JPH0222305A - Paste of photopolymerization initiator - Google Patents
Paste of photopolymerization initiatorInfo
- Publication number
- JPH0222305A JPH0222305A JP17179788A JP17179788A JPH0222305A JP H0222305 A JPH0222305 A JP H0222305A JP 17179788 A JP17179788 A JP 17179788A JP 17179788 A JP17179788 A JP 17179788A JP H0222305 A JPH0222305 A JP H0222305A
- Authority
- JP
- Japan
- Prior art keywords
- photopolymerization initiator
- paste
- meth
- ink
- acrylate
- 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
- 239000003999 initiator Substances 0.000 title claims abstract description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- -1 thioxanthone compound Chemical class 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 abstract description 2
- 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 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000037406 food intake Effects 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N phenyldimethylamine Natural products CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 2
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 2
- 208000010201 Exanthema Diseases 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 201000005884 exanthem Diseases 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical class CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- JYMNQRQQBJIMCV-UHFFFAOYSA-N 4-(dimethylamino)benzonitrile Chemical compound CN(C)C1=CC=C(C#N)C=C1 JYMNQRQQBJIMCV-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- BKRHVMFSILFMNK-UHFFFAOYSA-N CNC1(CC=C(C(=O)O)C=C1)NC Chemical class CNC1(CC=C(C(=O)O)C=C1)NC BKRHVMFSILFMNK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- HXTBYXIZCDULQI-UHFFFAOYSA-N bis[4-(methylamino)phenyl]methanone Chemical compound C1=CC(NC)=CC=C1C(=O)C1=CC=C(NC)C=C1 HXTBYXIZCDULQI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ALXIOUGHHXXLKX-UHFFFAOYSA-N n,n-dimethyl-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C)C ALXIOUGHHXXLKX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は光重合開始剤のペーストに関する。[Detailed description of the invention] Industrial applications The present invention relates to a photopolymerization initiator paste.
更に詳しくは紫外線硬化型コーチインゲス、紫外線硬化
型インキの製造に用いるのに最適な光重合開始剤のペー
ストに関する。More specifically, the present invention relates to a paste of a photopolymerization initiator that is most suitable for use in the production of ultraviolet curable coaching inks and ultraviolet curable inks.
従来の技術
紫外線硬化型コーチインゲス又は紫外線硬化型インキは
熱による乾燥工程が省略出来ること、短時間忙硬化する
こと、環境汚染が少ない事等の利点の為に、従来の溶媒
型（酸素硬化型）のそれに置き換えられ、更に最近では
基材に機能性を付与する観点からも、例えば熱に弱い基
材のコーティング等へと用途分野を拡大しつつある。Conventional technology Ultraviolet curing type ink or ultraviolet curing type ink is different from the conventional solvent type (oxygen curing type) due to its advantages such as omitting the drying process using heat, quick curing time, and less environmental pollution. Recently, from the viewpoint of imparting functionality to substrates, the field of application has been expanding to include coatings on substrates that are sensitive to heat, for example.
紫外線硬化型コーチインゲス又は紫外線硬化型インキは
通常ラジカル重合性二重結合を有するモノマー オリゴ
マー（ビヒクル）と元重合開始剤及び添加剤から成る。Ultraviolet curable coatings or ultraviolet curable inks usually consist of a monomer oligomer (vehicle) having a radically polymerizable double bond, a polymerization initiator, and additives.
このうち添加剤は着色剤、フィラー 重合禁止剤その他
のコーチインゲス又はインキ用の助剤例えば、界面活性
剤、粘度調整剤等である。充分なコーティング特性又は
インキ適性を得るためには、これらの成分が均一に微細
粒子状に混練されていなければならない。とりわけ最も
基本的な構成成分の１つである光重合開始剤を均一に微
分散させることは、平滑な塗膜を得るための必須条件で
ある。通常、三本ロールがこの目的の為に使用されるが
、均一な微分散状態にする為に摩擦熱の発生を伴う長時
間の混練は重合禁止剤が添加されていると言えども好ま
しくなく又生産性が悪い。従って、場合罠よりては固形
の光重合開始剤を光重合促進剤とともに必要最低限量の
有機溶媒に溶解させて、それを樹脂中に添加するなどの
便宜的な方法で均一な混和が短時間で達成されるような
方法がとられている。しかしながらこの場合、溶媒の除
去や溶媒の引火の危険性等の問題があり、得策ではない
。又、光重合開始剤の添加はコーチインゲス又はインキ
の調製過程の最終段階で添加されるのが好ましい。又、
既に混練済のコーチインゲス又はインキに更に各種の光
重合開始剤、光重合促進剤及びその他の助剤を添加して
最終製品とする場合もある。Among these, additives include colorants, fillers, polymerization inhibitors, and other coaching agents or auxiliary agents for ink, such as surfactants, viscosity modifiers, and the like. In order to obtain sufficient coating properties or ink suitability, these components must be uniformly kneaded into fine particles. In particular, it is essential to uniformly and finely disperse the photopolymerization initiator, which is one of the most basic components, in order to obtain a smooth coating film. Normally, three-roll rolls are used for this purpose, but in order to obtain a uniform finely dispersed state, long-term kneading with the generation of frictional heat is undesirable, even though polymerization inhibitors are added. Poor productivity. Therefore, in some cases, a convenient method such as dissolving a solid photopolymerization initiator together with a photopolymerization accelerator in the minimum necessary amount of organic solvent and adding it to the resin can achieve uniform mixing in a short time. A method has been adopted to achieve this. However, in this case, there are problems such as removal of the solvent and the risk of ignition of the solvent, so it is not a good idea. Further, it is preferable that the photopolymerization initiator is added at the final stage of the preparation process of the coating composition or ink. or,
In some cases, various photopolymerization initiators, photopolymerization accelerators, and other auxiliary agents are further added to the already kneaded coaching gel or ink to produce a final product.
これらの何れの場合も光重合開始剤又は光重合促進剤が
コーチインゲス又はインキ中に容易に。In any of these cases, the photopolymerization initiator or photopolymerization accelerator is easily included in the coating composition or ink.
且つ迅速に微分散される事が要望されている。Moreover, it is desired to be finely dispersed quickly.
このような目的の為には光重合開始剤 ペーストを用い
るのが好都合であり、このようなペーストが具備すべき
条件として次のものが挙げら高濃度であること。For this purpose, it is convenient to use a photopolymerization initiator paste, and such a paste must meet the following conditions: It must be highly concentrated.
（２） コーチインゲス又はインキ等のビヒクル及び
コーチインゲス又はインキとの相溶性が良いこと。(2) It has good compatibility with vehicles such as Coach Inguess or ink, and with Coach Inguess or ink.
（３） ペースト中の光重合開始剤が保存中に析出、
沈降又は凝集しないこと。(3) The photopolymerization initiator in the paste precipitates during storage,
Do not settle or aggregate.
（４）ペースト自体が光硬化反応に寄与し、硬化速度が
速いこと。(4) The paste itself contributes to the photocuring reaction and the curing speed is fast.
紫外線硬化型コーチインゲス又紫外線硬化型インキを調
製するにあたり光重合開始剤ペーストを従来の固形の光
重合開始剤とほぼ同様な処方で使用することができ、し
かもコーチインゲス及びインキそのものの物性や硬化後
の被膜の物性にあまり影響を与えない為にはペースト中
の光重合開始剤の濃度が高いこと及び、コーチインゲス
又はインキのビヒクルとペーストのビヒクルの性質が似
ていることが必要である。紫外線硬化型のコーチインゲ
ス又はインキのビヒクルは一般には単官能又は多官能の
（メタ）アクリレートが使用されるので、光重合開始剤
ペーストのビヒクルとしても（メタ）アクリレート類が
最適である。In preparing ultraviolet-curable coaching ingestion or ultraviolet-curing ink, the photoinitiator paste can be used in almost the same formulation as conventional solid photoinitiators, and the physical properties of the coaching ingestion and ink itself and after curing can be used. In order to not significantly affect the physical properties of the coating, it is necessary that the concentration of the photopolymerization initiator in the paste be high and that the properties of the paste vehicle be similar to those of the coach ingestion or ink vehicle. Since monofunctional or polyfunctional (meth)acrylates are generally used as vehicles for ultraviolet curable coating inks or inks, (meth)acrylates are also optimal as vehicles for photopolymerization initiator pastes.
光重合開始剤ペーストは、一般的には固形の光重合開始
剤を（メタ）アクリレート類に加え、加熱溶解した後冷
却下に強力に激しく攪拌しながら、微細粒子を生成させ
るか又は光重合開始剤を機械的に（ボールミル等で）微
粉砕した後、（メタ）アクリレート類に添加して（場合
によっては熱時に）調製される。このように調製された
微細粒子から成るペーストは保存期間中に光重合開始剤
の沈降、析出、粒子径の増大、微細粒子の凝集等の現象
がしばしば観察される。Photopolymerization initiator paste is generally produced by adding a solid photopolymerization initiator to (meth)acrylates, heating and dissolving it, and then stirring vigorously while cooling to generate fine particles or to initiate photopolymerization. It is prepared by mechanically pulverizing the agent (such as with a ball mill) and then adding it to (meth)acrylates (sometimes under heat). Phenomena such as precipitation and precipitation of the photopolymerization initiator, increase in particle size, and aggregation of the fine particles are often observed during storage of the paste made of fine particles prepared in this manner.
発明が解決しようとする課題
長期間保存しても光重合開始剤が沈降、析出したり、粒
子径が増大、微細粒子の凝集等の現象を起さず紫外線硬
化型コーチインゲス、インキあるいはそれらのビヒクル
との相溶性が良好な光重合開始剤ペーストが求められて
いる。なおそのようなペーストのビヒクルとしては皮膚
刺激性（かぶれを起さないこと）の低い事が望ましい。Problems to be Solved by the Invention: UV-curable coatings, inks, or their vehicles that do not cause phenomena such as precipitation or precipitation of the photopolymerization initiator, increase in particle size, or aggregation of fine particles even after long-term storage. There is a need for a photopolymerization initiator paste that has good compatibility with. It is desirable that the vehicle for such a paste has low skin irritation (does not cause rash).
課題を解決する為の手段
本発明者らは前記したような課題を解決すべく鋭意研究
を重ねた結果本発明に至った。即ち本発明は２５℃にお
いて液状である多官能（メタ）アクリレート１００重量
部に対して融点が４０℃以上の光重合開始剤を１０〜２
００重量部の割合で含有゛することを特徴とする光重合
開始剤ペーストを提供する。そして本発明の光重合開始
剤ペーストを調製する為の特に好ましい光重合開始剤は
次の式（Ｉ）
（式（Ｉ）中、Ｒ，、Ｒ２はそれぞれ独立して水素原子
、クロル原子、低級アルキル基又は低級アルコキシ基を
表す）
で表されるチオキサントン系化合物である。Means for Solving the Problems The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result they have arrived at the present invention. That is, in the present invention, 10 to 2 parts of a photopolymerization initiator having a melting point of 40°C or higher is added to 100 parts by weight of a polyfunctional (meth)acrylate that is liquid at 25°C.
A photopolymerization initiator paste is provided, characterized in that the paste contains a photopolymerization initiator in an amount of 0.00 parts by weight. A particularly preferable photopolymerization initiator for preparing the photopolymerization initiator paste of the present invention is represented by the following formula (I) (in formula (I), R, and R2 are each independently a hydrogen atom, a chloro atom, a lower It is a thioxanthone compound represented by (representing an alkyl group or a lower alkoxy group).
本発明の光重合開始剤ペーストにつき詳細に説明する。The photopolymerization initiator paste of the present invention will be explained in detail.
本発明の光重合開始剤ペーストのビヒクルである２５℃
において液状である多官能（メタ）アクリレートとして
はトリメチロールプロパントリ（メタ）アクリレート、
トリメチロールプロパンとエチレンオキサイド又はプロ
ピオンキサイドの付加物のトリ（メタ）アクリレート、
ペンタエリストールのトリ又はテトラ（メタ）アクリレ
ート、ヘンタエリストールのエチレンオキサイド又はプ
ロピオンキサイドの付加物のトリ又はテトラ（メタ）ア
クリレート、ジペンタエリストールのペンタ又はへキサ
（メタ）アクリレート、ビスフェノールＡとエチレンオ
キサイド又はプロピオンキサイドの付加物のジ（メタ）
アクリレート及びビスフェノールＡとエピクロルヒドリ
ンの反応生成物のジ（メタ）アクリレート等の多官能（
メタコアクリレート等が挙げられ、これらのうち２５℃
における粘度が１００センチポイズ以上のものが好まし
い。25°C, which is the vehicle for the photopolymerization initiator paste of the present invention.
Examples of liquid polyfunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate,
Tri(meth)acrylate of adduct of trimethylolpropane and ethylene oxide or propionoxide,
Tri- or tetra(meth)acrylate of pentaerythrol, tri- or tetra(meth)acrylate of adduct of ethylene oxide or propionoxide of hentaerythrol, penta- or hexa(meth)acrylate of dipentaerythrol, bisphenol A Di(meth) adduct of ethylene oxide or propionoxide
Polyfunctional (meth)acrylates such as acrylates and di(meth)acrylates, which are reaction products of bisphenol A and epichlorohydrin.
Metacoacrylate etc. are mentioned, and among these, 25℃
It is preferable that the viscosity is 100 centipoise or more.
又、これらの混合物であっても良い。これらの内特に好
ましいものはペンタエリストールのトリ又はテトラアク
リレート、ジペンタエリストールペ／り又はヘキサアク
リレートである。Alternatively, a mixture of these may be used. Particularly preferred among these are tri- or tetraacrylates of pentaerythritol, dipentaerythritol, or hexaacrylates.
又融点が４０℃以上の光重合開始剤としてはべ／ジフェ
ノ／、４−クロルベンゾフェノン、ベンジル、メチルオ
ルンペンゾイルペンゾエート、ベンジルジメチルケター
ル、２．２−モルホリノメチル−４′メチルチオプロピ
オフエノン、２−エチルアントラキノ／、２−クロルア
ノトラキノ／、１−クロルア／トラキノ／、チオキサノ
ド／、２−クロルチオキサントノ、２−メチルチオキサ
７トン、２，４−ジイソプロピルチオキサント／、２，
４−ジメチルチオキサ７トン、２．４−ジエチルチオキ
サ７トン、２−インクロビルチオキサントン、２−エチ
ルチオキサ７トン、フルオレノン等が挙げられる。又、
これらの光重合開始剤の混合物又は室温で液状の光重合
開始剤、例えば２．２−ジヒドロキシメチルプロピオフ
ェノ７等の混合物であってもよい。これらの内好ましい
ものは、インクロビルチオキサントン、２−クロルチオ
キサ７トン、２，４−ジエチルチオキサ７トン、２−エ
チルアントラキノン、ベンジルジメチルケタール、２．
２−モルホリノメチル−４′メチルチオプロピオフエノ
７である。Photopolymerization initiators with a melting point of 40°C or higher include benzyl diphenol, 4-chlorobenzophenone, benzyl, methylolumpenzoyl penzoate, benzyl dimethyl ketal, 2,2-morpholinomethyl-4'methylthiopropiophenone, 2-Ethylanthraquino/, 2-chloroanotraquino/, 1-chlorua/traquino/, thioxanodo/, 2-chlorothioxanthon, 7 tons of 2-methylthioxanthon, 2,4-diisopropylthioxanth/, 2 ，
Examples include 7 tons of 4-dimethylthioxa, 7 tons of 2,4-diethylthioxa, 2-incrovirthioxanthone, 7 tons of 2-ethylthioxa, and fluorenone. or,
A mixture of these photopolymerization initiators or a photopolymerization initiator that is liquid at room temperature, such as 2,2-dihydroxymethylpropiopheno 7, may be used. Among these, preferred are inclovirthioxanthone, 7 tons of 2-chlorothioxa, 7 tons of 2,4-diethylthioxa, 2-ethylanthraquinone, benzyl dimethyl ketal, 2.
2-morpholinomethyl-4'methylthiopropiofeno7.
本発明の光重合開始剤ペーストには必要なら光重合促進
剤として脂肪族又は芳香族第三級アミンが添加されても
よい。脂肪族アミンとじてはＮ、Ｎ、Ｎ−）リエタノー
ルアミン、Ｎ、 Ｎ、 Ｎ−メチルジェタノールアミン
、Ｎ、Ｎ、Ｎ−ジメチルエタノールアミン、トリプロピ
ルアミン、トリブチルアミン等が挙げられる。芳香族第
三級アミンとしては４，４′−ジメチルアミノベンゾフ
ェノン、４．４’−ジエチルアミノベンゾフェノン、２
．６−ジメチルＮ、 Ｎ−ジメチルアニリン、２，６−
ジイソプロピルＮ、 Ｎ−ジメチルアニリン、４−ｌロ
ルＮ、 Ｎ−ジメチルアニリン、４−シアノＮ、Ｎ−ジ
メチルアニリン、４−Ｎ、Ｎ−ジメチルアミノベンズア
ルデヒド、４．４−ジメチルアミノ安息香酸エステル類
例えば、メチルエステル、エチルエステル、フロビルエ
ステル、インアミルエステル、オクチルエステル等が挙
げられる。If necessary, an aliphatic or aromatic tertiary amine may be added to the photopolymerization initiator paste of the present invention as a photopolymerization accelerator. Examples of aliphatic amines include N,N,N-)liethanolamine, N,N,N-methyljetanolamine, N,N,N-dimethylethanolamine, tripropylamine, and tributylamine. Aromatic tertiary amines include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2
．． 6-dimethyl N, N-dimethylaniline, 2,6-
Diisopropyl N, N-dimethylaniline, 4-lol N, N-dimethylaniline, 4-cyano N, N-dimethylaniline, 4-N,N-dimethylaminobenzaldehyde, 4,4-dimethylaminobenzoic acid esters, e.g. , methyl ester, ethyl ester, furoyl ester, inamyl ester, octyl ester and the like.
又、これらの混合物であってもよい。これらのうち好ま
しいものは、Ｎ、Ｎ−ジメチルアミノ安息香酸エステル
類、エチルエステル、イソアミルエステル、オクチルエ
ステルである。Alternatively, a mixture of these may be used. Among these, preferred are N,N-dimethylaminobenzoic acid esters, ethyl ester, isoamyl ester, and octyl ester.
本発明の光重合開始剤ペーストは前記したような多官能
（メタ）アクリレート１００重量部に対して前記したよ
うな光重合開始剤１０〜２００重量部より好ましくは２
０〜１００重量部を添加して加熱溶解させるか、機械的
に微粉砕した光重合開始剤を多官能（メタ）アクリレー
トに添加して調製される。又必要に応じて添加される光
重合促進剤の添加量は多官能（メタ）アクリレート１０
０重量部に対して１０〜１００重量部である。The photopolymerization initiator paste of the present invention preferably contains 10 to 200 parts by weight of the above-mentioned photopolymerization initiator per 100 parts by weight of the above-mentioned polyfunctional (meth)acrylate.
It is prepared by adding 0 to 100 parts by weight and heating and dissolving it, or by adding a mechanically pulverized photopolymerization initiator to a polyfunctional (meth)acrylate. The amount of the photopolymerization accelerator added as necessary is 10% of the polyfunctional (meth)acrylate.
The amount is 10 to 100 parts by weight relative to 0 parts by weight.
本発明の光重合開始剤ペーストは紫外線硬化型コーチイ
ノゲス、あるいは紫外線硬化型インキのビヒクルあるい
は既成の紫外線硬化型コーチインゲスあるいは紫外線硬
化型インキとの相溶性にすぐれかつそれらツーティ／ゲ
スあるいはインキの本来の性質を損うことがない。即ち
既に調製されている紫外線硬化型コーチインゲスや紫外
線硬化型インキに対して本発明のペーストを加え、使用
に先立って、簡単な混合を実施するだけで均一になり、
硬化速度を大幅に早め、大幅に生産性を改善する事がで
きる。又、紫外線硬化型コーチインゲスや紫外線硬化型
インキを新たに調製する場合でも、必要な量の光重合開
始剤に相当する本発明のペーストを添加すれば、簡単な
混合で、目的とする紫外線硬化型コーチインゲスや紫外
線硬化型インキを得ることができる。The photopolymerization initiator paste of the present invention has excellent compatibility with a UV-curable coach ink, a vehicle for a UV-curable ink, or an existing UV-curable coach ink or an existing UV-curable coach ink, and has inherent properties of the ink. There is no harm to it. That is, by adding the paste of the present invention to an already prepared ultraviolet curable coaching gel or ultraviolet curable ink, and performing a simple mixing prior to use, the paste becomes homogeneous.
It can significantly speed up the curing speed and greatly improve productivity. Furthermore, even when preparing a new UV-curable coating gel or UV-curable ink, by adding the paste of the present invention corresponding to the required amount of photopolymerization initiator, the desired UV-curable ink can be prepared with simple mixing. Coaching inks and ultraviolet curing inks can be obtained.
実施例
次に本発明を実施例によって更に具体的に説明するが、
本発明シま、これらの実施例のみに限定されるものでは
ない。実施例中、部は重量部を表す。EXAMPLES Next, the present invention will be explained in more detail by examples.
The present invention is not limited to these examples. In the examples, parts represent parts by weight.
実施例１〜１６
下記の表−１の（メタ）アクリレートを使用し、ペース
ト調製法Ａ（光重合開始剤としてジエチルチオキサ７ト
ン（ＤＴＸ）を使用）又はＢ（ｆｔ重合開始剤としてク
ロルチオキサントン（ＣＴＸ）を使用）によって、各々
本発明のペーストを調製した。Examples 1 to 16 Paste preparation method A (using 7 tons of diethylthioxa (DTX) as a photoinitiator) or B (using chlorothioxanthone as a ft polymerization initiator) using the (meth)acrylates shown in Table 1 below. Each paste of the invention was prepared by (using CTX).
このペーストを０〜５１に１ケ月放置してペースト中の
光重合開始剤粒子の沈降、二次凝集、及び粒子径の増大
について調製直後のそれと比較して、表−１の結果を碍
た。This paste was left for one month at a temperature of 0 to 51, and the results shown in Table 1 were compared with those immediately after preparation regarding sedimentation, secondary aggregation, and increase in particle size of photopolymerization initiator particles in the paste.
化合物
Ａ ：
化合物
Ｂ ：
＊ ２ Ｐｒｉｍａｒｙ ５ｋｉｎ Ｉｒｒｉｔａｔ
ｉｏｎ Ｉｎｄｅｘ ： ８段階あり、数値の小さい
方がかぶれが少ない。Compound A: Compound B: *2 Primary 5kin Irritat
ion Index: There are 8 levels, the lower the number, the less rash.
・３ （メタ）アクリレート１００部に対する光重合開
始剤の重量部。-3 Parts by weight of photopolymerization initiator based on 100 parts of (meth)acrylate.
・４０印、Δ印、Ｘ印はそれぞれ以下の状態を表してい
る。・The 40 mark, Δ mark, and X mark each represent the following conditions.
○印：元重合開始剤の粒子の沈降、二次凝集、粒子径の
増大が全く認められ
ない。O mark: No sedimentation, secondary aggregation, or increase in particle size of particles of the original polymerization initiator is observed.
Δ印：光重合開始剤の粒子の沈降、二次凝集、粒子径の
増大が僅かに認めら
れる。Δ mark: Slight precipitation, secondary aggregation, and increase in particle size of photopolymerization initiator particles are observed.
×印：光重合開始剤の粒子の沈降、二次凝集、粒子径の
増大が明らかに認め
られる。× mark: Sedimentation, secondary aggregation, and increase in particle size of photopolymerization initiator particles are clearly observed.
（メタ）アクリレート１００部と光重合開始剤の所定量
を取り、力ロ熱攪拌して均一な溶液とし、室温迄冷却し
ながら、強烈な攪拌を続け、光重合開始剤が均一に分散
した重合開始剤ペーストを碍る。Take 100 parts of (meth)acrylate and a predetermined amount of photopolymerization initiator, stir vigorously and heat to form a homogeneous solution, continue to stir vigorously while cooling to room temperature, and polymerize with uniformly dispersed photopolymerization initiator. Add initiator paste.
（メタ）アクリレート１００部と予めボールミル等の粉
砕機によって、充分に微粒子化された光重合開始剤の所
定量を取り、室温で強烈な攪拌を続け、光重合開始剤が
た
均一に溶解又は分散しに重合開始剤ペーストを得る。Take 100 parts of (meth)acrylate and a predetermined amount of the photopolymerization initiator, which has been sufficiently made into fine particles using a pulverizer such as a ball mill, and continue to stir vigorously at room temperature to uniformly dissolve or disperse the photopolymerization initiator. Then, obtain a polymerization initiator paste.
表−１の結果、ペーストのビヒクルとして高粘度（２５
℃で１００センチポイズ以上）の多官能メタ）アクリレ
ートを使用した場合は、低粘度のそれを使用した時と比
較して、保存期間中に光開始剤の分散状態の変化が高濃
度においても認められず、従って、紫外線硬化型コーチ
インゲス又は紫外線硬化型インキに添加するペーストと
して適している。As a result of Table 1, high viscosity (25
When using polyfunctional meth)acrylates with a viscosity of 100 centipoise or higher at ℃, changes in the dispersion state of the photoinitiator were observed during storage, even at high concentrations, compared to when using low viscosity ones. Therefore, it is suitable as a paste to be added to an ultraviolet curable coaching ink or an ultraviolet curable ink.
尚、高粘度の（メタコアクリレートは、低粘度のそれと
比較して、皮膚刺激性が低（、作業衛生上の点からも優
れている。In addition, high-viscosity (methacrylate) has lower skin irritation than low-viscosity (methacrylate) and is also superior in terms of work hygiene.
実施例１７〜３５
下記の表−２の多官能（メタ）アクリレート、光重合開
始剤、及び光重合促進剤を使用し、実施例１と同様に本
発明のペーストを調製し、保存後の光重合開始剤粒子の
分散状態を観察して表−２の結果を舟た。結果は何れも
一ケ月後の分散状態は良好で優れた光重合開始剤ペース
ト特性を示した。Examples 17 to 35 A paste of the present invention was prepared in the same manner as in Example 1 using a polyfunctional (meth)acrylate, a photopolymerization initiator, and a photopolymerization accelerator shown in Table 2 below, and the paste of the present invention after storage was The dispersion state of the polymerization initiator particles was observed and the results shown in Table 2 were obtained. The results showed that the dispersion state after one month was good and the photopolymerization initiator paste had excellent properties.
拳５
Ａ：クロルチオキサントン Ｂ：ベン
ジルジメチルチタール Ｃ：２．２−モルホリノメチル
チオプロビオフヱノノ
Ｄ＝２−二チルアントラキノン Ｅ：
２−クロルアントラキノ７ Ｆ：２，４−ジメチルチオ
キサ７トン Ｇ：２−
メチルチオキサ７トン Ｈ：２−メト
エステル （２）Ｎ、Ｎ−ジメチルア〒箋息香酸イソ
アミルエステル （３） ４．４’−ジエチルアミノ
ベンゾフェノン
（４７Ｐ −Ｎ、Ｎ−ジメチル安息香酸２−エチルヘキ
シルエステル （５） Ｐ −Ｎ、Ｎ−ジメチルベン
ズアルデヒド
会７ （メタ）アクリレート１００部に対する、光重合
開始剤／九重合促進剤の重
量部を示す。Fist 5 A: Chlorthioxanthone B: Benzyl dimethyl tital C: 2.2-morpholinomethylthioprobiophene D = 2-dithylanthraquinone E: 2-chloroanthraquino 7 F: 2,4-dimethylthioxa 7 tons G: 7 tons of 2-methylthioxa H: 2-methester (2) N,N-dimethylbenzoic acid isoamyl ester (3) 4.4'-diethylaminobenzophenone (47P -N,N-dimethylbenzoic acid 2- Ethylhexyl ester (5) P -N, N-dimethylbenzaldehyde group 7 Parts by weight of the photopolymerization initiator/nine polymerization accelerator are shown based on 100 parts of (meth)acrylate.
発明の効果
光重合開始剤が高濃度であり、紫外線硬化型コーチイン
ゲス又は紫外線硬化型インキとの相容性が良く、ペース
ト中の光重合開始剤が保存中に析出、沈降又は凝集せず
、ペースト自体が光硬化反応に寄与し、硬化速度が速い
光重合開始剤ペーストが得られた。Effects of the invention The photopolymerization initiator is highly concentrated, has good compatibility with UV-curable coaching gels or UV-curable inks, and the photopolymerization initiator in the paste does not precipitate, settle, or aggregate during storage, making the paste A photopolymerization initiator paste that itself contributed to the photocuring reaction and had a fast curing speed was obtained.
Claims (1)
ート１００重量部に対して融点が ４０℃以上の光重合開始剤を１０〜２００重量部の割合
で含有することを特徴とする光重合開始剤ペースト。 ２、光重合開始剤が式（ I ） ▲数式、化学式、表等があります▼（ I ） （式（ I ）中Ｒ＿１、Ｒ＿２はそれぞれ独立して水素
原子、クロル原子、低級アルキル基又は低級 アルコキシ基を表す） で表されるチオキサントン系化合物である特許請求の範
囲第１項に記載の光重合開始剤ペースト。[Claims] 1. A photopolymerization initiator having a melting point of 40°C or higher is contained in a ratio of 10 to 200 parts by weight per 100 parts by weight of a polyfunctional (meth)acrylate that is liquid at 25°C. photopolymerization initiator paste. 2. The photopolymerization initiator has the formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula (I), R_1 and R_2 each independently represent a hydrogen atom, a chloro atom, a lower alkyl group, or a lower alkoxy The photopolymerization initiator paste according to claim 1, which is a thioxanthone compound represented by (representing a group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17179788A JPH0222305A (en) | 1988-07-12 | 1988-07-12 | Paste of photopolymerization initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17179788A JPH0222305A (en) | 1988-07-12 | 1988-07-12 | Paste of photopolymerization initiator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0222305A true JPH0222305A (en) | 1990-01-25 |
Family
ID=15929879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17179788A Pending JPH0222305A (en) | 1988-07-12 | 1988-07-12 | Paste of photopolymerization initiator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0222305A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043638A1 (en) * | 2004-10-20 | 2006-04-27 | Mitsubishi Chemical Corporation | Photosensitive composition, image-forming base material, image-forming material, and image-forming method |
-
1988
- 1988-07-12 JP JP17179788A patent/JPH0222305A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043638A1 (en) * | 2004-10-20 | 2006-04-27 | Mitsubishi Chemical Corporation | Photosensitive composition, image-forming base material, image-forming material, and image-forming method |
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