ）アクリレートの使用量は、０〜３０重量部、好
ましくは５〜２０重量部であり、３０重量部を超える
と、硬化物の耐熱性、機械的強度が不十分となる。The amount of the polyalkylene glycol di (meth) acrylate used as the component (C) is 0 to 30 parts by weight, preferably 5 to 20 parts by weight. When it exceeds 30 parts by weight, the heat resistance of the cured product, The mechanical strength becomes insufficient.
【００２０】（Ｄ）成分の光重合開始剤は、光によりラ
ジカル種を生成し重合を開始させるものである。光重合
開始剤としては、例えば２−ヒドロキシ−２−メチル−
１−フェニルプロパン−１−オン、１−ヒドロキシシク
ロヘキシルフェニルケトン、メチルフェニルグリオキシ
レート、アセトフェノン、ベンゾフェノン、２，２−ジ
メトキシ−２−フェニルアセトフェノン、２−メチル
［−４−（メチルチオ）フェニル−］モルフォリノ−１
−プロパノン、ベンジル、ベンゾインメチルエーテル、
ベンゾインエチルエーテル、２−クロロチオキサント
ン、イソプロピルチオキサントン、２，４，６−トリメ
チルベンゾイルジフェニル−フォスフィンオキサイド、
ビス−（２，６−ジメトキシベンゾイル）−２，４，４
−トリメチルペンチル−フォスフィンオキサイド、カン
ファーキノン、ビス（シクロペンタジエニル）−ビス
（２，６−ジフルオロ−３−ピロリルフェニル）チタニ
ウム等が挙げられる。The photopolymerization initiator of the component (D) is one which produces radical species by light to initiate polymerization. Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-
1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, methylphenylglyoxylate, acetophenone, benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl [-4- (methylthio) phenyl-] Morpholino-1
-Propanone, benzyl, benzoin methyl ether,
Benzoin ethyl ether, 2-chlorothioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide,
Bis- (2,6-dimethoxybenzoyl) -2,4,4
-Trimethylpentyl-phosphine oxide, camphorquinone, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyrrolylphenyl) titanium and the like.
【００２１】また、（Ｄ）成分の光重合開始剤の効果を
より高めるために、過酸化ベンゾイル、ジイソプロピル
パーオキシパーカーボネート、ｔ−ブチルパーオキシイ
ソブチレート、ｔ−ブチルパーオキシ−２−エチルヘキ
サノエート、クメンヒドロパーオキシド、アゾビスイソ
ブチロニトリル等の有機過酸化物、トリエチルアミン、
メチルジエチルアミン、ジエタノールアミン等の硬化促
進剤、クマリン、ケトクマリン等の色素増感剤等を本発
明の効果を損なわない範囲で配合してもよい。In order to further enhance the effect of the photopolymerization initiator as the component (D), benzoyl peroxide, diisopropyl peroxypercarbonate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethyl. Hexanoate, cumene hydroperoxide, organic peroxides such as azobisisobutyronitrile, triethylamine,
A curing accelerator such as methyldiethylamine and diethanolamine, a dye sensitizer such as coumarin and ketocoumarin, and the like may be added within a range that does not impair the effects of the present invention.
【００２２】（Ｄ）成分の光重合開始剤の使用量は、前
記の（Ａ）、（Ｂ）及び（Ｃ）成分の合計量１００重量
部に対して０．０１〜１０重量部であり、０．０１重量
部未満では、硬化性が不十分であり、１０重量部を超え
ると、深部硬化性が不良となり、必要な厚さの硬化層を
得ることができなくなる場合があり好ましくない。The amount of the photopolymerization initiator used as the component (D) is 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the components (A), (B) and (C). If it is less than 0.01 part by weight, the curability is insufficient, and if it exceeds 10 parts by weight, the deep part curability becomes poor, and it may not be possible to obtain a cured layer having a required thickness, which is not preferable.
【００２３】本発明の樹脂組成物には、本発明の効果を
損なわない範囲で、その他の共重合可能な化合物や添加
剤が配合されていてもよく、例えば樹脂組成物に耐熱
性、機械的強度等の改良の目的で、ヘキサメチレンジ
（メタ）アクリレート、ネオペンチルグリコールグリコ
ールジ（メタ）アクリレート、トリメチロールエタント
リ（メタ）アクリレート、トリメチロールプロパントリ
（メタ）アクリレート、ペンタエリスリトールトリ（メ
タ）アクリレート、トリス（メタ）アクリロキエチルイ
ソシアヌレート、ペンタエリスリトールテトラ（メタ）
アクリレート、ジペンタエリスリトールペンタ（メタ）
アクリレート、ジペンタエリスリトールヘキサ（メタ）
アクリレート、ウレタン（メタ）アクリレート、エポキ
シ（メタ）アクリレート、ポリエステル（メタ）アクリ
レート等を配合してもよく、また、熱酸化安定剤、紫外
線吸収剤、レベリング剤、消泡剤、ポリマー等の添加剤
や酸化チタン、タルク、炭酸カルシウム、ガラスビー
ズ、プラスチックビーズ等の充填剤等を配合することも
できる。The resin composition of the present invention may contain other copolymerizable compounds and additives within a range that does not impair the effects of the present invention. For example, the resin composition may have heat resistance and mechanical properties. Hexamethylene di (meth) acrylate, neopentyl glycol glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth), for the purpose of improving strength and the like. Acrylate, tris (meth) acryloxyethyl isocyanurate, pentaerythritol tetra (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol hexa (meth)
Acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like may be blended, and additives such as thermal oxidation stabilizer, ultraviolet absorber, leveling agent, defoaming agent and polymer. Fillers such as titanium oxide, talc, calcium carbonate, glass beads, and plastic beads can also be added.
【００２４】本発明の樹脂組成物は、光による優れた硬
化性を有し、硬化に用いられる光源としては、可視光、
紫外光、赤外光、可視レーザ、紫外レーザ、赤外レーザ
等が挙げられる。The resin composition of the present invention has an excellent curability by light, and the light source used for curing is visible light,
Examples thereof include ultraviolet light, infrared light, visible laser, ultraviolet laser and infrared laser.
【００２５】本発明の樹脂組成物は、光学的立体造形用
として有用なるものであり、本発明の樹脂組成物を用い
て三次元立体物を造形する方法としては、レーザで液面
を走査し選択的に硬化する方法、特定形状のマスクを介
して液面を一括露光し選択的に硬化する方法等により平
面状の特定形状の硬化層を形成し、続いて硬化層を液面
下に一層分だけ移動させ或いは硬化層に樹脂液を供給し
硬化層上の新たな液面にレーザ照射を行い硬化層を形成
するという積層操作の繰り返しにより最終的に三次元立
体物を造形する方法等が挙げられる。The resin composition of the present invention is useful for optical three-dimensional modeling. As a method of modeling a three-dimensional three-dimensional object using the resin composition of the present invention, the liquid surface is scanned with a laser. A selective hardening method, a method of collectively exposing the liquid surface through a mask of a specific shape, and a method of selectively hardening it, to form a hardened layer having a specific flat shape, and then applying the hardened layer one layer below the liquid surface. A method of finally modeling a three-dimensional three-dimensional object by repeating the stacking operation of moving the resin or supplying the resin liquid to the hardened layer and irradiating a new liquid surface on the hardened layer with laser to form the hardened layer. Can be mentioned.
【００２６】より具体的には、樹脂液を容器に入れ、液
中に立体造形用の基盤を液面から硬化層一層分に相当の
深さの位置に沈め、基盤上の樹脂液をレーザ走査或いは
マスクを介し特定形状に露光して硬化層を形成し、次い
で樹脂液中の基盤を沈めるか或いは硬化層上に樹脂液を
供給して硬化層上に一層分の樹脂液層を設けレーザ走査
或いは露光して硬化層を形成し、この繰り返しにより最
終的に三次元立体物を造形する方法が挙げられ、この方
法は一般に自由液面法と呼ばれている。More specifically, the resin liquid is placed in a container, the base for three-dimensional modeling is submerged in the liquid at a position corresponding to one layer of the cured layer, and the resin liquid on the base is laser-scanned. Alternatively, a specific shape is exposed through a mask to form a hardened layer, and then the substrate in the resin liquid is submerged, or the resin liquid is supplied onto the hardened layer to form a resin liquid layer for one layer and laser scanning. Alternatively, there is a method of forming a hardened layer by exposure and finally forming a three-dimensional solid object by repeating this, and this method is generally called a free liquid surface method.
【００２７】また、別の方法として、樹脂液を透明容器
に入れ、容器の壁面から一層分の位置に立体造形用の基
盤を沈め、透明壁面より壁面と基盤間の樹脂液をレーザ
走査或いはマスクを介し特定形状に露光して硬化層を形
成し、次いで樹脂液中の基盤を壁面から一層分離れるよ
う移動し壁面と硬化層間に樹脂液を流入させてレーザ走
査或いは露光して硬化層を形成し、この繰り返しにより
最終的に三次元立体物を造形する方法が挙げられ、この
方法は一般に規制液面法と呼ばれている。As another method, the resin liquid is put in a transparent container, the base for three-dimensional modeling is sunk in a position for one layer from the wall surface of the container, and the resin liquid between the wall surface and the base is laser-scanned or masked from the transparent wall surface. To form a hardened layer by exposing the base material in the resin liquid so as to separate it from the wall surface and let the resin liquid flow between the wall surface and the hardened layer by laser scanning or exposure to form a hardened layer. However, there is a method of finally forming a three-dimensional solid object by repeating this, and this method is generally called a regulated liquid level method.
【００２８】また、三次元立体物の造形後に、樹脂液中
から造形物を取り出し、有機溶剤、モノマー、水、洗剤
等で洗浄して未硬化の樹脂液を取り除く方法、或いはま
た加熱、可視光や紫外光の照射等によりポストキュアす
る方法を適宜用いることもできる。In addition, after the three-dimensional three-dimensional object is molded, the molded object is taken out of the resin liquid and washed with an organic solvent, a monomer, water, a detergent or the like to remove the uncured resin liquid, or by heating or visible light. Alternatively, a method of post-curing by irradiation with ultraviolet light or the like can be appropriately used.
【００２９】[0029]
【実施例】以下、本発明を実施例により具体的に説明す
る。The present invention will be described below in more detail with reference to examples.
【００３０】（実施例１） ＜（Ａ）成分の合成＞２リットル三つ口フラスコに、メ
タキシリレンジイソシアネート５６４重量部、２−ヒド
ロキシエチルメタクリレート７９０重量部、触媒として
ジブチルチンジラウリレート０．１重量部、ハイドロキ
ノンモノメチルエーテル０．７重量部を入れ、５０℃で
２時間、次いで７０℃で５時間反応させてウレタンジメ
タクリレート（ＸＤＭＡ１）を合成した。(Example 1) <Synthesis of component (A)> In a 2-liter three-necked flask, 564 parts by weight of metaxylylene diisocyanate, 790 parts by weight of 2-hydroxyethyl methacrylate, and 0.1% of dibutyltin dilaurate as a catalyst. By weight, 0.7 part by weight of hydroquinone monomethyl ether was added and reacted at 50 ° C. for 2 hours and then at 70 ° C. for 5 hours to synthesize urethane dimethacrylate (XDMA1).
【００３１】このウレタンジメタクリレート（ＸＤＭＡ
１）を用い次の組成に配合して樹脂組成物を得た。 ＸＤＭＡ１ ７０重量部 テトラヒドロフルフリルアクリレート（ＴＨＦＡ） ２０重量部 ノナブチレングリコールジアクリレート（９ＢＤＡ） １０重量部 １−ヒドロキシシクロヘキシルフェニルケトン（ＰＩ１） １重量部 得られた樹脂組成物はＥ型粘度計で２５℃で測定したと
ころ１００ｃｐｓと非常に低粘度の液状を呈するもので
あった。This urethane dimethacrylate (XDMA
1) was blended in the following composition to obtain a resin composition. XDMA1 70 parts by weight Tetrahydrofurfuryl acrylate (THFA) 20 parts by weight Nonabutylene glycol diacrylate (9BDA) 10 parts by weight 1-Hydroxycyclohexyl phenyl ketone (PI1) 1 part by weight The obtained resin composition is 25 in E type viscometer. When measured at 0 ° C., it was a liquid having a very low viscosity of 100 cps.
【００３２】この樹脂組成物を縦５０ｍｍ、横５０ｍ
ｍ、深さ１０ｍｍの金型に注入し、液面に高圧水銀灯に
て紫外線を１０００ｍＪ／ｃｍ2照射して樹脂組成物を
重合硬化させた。その後、金型より外し、１３０℃で１
時間のポストキュアを行った。得られた硬化物につい
て、１０ｍｍ×５ｍｍ×５０ｍｍに切り出し３点曲げ試
験を行い曲げ弾性率を、１０ｍｍ×１０ｍｍ×５０ｍｍ
に切り出しアイゾット衝撃試験（ノッチ無し）を行い耐
衝撃強さを、１０ｍｍ×１０ｍｍ×５ｍｍに切り出しＴ
ＭＡ測定を行いＴｇをそれぞれ求め表１に示したが、硬
化物は、高弾性率、高耐衝撃性を有するものであった。This resin composition is 50 mm long and 50 m wide.
The resin composition was polymerized and cured by irradiating the liquid surface with ultraviolet rays of 1000 mJ / cm 2 with a high pressure mercury lamp. After that, remove from the mold, and 1 at 130 ℃
I did a time post cure. The obtained cured product is cut into 10 mm × 5 mm × 50 mm and subjected to a three-point bending test to obtain a bending elastic modulus of 10 mm × 10 mm × 50 mm.
Izod impact test (without notch) is carried out to obtain impact resistance strength of 10 mm x 10 mm x 5 mm T
MA measurement was performed and Tg was calculated, respectively, and shown in Table 1. The cured product had a high elastic modulus and a high impact resistance.
【００３３】（実施例２）実施例１において、紫外線照
射に代えて収束したＨｅ−Ｃｄレーザ（出力２０ｍＷ、
波長３２５μｍ）を液面から垂直に５０ｍｍ×５０ｍｍ
×１０ｍｍの矩形が得られるように照射する以外は、実
施例１と同様にして硬化物を得た。得られた硬化物を実
施例１と同様にして評価し、曲げ弾性率、耐衝撃強さ及
びＴｇを表１に示した。(Example 2) In Example 1, instead of irradiating the ultraviolet rays, a converged He-Cd laser (output 20 mW,
Wavelength of 325 μm) perpendicular to the liquid surface 50 mm x 50 mm
A cured product was obtained in the same manner as in Example 1 except that irradiation was performed so that a rectangle of × 10 mm was obtained. The obtained cured product was evaluated in the same manner as in Example 1, and the flexural modulus, impact strength and Tg are shown in Table 1.
【００３４】（実施例３）実施例１において、樹脂組成
物の配合を ＸＤＭＡ１ ７０重量部 イソボルニルアクリレート（ＩＢＸＡ） ３０重量部 ９ＢＤＡ ０重量部 ＰＩ１ １重量部 とする以外は、実施例１と同様にして硬化物を得た。得
られた硬化物を実施例１と同様にして評価し、曲げ弾性
率、耐衝撃強さ及びＴｇを表１に示した。(Example 3) Example 3 was repeated except that the resin composition was compounded as follows: XDMA1 70 parts by weight Isobornyl acrylate (IBXA) 30 parts by weight 9BDA 0 parts by weight PI1 1 part by weight. A cured product was obtained in the same manner. The obtained cured product was evaluated in the same manner as in Example 1, and the flexural modulus, impact strength and Tg are shown in Table 1.
【００３５】（実施例４）実施例１において、ＸＤＭＡ
１を、（Ａ）成分の合成の際、ジイソシアネートとして
テトラメチルキシリレンジイソシアネートを用い、ヒド
ロキシル基含有アクリレートとして２−ヒドロキシプロ
ピルアクリレートを用い、同様のモル比で反応させて合
成したウレタンジアクリレート（ＸＤＭＡ２）に代えて
用いる以外は、実施例１と同様にして硬化物を得た。得
られた硬化物を実施例１と同様にして評価し、曲げ弾性
率、耐衝撃強さ及びＴｇを表１に示した。(Fourth Embodiment) In the first embodiment, XDMA
In the synthesis of component (A), urethane diacrylate (XDMA2) was synthesized by reacting 1 with tetramethylxylylene diisocyanate as the diisocyanate and 2-hydroxypropyl acrylate as the hydroxyl group-containing acrylate at the same molar ratio. A cured product was obtained in the same manner as in Example 1 except that it was used instead of). The obtained cured product was evaluated in the same manner as in Example 1, and the flexural modulus, impact strength and Tg are shown in Table 1.
【００３６】（比較例１〜２）樹脂組成物として市販の
光学的立体造形用樹脂アデカラスキュアＨＳ−６６０、
ＨＳ−６６３（旭電化（株）製）を用い、実施例１と同
様にして硬化物を得た。得られた硬化物を実施例２と同
様にして評価し、曲げ弾性率、耐衝撃強さ及びＴｇを表
１に示したが、いずれも高弾性率、高耐衝撃性を同時に
満足するものではなかった。(Comparative Examples 1 and 2) Adekaraskure HS-660, a resin for optical stereolithography, which is commercially available as a resin composition,
A cured product was obtained in the same manner as in Example 1 using HS-663 (manufactured by Asahi Denka Co., Ltd.). The obtained cured product was evaluated in the same manner as in Example 2 and the flexural modulus, impact strength and Tg are shown in Table 1. However, in the case where all of them satisfy high modulus and high impact resistance at the same time. There wasn't.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】本発明の光学的立体造形用樹脂組成物
は、粘度が低く、立体造形物を作業性良好に得ることが
でき、また造形速度が大きく、得られる硬化物は、高耐
熱性、高弾性率及び高衝撃性を有することから、高耐熱
性、高弾性率で、かつ高衝撃性の立体造形物を得ること
ができる。EFFECTS OF THE INVENTION The resin composition for optical three-dimensional modeling of the present invention has a low viscosity, a three-dimensional molded article can be obtained with good workability, a molding rate is high, and the obtained cured product has high heat resistance. Since it has high elastic modulus and high impact resistance, it is possible to obtain a three-dimensional molded article having high heat resistance, high elastic modulus and high impact resistance.
Claims (3)
成分からなる光学的立体造形用樹脂組成物。 （Ａ）下記一般式（１）で示されるジイソシアネート１
モルに対し下記一般式（２）で示されるヒドロキシル基
含有（メタ）アクリレート１．５〜２．５モルの比で反
応させたウレタンジ（メタ）アクリレート ５０〜９０
重量部 【化１】 【化２】 （Ｂ）単官能希釈モノマー １０〜４０重量部 （Ｃ）ポリアルキレングリコールジ（メタ）アクリレー
ト ０〜３０重量部 （Ｄ）光重合開始剤 （Ａ）、（Ｂ）及び（Ｃ）成分の
合計量１００重量部に対し０．０１〜１０重量部1. The following (A), (B), (C) and (D)
A resin composition for optical three-dimensional modeling comprising components. (A) Diisocyanate 1 represented by the following general formula (1)
Urethane di (meth) acrylate 50 to 90 reacted with a hydroxyl group-containing (meth) acrylate represented by the following general formula (2) in a ratio of 1.5 to 2.5 mol per mol.
Parts by weight Embedded image (B) Monofunctional diluting monomer 10-40 parts by weight (C) Polyalkylene glycol di (meth) acrylate 0-30 parts by weight (D) Photopolymerization initiator Total amount of components (A), (B) and (C) 0.01 to 10 parts by weight per 100 parts by weight
メタキシリレンジイソシアネート及びテトラメチルキシ
リレンジイソシアネートの群から選ばれる一つであり、
ヒドロキシル基含有（メタ）アクリレートが２−ヒドロ
キシエチル（メタ）アクリレート及び２−ヒドロキシプ
ロピル（メタ）アクリレートの群から選ばれる一つであ
る請求項１記載の光学的立体造形用樹脂組成物。2. The diisocyanate in the component (A) is one selected from the group consisting of metaxylylene diisocyanate and tetramethylxylylene diisocyanate,
The resin composition for optical stereolithography according to claim 1, wherein the hydroxyl group-containing (meth) acrylate is one selected from the group consisting of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
香族アクリレート、脂環族アクリレート及びアクリルア
ミドの群から選ばれる少なくとも一つである請求項１ま
たは請求項２記載の光学的立体造形用樹脂組成物。3. The optical three-dimensional modeling according to claim 1 or 2, wherein the monofunctional diluent monomer as the component (B) is at least one selected from the group consisting of aromatic acrylates, alicyclic acrylates and acrylamides. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02621896A JP3668310B2 (en) | 1996-01-22 | 1996-01-22 | Optical three-dimensional molding resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02621896A JP3668310B2 (en) | 1996-01-22 | 1996-01-22 | Optical three-dimensional molding resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09194540A true JPH09194540A (en) | 1997-07-29 |
| JP3668310B2 JP3668310B2 (en) | 2005-07-06 |
Family
ID=12187271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02621896A Expired - Fee Related JP3668310B2 (en) | 1996-01-22 | 1996-01-22 | Optical three-dimensional molding resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3668310B2 (en) |
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