JPH02208305A - Photocurable composition - Google Patents
Photocurable compositionInfo
- Publication number
- JPH02208305A JPH02208305A JP2926089A JP2926089A JPH02208305A JP H02208305 A JPH02208305 A JP H02208305A JP 2926089 A JP2926089 A JP 2926089A JP 2926089 A JP2926089 A JP 2926089A JP H02208305 A JPH02208305 A JP H02208305A
- Authority
- JP
- Japan
- Prior art keywords
- cured product
- composition
- photocurable composition
- light beam
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- -1 acrylic ester Chemical class 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229940111759 benzophenone-2 Drugs 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、光硬化性組成物に関する。さらに詳しくは、
立体形状の硬化体を製造する際に用いられる光硬化性組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photocurable composition. For more details,
The present invention relates to a photocurable composition used in producing a three-dimensional cured product.
［従来の技術］
従来、塗料用、インキ用、接着剤用、感光樹脂成用など
の光硬化性組成物が知られている。[Prior Art] Photocurable compositions for use in paints, inks, adhesives, photosensitive resins, and the like are conventionally known.
［発明が解決しようとする課題］
しかし、従来の光硬化性組成物を光硬化性組成物に光束
を照射して、照射された部分を硬化させた後に硬化物の
周辺部の未硬化の光硬化性組成物に光束を照射して硬化
させ以後これを繰り返して立体形状の硬化体を製造する
際に用いると、立体形状の硬化体を製造中に硬化体に歪
や亀裂が発生したり、硬化体が得られても、その寸法精
度が劣るという問題があった。[Problems to be Solved by the Invention] However, after the conventional photocurable composition is irradiated with a light flux and the irradiated area is cured, uncured light in the peripheral area of the cured product is removed. If a curable composition is used to produce a three-dimensional cured product by irradiating a light beam to cure it and then repeating this process, distortion or cracks may occur in the cured product during the production of the three-dimensional cured product. Even if a cured product was obtained, there was a problem that its dimensional accuracy was poor.
［課題を解決するための手段］
本発明者らは、立体形状の硬化体の製造に適した光硬化
性組成物を検討した結果、本発明に到達した。すなわち
、本発明は、一般式（］）［式中、Ｒ１、Ｒ２、Ｒ３、
Ｒ４は水素原子、メチル基、エチル基またはＣＦ３基、
Ａはエチレン基またはプロピレン基、ｍＸｎは１−１０
である］で示される （メタ）アクリル酸エステルを６
５重量％以上含有してなる、光硬化性組成物に光束を照
射して照射された部分を硬化させた後に硬化物の周辺部
の未硬化の該光硬化性組成物を同様に光束を照射して硬
化させ、以後この工程を繰り返して立体形状の硬化体を
製造する際に用いられる光硬化性組成物である。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of studying a photocurable composition suitable for producing a three-dimensional cured product. That is, the present invention relates to the general formula (]) [wherein R1, R2, R3,
R4 is a hydrogen atom, a methyl group, an ethyl group, or a CF3 group,
A is ethylene group or propylene group, mXn is 1-10
is the (meth)acrylic acid ester represented by 6
After irradiating a photocurable composition containing 5% by weight or more with a light beam and curing the irradiated portion, the uncured photocurable composition in the peripheral area of the cured product is similarly irradiated with a light beam. This is a photocurable composition used when producing a three-dimensional cured product by curing the composition and repeating this process thereafter.
一般式（ｌン（こおいて、ｍ、ｎは１〜ＩＱであり、好
ましくは２〜８である。ｍＸｎが１未満であると室温で
固体またはペースト状であり、立体形状の硬化体を製造
するのに適さない。また、ｒｎＸｎがＩＯを越えると組
成物の粘度が高くなったり、硬化体の硬度が低くなった
りする。General formula (1) where m and n are 1 to IQ, preferably 2 to 8. If m In addition, if rnXn exceeds IO, the viscosity of the composition increases and the hardness of the cured product decreases.
一般式（１）で示される （メタ）アクリル酸エステル
は公知の方法で製造することができる。例えば、ビスフ
ェノールＡ１ビスフエノールＦなどのビスフェノール類
にエチレンオキサイドおよび／またはプロピレンオキサ
イドを付加させた後、 （メタ）アクリル酸とエステル
化することにより製造することができる。The (meth)acrylic acid ester represented by the general formula (1) can be produced by a known method. For example, it can be produced by adding ethylene oxide and/or propylene oxide to bisphenols such as bisphenol A1 and bisphenol F, and then esterifying it with (meth)acrylic acid.
本発明における組成物は必要に応じて、公知の光硬化性
オリゴマー、モノマーと併用することができる。使用さ
れるオリゴマー、モノマーは、特に限定されないが、組
成物の粘度および硬化収縮率の観点から、粘度が低く、
かつ、 （メタ）アクロイル基１個当りの分子量が大き
い物が好ましい。The composition of the present invention can be used in combination with known photocurable oligomers and monomers, if necessary. The oligomers and monomers used are not particularly limited, but from the viewpoint of the viscosity of the composition and curing shrinkage rate, the viscosity is low,
In addition, those having a large molecular weight per (meth)acroyl group are preferable.
オリゴマーとしては、例えば、分子量５００〜５０００
のポリプロピレングリコールまたはそのモノエーテル、
モノエステルなどとポリイソシアネートとＮＣ○過剰で
反応させ更に水酸基含有（メタ）アクリル酸エステルと
反応させた物があげられる。As an oligomer, for example, a molecular weight of 500 to 5000
polypropylene glycol or its monoether,
An example is a product obtained by reacting a monoester or the like with a polyisocyanate in an excess of NC○, and further reacting with a hydroxyl group-containing (meth)acrylic acid ester.
また、モノマーとしては、例えば、分子量２０００未満
のポリプロピレングリコールのモノエーテルおよび／ま
たはモノエステルおよびアルキル（アルキル基の炭素数
は通常１〜２０）フェノールのアルキレンオキサイド付
加物と （メタ）アクリル酸とのエステル化物があげら
れる。Examples of monomers include monoethers and/or monoesters of polypropylene glycol with a molecular weight of less than 2000, alkylene oxide adducts of alkyl (alkyl group usually has 1 to 20 carbon atoms) phenol, and (meth)acrylic acid. Examples include esterified products.
本発明において、必要に応じて公知の光重合開始剤を配
合することができる。光重合開始剤としては、例えば、
ベンゾインアルキルエーテル、ベンジルジメチルケター
ル、■−ヒドロキシシクロへキシルフェニルケトン、２
−ヒドロキシ−２−メチル−１−フェニルプロパン−１
−オン、ペンツフェノン、メチルベンゾイルフォーメー
ト、イソプロピルチオキサントンなどがあげられる。In the present invention, a known photopolymerization initiator may be blended as necessary. As the photopolymerization initiator, for example,
Benzoin alkyl ether, benzyl dimethyl ketal, ■-hydroxycyclohexylphenyl ketone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-one, pentuphenone, methylbenzoyl formate, isopropylthioxanthone, and the like.
本発明の組成物において、一般式（１）で示される（メ
タ）アクリル酸エステルの量は組成物の重量に基づいて
６５％以上、好ましくは７０％以上である。６５％未満
では、硬化収縮率が大きくなり硬化体の製造中に歪や亀
裂が発生したり、硬化体の寸法精度が低下する。In the composition of the present invention, the amount of the (meth)acrylic ester represented by general formula (1) is at least 65%, preferably at least 70%, based on the weight of the composition. If it is less than 65%, the curing shrinkage rate becomes large, causing distortions and cracks during the production of the cured product, and the dimensional accuracy of the cured product decreases.
公知の光硬化性オリゴマー、モノマーの量は組成物の重
量に基づいて０〜３５％、好ましくは０〜３０％である
。The amount of known photocurable oligomers and monomers is from 0 to 35%, preferably from 0 to 30%, based on the weight of the composition.
光重合開始剤の配合量は特に限定されないが、組成物の
重量に基づいて通常、０．１〜１０％、好ましくは１．
５〜５％である。The amount of the photopolymerization initiator is not particularly limited, but is usually 0.1 to 10%, preferably 1.0% based on the weight of the composition.
It is 5-5%.
本発明において、光硬化性組成物に光束を照射して、照
射された部分を硬化させた後、硬化物の周辺部の未硬化
の光硬化性組成物に同様に光束を照射して硬化させ、以
後これを繰り返して立体形状の硬化体を製造する際には
硬化装置が用いられる。用いられる硬化装置は、特に限
定されないが、例えば、第１図に示したものがあげられ
る。すなわち、攪拌機１０を備えた容器ｌｌ内に本発明
の光硬化性組成物が収容され、その液面１３に向けて光
束１４を照射するようにレンズ１５、ミラー１６、ミラ
ー回転駆動装置１７、光源２０等よりなる光学系が設け
られている。In the present invention, the photocurable composition is irradiated with a light beam to cure the irradiated portion, and then the uncured photocurable composition at the periphery of the cured product is similarly irradiated with the light beam and cured. A curing device is used when repeating this process to produce a three-dimensional cured product. The curing device used is not particularly limited, but for example, the one shown in FIG. 1 can be mentioned. That is, the photocurable composition of the present invention is housed in a container 11 equipped with a stirrer 10, and a lens 15, a mirror 16, a mirror rotation drive device 17, and a light source are installed so as to irradiate a light beam 14 toward the liquid surface 13. An optical system consisting of 20 etc. is provided.
容器１１内にはテーブル２１が設置され、該テーブル２
１はエレベータ２２により昇降可能とれれている。これ
ら駆動装置１７、エレベータ２２はコンピュータ２３に
より制御される。A table 21 is installed inside the container 11, and the table 2
1 can be raised and lowered by an elevator 22. These driving device 17 and elevator 22 are controlled by a computer 23.
上記装置により硬化体を製造する場合、まずテーブル２
１上の基板２１ａを液面１３よりもわずか下方に位置さ
せ、光束１４を目的形状物の水平断面に倣って走査させ
る。この走査はコンピュータ制御されたミラー１６の回
転により行われる。When producing a cured body using the above device, first the table 2
The substrate 21a on the liquid surface 13 is positioned slightly below the liquid level 13, and the light beam 14 is scanned along the horizontal cross section of the target object. This scanning is performed by computer-controlled rotation of mirror 16.
目的形状物の一つの水平断面（この場合は底面に相当す
る部分）のすべてに光を照射した後、テーブル２１をわ
ずかに下降させ、硬化物２４の上に未硬化の光硬化性組
成物を流入させた後、上記と同様の光照射を行う。この
手順を繰り返すことにより、目的形状の硬化体が得られ
る。After irradiating the entire horizontal cross section of the target shape (in this case, the portion corresponding to the bottom surface), the table 21 is lowered slightly and the uncured photocurable composition is placed on the cured product 24. After flowing in, the same light irradiation as above is performed. By repeating this procedure, a cured product having the desired shape can be obtained.
また、光学系は光ファイバを採用してもよい。Further, the optical system may employ an optical fiber.
さらに、光学系は静止させ、容器１１を移動させること
によって光束１４を液面１３に対し相対的に移動させる
ようにしてもよい。Furthermore, the optical system may be kept stationary and the light beam 14 may be moved relative to the liquid surface 13 by moving the container 11.
第１図では、光を液面の上方から照射するようにしてい
るが、容器１１の少なくとも所要箇所を光透過性とし、
該容器１１の底面や側面などから光を照射するようにし
てもよい。この場合、テーブルは成形過程において徐々
に上方に引き上げたり、側方に移動さぜたりすればよい
。In FIG. 1, light is irradiated from above the liquid surface, but at least required parts of the container 11 are made light-transmissive,
Light may be irradiated from the bottom or side of the container 11. In this case, the table may be gradually pulled upward or moved sideways during the molding process.
［実施例］
以下に本発明を実施例により説明するが、本発明はこれ
に限定されるものではない。実施例中の部は重量部を示
す。[Example] The present invention will be explained below using Examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight.
実施例１
本発明に係わる一般式（１）において、ｍ、ｎがそれぞ
れ平均４であるアクリル酸エステル８０部、ノニルフェ
ノールのエチレンオキサイド２モル付加物とアクリル酸
とからのアクリル酸エステル２０部およびベンゾインイ
ソプロピルエーテル４部を混合、溶解して本発明の光硬
化性組成物を得た。Example 1 80 parts of an acrylic ester in which m and n each have an average of 4 in the general formula (1) according to the present invention, 20 parts of an acrylic ester obtained from an adduct of 2 moles of ethylene oxide of nonylphenol and acrylic acid, and benzoin. A photocurable composition of the present invention was obtained by mixing and dissolving 4 parts of isopropyl ether.
実施例２
本発明に係わる一般式（１）において、ｒｎ、 ｎがそ
れぞれ平均８であるメタクリル酸エステル１００部およ
びベンジルジメチルケタール３部を混合、溶解して本発
明の光硬化性組成物を得た。Example 2 A photocurable composition of the present invention was obtained by mixing and dissolving 100 parts of a methacrylic ester having general formula (1) in which rn and n are each 8 on average and 3 parts of benzyl dimethyl ketal. Ta.
実施例３
本発明に係わる一般式（１）において、ｍ、ｎがそれぞ
れ平均２であるアクリル酸エステル７０部、分子量２０
００のポリプロピレングリコールモノブチルエーテルと
イソホロンジイソシアネートとヒドロキシエチルメタク
リレートとからのオリゴマー３０部、ベンゾフェノン２
．５部およびＩ−ヒドロキシシクロへキシルフェニルケ
トン２．５部を混合、溶解して本発明の光硬化性組成物
を得た。Example 3 In the general formula (1) according to the present invention, 70 parts of an acrylic ester in which m and n each have an average of 2, and a molecular weight of 20
00 polypropylene glycol monobutyl ether, isophorone diisocyanate and hydroxyethyl methacrylate oligomer 30 parts, benzophenone 2
．． A photocurable composition of the present invention was obtained by mixing and dissolving 5 parts of I-hydroxycyclohexyl phenyl ketone and 2.5 parts of I-hydroxycyclohexylphenyl ketone.
比較例１
本発明に係わる一般式（１）において、ｍＸｎがそれぞ
れ平均２であるアクリル酸エステル６０部、ネオペンチ
ルグリコールのプロピレンオキサイド４モル付加物とア
クリル酸からのアクリル酸エステル４０部、ベンゾフェ
ノン２．５部および１−ヒドロキシシクロへキシルフェ
ニルケトン２．５部ヲ混合、溶解して比較用の光硬化性
組成物を得た。Comparative Example 1 In the general formula (1) according to the present invention, 60 parts of an acrylic ester each having an average mXn of 2, 40 parts of an acrylic ester from a 4 mol adduct of neopentyl glycol with propylene oxide and acrylic acid, and 2 parts of benzophenone. .5 parts of 1-hydroxycyclohexyl phenyl ketone were mixed and dissolved to obtain a comparative photocurable composition.
試験例１
実施例１から３および比較例１．２で得られた光硬化性
組成物を第１図に示した硬化装置を用いて硬化体の製造
試験をした。試験結果を表−１に示す。Test Example 1 The photocurable compositions obtained in Examples 1 to 3 and Comparative Examples 1.2 were tested for producing cured products using the curing apparatus shown in FIG. The test results are shown in Table-1.
［発明の効果］
本発明の光硬化性組成物は従来の光硬化性組成物と比べ
て、光硬化性組成物に光束を照射して照射された部分を
硬化させた後に硬化物の周辺部の＝１０
未硬化の該光硬化性組成物を同様に光束を照射して硬化
させ、以後これを繰り返して立体形状の硬化体を製造す
る際に用いると、得られた硬化体に歪や亀裂の発生がみ
られず、また、硬化体に変形もなく、寸法精度が優れて
いる。[Effects of the Invention] Compared to conventional photocurable compositions, the photocurable composition of the present invention is superior in that after irradiating the photocurable composition with a light flux and curing the irradiated area, the peripheral area of the cured product is = 10 If the uncured photocurable composition is similarly irradiated with a light beam to cure it, and then used to produce a three-dimensional cured product by repeating this process, the resulting cured product will have no distortion or cracks. There is no occurrence of this, and there is no deformation in the cured product, and the dimensional accuracy is excellent.
第１図は本発明の光硬化性組成物を用いて立体形状の硬
化体を得るための硬化装置の構成図である。FIG. 1 is a configuration diagram of a curing apparatus for obtaining a three-dimensional cured product using the photocurable composition of the present invention.
Claims (1)
メチル基、エチル基またはＣＦ＿３基、Ａはエチレン基
またはプロピレン基、ｍ、ｎは１〜１０である］で示さ
れる（メタ）アクリル酸エステルを６５重量％以上含有
してなる、光硬化性組成物に光束を照射して照射された
部分を硬化させた後に硬化物の周辺部の未硬化の該光硬
化性組成物を同様に光束を照射して硬化させ、以後この
工程を繰り返して立体形状の硬化体を製造する際に用い
られる光硬化性組成物。[Claims] 1. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, R_1, R_2, R_3, R_4 are hydrogen atoms,
A photocurable composition containing 65% by weight or more of a (meth)acrylic acid ester represented by a methyl group, an ethyl group, or a CF_3 group, A is an ethylene group or a propylene group, and m and n are 1 to 10. After irradiating the object with a light beam and curing the irradiated part, the uncured photocurable composition in the peripheral area of the cured object is similarly irradiated with a light beam to harden it, and this process is repeated thereafter to form a three-dimensional shape. A photocurable composition used in producing a cured product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2926089A JPH02208305A (en) | 1989-02-07 | 1989-02-07 | Photocurable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2926089A JPH02208305A (en) | 1989-02-07 | 1989-02-07 | Photocurable composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02208305A true JPH02208305A (en) | 1990-08-17 |
Family
ID=12271310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2926089A Pending JPH02208305A (en) | 1989-02-07 | 1989-02-07 | Photocurable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208305A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849459A (en) * | 1994-11-29 | 1998-12-15 | Teijin Seiki Co., Ltd. | Resin composition for stereolithography |
| US5981616A (en) * | 1996-12-13 | 1999-11-09 | Dsm N.V. | Photo-curable resin composition used for photo fabication of three-dimensional objects |
| US6036910A (en) * | 1996-09-25 | 2000-03-14 | Teijin Seiki Co., Ltd. | Three-dimensional object by optical stereography and resin composition containing colorant for producing the same |
| US6096796A (en) * | 1996-12-10 | 2000-08-01 | Dsm N.V. | Photo-curable resin composition |
| US6127085A (en) * | 1996-10-14 | 2000-10-03 | Dsm N.V. | Photo-curable resin composition |
| WO2006082845A1 (en) * | 2005-02-04 | 2006-08-10 | Daikin Industries, Ltd. | Curable composition and optical member obtained by curing same |
| EP1961773A2 (en) | 2007-02-20 | 2008-08-27 | FUJIFILM Corporation | Photopolymerizable composition |
| US8207239B2 (en) | 2005-06-16 | 2012-06-26 | Dsm Ip Assets B.V. | Radioactive ray-curable liquid resin composition for use in optical stereolithography, and optically shaped article produced by curing the composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS524203A (en) * | 1975-06-30 | 1977-01-13 | Yokogawa Hokushin Electric Corp | Optical signal record play back system |
| JPS5755910A (en) * | 1980-09-19 | 1982-04-03 | Osaka Soda Co Ltd | Acrylate resin composition |
| JPS6451413A (en) * | 1987-08-24 | 1989-02-27 | Toyo Ink Mfg Co | Photo-setting covering material |
-
1989
- 1989-02-07 JP JP2926089A patent/JPH02208305A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS524203A (en) * | 1975-06-30 | 1977-01-13 | Yokogawa Hokushin Electric Corp | Optical signal record play back system |
| JPS5755910A (en) * | 1980-09-19 | 1982-04-03 | Osaka Soda Co Ltd | Acrylate resin composition |
| JPS6451413A (en) * | 1987-08-24 | 1989-02-27 | Toyo Ink Mfg Co | Photo-setting covering material |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849459A (en) * | 1994-11-29 | 1998-12-15 | Teijin Seiki Co., Ltd. | Resin composition for stereolithography |
| US6162576A (en) * | 1994-11-29 | 2000-12-19 | Teijin Seiki Co., Ltd. | Resin composition for stereolithography |
| US6036910A (en) * | 1996-09-25 | 2000-03-14 | Teijin Seiki Co., Ltd. | Three-dimensional object by optical stereography and resin composition containing colorant for producing the same |
| US6127085A (en) * | 1996-10-14 | 2000-10-03 | Dsm N.V. | Photo-curable resin composition |
| US6096796A (en) * | 1996-12-10 | 2000-08-01 | Dsm N.V. | Photo-curable resin composition |
| US5981616A (en) * | 1996-12-13 | 1999-11-09 | Dsm N.V. | Photo-curable resin composition used for photo fabication of three-dimensional objects |
| US6365644B1 (en) | 1996-12-13 | 2002-04-02 | Dsm N.V. | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
| USRE42593E1 (en) | 1996-12-13 | 2011-08-02 | Dsm Ip Assets B.V. | Photo-curable resin composition used for photo-fabrication of three-dimensional object |
| WO2006082845A1 (en) * | 2005-02-04 | 2006-08-10 | Daikin Industries, Ltd. | Curable composition and optical member obtained by curing same |
| US8207239B2 (en) | 2005-06-16 | 2012-06-26 | Dsm Ip Assets B.V. | Radioactive ray-curable liquid resin composition for use in optical stereolithography, and optically shaped article produced by curing the composition |
| EP1961773A2 (en) | 2007-02-20 | 2008-08-27 | FUJIFILM Corporation | Photopolymerizable composition |
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