JP5842459B2 - Actinic ray curable composition and actinic ray curable ink jet ink - Google Patents
Actinic ray curable composition and actinic ray curable ink jet ink Download PDFInfo
- Publication number
- JP5842459B2 JP5842459B2 JP2011179578A JP2011179578A JP5842459B2 JP 5842459 B2 JP5842459 B2 JP 5842459B2 JP 2011179578 A JP2011179578 A JP 2011179578A JP 2011179578 A JP2011179578 A JP 2011179578A JP 5842459 B2 JP5842459 B2 JP 5842459B2
- Authority
- JP
- Japan
- Prior art keywords
- actinic ray
- ray curable
- curable composition
- composition according
- ink
- 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
Landscapes
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Description
本発明は、活性光線硬化組成物及び該組成物を用いた活性光線硬化型インクジェット用インクに関する。 The present invention relates to an actinic ray curable composition and an actinic ray curable inkjet ink using the composition.
活性光線硬化組成物として、ラジカル反応性(重合性)化合物と光ラジカル重合開始剤からなる組成物は広く知られている。このラジカル重合性硬化組成物は、高速で硬化する反面、光照射により発生するラジカルが空気中の酸素により直ぐに失活して反応が停止してしまうという問題があった。その場合、VOC(揮発性有機化合物)である低分子量のラジカルモノマーが残留することになり、安全性等に問題が生じることになる。
また、カチオン反応性(重合性)化合物と光酸発生剤からなる組成物も知られている。この組合せでは、反応活性種である強酸が酸素による阻害を受けないため(水分や塩基による阻害は受けるが)、光照射後も反応が進行(後硬化)し、残留モノマーを低減できる特徴がある。しかし、強酸が存在するため、硬化物周辺の腐食、変性等の問題が生じることがあった。
またアニオン反応性(重合性)化合物と光塩基発生剤からなる組成物も知られている。この組合せでは、カチオン系の場合と同様に、光照射後も反応が進行することに加えて、弱塩基を使えるため、腐食、変性等の問題が生じにくい。しかし、この系は、反応速度が非常に遅く、高速硬化が求められる用途では、使いにくいという問題があった。
なお、本発明で用いるのと同一又は類似の化合物を用いた技術は公知であるが(特許文献1、非特許文献1など)、本発明とはモノマーの使用形態、用途などが異なる。
As an actinic ray curable composition, a composition comprising a radical reactive (polymerizable) compound and a radical photopolymerization initiator is widely known. Although this radical polymerizable curable composition is cured at high speed, the radical generated by light irradiation is immediately deactivated by oxygen in the air and the reaction is stopped. In this case, a low molecular weight radical monomer that is VOC (volatile organic compound) remains, which causes a problem in safety and the like.
A composition comprising a cation reactive (polymerizable) compound and a photoacid generator is also known. In this combination, the strong acid, which is a reactive species, is not inhibited by oxygen (although it is inhibited by moisture or base), the reaction proceeds (post-curing) even after light irradiation, and the residual monomer can be reduced. . However, due to the presence of a strong acid, problems such as corrosion and modification around the cured product may occur.
A composition comprising an anion reactive (polymerizable) compound and a photobase generator is also known. In this combination, as in the case of the cationic system, in addition to the progress of the reaction after the light irradiation, a weak base can be used, so that problems such as corrosion and denaturation hardly occur. However, this system has a problem that the reaction rate is very slow and it is difficult to use in applications where high-speed curing is required.
In addition, although the technique using the same or similar compound used by this invention is well-known (patent document 1, nonpatent literature 1, etc.), the use form of a monomer, an application, etc. differ from this invention.
本発明は、上記従来技術の問題点を解決するためになされたものであり、高速硬化が可能で硬化反応が停止しにくい活性光線硬化組成物の提供を目的とする。 The present invention has been made to solve the above-described problems of the prior art, and an object thereof is to provide an actinic ray curable composition that can be cured at high speed and that does not easily stop the curing reaction.
上記課題は、次の1)〜5)の発明によって解決される。
1) 下記一般式(1)で表される塩基反応性化合物及び光塩基発生剤を含むことを特徴とする活性光線硬化組成物。
2) 更に光ラジカル重合開始剤を含むことを特徴とする1)に記載の活性光線硬化組成物。
3) 更に、ラジカル重合性化合物を含むことを特徴とする1)又は2)に記載の活性光線硬化組成物。
4) 前記ラジカル重合性化合物が多官能モノマーであることを特徴とする3)に記載の活性光線硬化組成物。
5) 1)〜4)のいずれかに記載の活性光線硬化組成物を含むことを特徴とする活性光線硬化型インクジェット用インク。
The above problems are solved by the following inventions 1) to 5).
1) An actinic ray curable composition comprising a base-reactive compound represented by the following general formula (1) and a photobase generator.
2) The actinic ray curable composition according to 1), further comprising a photoradical polymerization initiator.
3) The active ray curable composition according to 1) or 2), further comprising a radical polymerizable compound.
4) The actinic ray curable composition according to 3), wherein the radical polymerizable compound is a polyfunctional monomer.
5) An actinic radiation curable inkjet ink comprising the actinic radiation curable composition according to any one of 1) to 4).
本発明によれば、高速硬化が可能で硬化反応が停止しにくい活性光線硬化組成物を提供することができる。 According to the present invention, it is possible to provide an actinic ray curable composition that can be cured at high speed and does not easily stop the curing reaction.
以下、上記本発明について詳しく説明する。
前述したように、ラジカル反応性化合物は高速で硬化する半面、反応を完全に進行することが難しく、VOC等の問題が生じる。一方、アニオン反応性化合物は、後硬化が期待できるのでVOC等の問題が生じにくくなるが、反応が遅い。
そこで、硬化速度の非常に速いラジカル反応と、反応速度は遅いが後硬化がありVOC等の問題を生じにくいアニオン反応を組み合わせれば、お互いの欠点を補えることになる。
本発明は、アニオン反応性を有すると同時にラジカル反応性も有する化合物を用いることにより、上記2種類の反応の組み合わせを実現したものである。
Hereinafter, the present invention will be described in detail.
As described above, the radical-reactive compound cures at high speed, but it is difficult to complete the reaction and causes problems such as VOC. On the other hand, since an anion reactive compound can be expected to be postcured, problems such as VOC are less likely to occur but the reaction is slow.
Thus, combining a radical reaction with a very fast curing speed and an anionic reaction with a slow reaction speed but post-curing and less likely to cause problems such as VOC can compensate for each other's drawbacks.
The present invention realizes a combination of the above two types of reactions by using a compound having an anion reactivity and at the same time a radical reactivity.
本発明の活性光線硬化組成物は、下記一般式(1)で表される塩基反応性化合物を含むことを特徴とする。
具体的には、Aは5〜7員環であり、環はアルキル基、アルコキシ基、エステル基等を有していても良く、これらの基の炭素数は1〜6が好ましい。
具体例としては以下のようなものが挙げられるが、これらに限定されるものではない。
The actinic ray curable composition of the present invention includes a base-reactive compound represented by the following general formula (1).
Specifically, A is a 5- to 7-membered ring, and the ring may have an alkyl group, an alkoxy group, an ester group, or the like, and these groups preferably have 1 to 6 carbon atoms.
Specific examples include, but are not limited to, the following.
これらの塩基反応性化合物と光塩基発生剤を組み合わせると、活性光線照射により生成した塩基がトリガーとなり、塩基反応性化合物が反応して硬化することとなる。またその塩基は、アルカリ金属やアルキルリチウム等の非常に強い塩基ではなく、アミン、アミジン、グアニジン、ホスファゼン等の有機塩基で良いため、所謂有機塩基を発生する光塩基発生剤と組み合わせることができる。その結果、硬化組成物周辺の腐食、変性等の問題を回避することができる。
光塩基発生剤は、各種公知の化合物を用いることができるが、好ましくは、オキシムエステル類、4級アンモニウム塩類、アシル化合物類、カルバメート類、アミノアセトフェノン類、等を用いる。
When these base-reactive compounds and photobase generators are combined, a base generated by actinic ray irradiation becomes a trigger, and the base-reactive compound reacts and cures. Further, the base is not a very strong base such as alkali metal or alkyl lithium, but may be an organic base such as amine, amidine, guanidine, or phosphazene. Therefore, it can be combined with a photobase generator that generates a so-called organic base. As a result, problems such as corrosion and modification around the cured composition can be avoided.
Various known compounds can be used as the photobase generator, but preferably oxime esters, quaternary ammonium salts, acyl compounds, carbamates, aminoacetophenones, and the like are used.
前記塩基反応性化合物のうち環構成原子として酸素原子を含むもので、ラジカル反応性もあるものは、光ラジカル重合開始剤を添加することにより、硬化速度の高速化を達成することができる。光ラジカル重合開始剤は、各種公知の化合物を用いることができるが、好ましくは、ベンゾフェノン類、アルキルフェノン類、アシルホスフィンオキシド類、オキシフェニル酢酸エステル類、ベンゾインエーテル類、オキシムエステル類、チオキサントン類、等を用いることができる。
また、その他のラジカル重合性化合物、特に多官能モノマーを用いれば、より高速に硬化できるようになる。
Among the basic reactive compounds, those having an oxygen atom as a ring-constituting atom and also having radical reactivity can achieve a high curing rate by adding a photo radical polymerization initiator. As the radical photopolymerization initiator, various known compounds can be used. Preferably, benzophenones, alkylphenones, acylphosphine oxides, oxyphenyl acetates, benzoin ethers, oxime esters, thioxanthones, Etc. can be used.
Further, when other radical polymerizable compounds, particularly polyfunctional monomers are used, curing can be performed at a higher speed.
前記ラジカル重合性化合物の具体例としては、ビニル化合物、(メタ)アクリレート化合物、クロトン酸化合物、アクリルアミド化合物等が挙げられるが、硬化速度の面から、(メタ)アクリレート化合物、(メタ)アクリルアミド化合物が好ましい。
さらに、本発明の活性光線硬化組成物には、必要に応じて各種公知の着色剤、増感剤、粘度調整剤、界面活性剤等を添加することができる。
また、上述の活性光線硬化組成物の用途は、一般に光硬化材料が用いられている分野であれば特に限定されないが、活性光線硬化型インクジェット用インクとして用いることが好ましい。
Specific examples of the radical polymerizable compound include vinyl compounds, (meth) acrylate compounds, crotonic acid compounds, and acrylamide compounds. From the viewpoint of curing speed, (meth) acrylate compounds and (meth) acrylamide compounds are exemplified. preferable.
Furthermore, various known colorants, sensitizers, viscosity modifiers, surfactants, and the like can be added to the actinic ray curable composition of the present invention as necessary.
The use of the above-mentioned actinic ray curable composition is not particularly limited as long as it is a field in which a photocurable material is generally used, but it is preferably used as an actinic ray curable inkjet ink.
インクジェット用インクとして用いる場合の着色剤としては、各種公知の染料及び顔料を用いることができ、顔料を用いた場合には、必要に応じて分散剤等を用いても良い。
着色剤としては、耐光性に優れ、色再現性に富んだものが好ましく、硬化反応に影響を及ぼさず、重合を阻害しないものが好ましい。
本発明のインクジェット用インクを適用できるインク受容体としては、普通紙、コート紙等の紙類、非浸透性のプラスチックや金属、ガラス等の各種公知のものが挙げられる。
本発明の活性光線硬化組成物に対し、活性光線を照射する光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、LED等、各種公知のものを使用できる。
As a colorant when used as an inkjet ink, various known dyes and pigments can be used. When a pigment is used, a dispersant or the like may be used as necessary.
As the colorant, those excellent in light resistance and rich in color reproducibility are preferable, and those which do not affect the curing reaction and do not inhibit the polymerization are preferable.
Examples of the ink receptor to which the ink jet ink of the present invention can be applied include papers such as plain paper and coated paper, and various known materials such as non-permeable plastic, metal, and glass.
Various light sources such as a mercury lamp, a metal halide lamp, a xenon lamp, and an LED can be used as the light source for irradiating the active light curable composition of the present invention with active light.
以下、実施例及び比較例を示して本発明を更に具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.
実施例1〜8、比較例1〜2
表1の実施例及び比較例の各欄に示す組成比の材料を混合撹拌して活性光線硬化組成物を調製した。また、実施例5、6及び比較例2では更に顔料を加えて混合撹拌し、活性光線硬化型インクジェット用インクを調製した。表中の( )内の数値は重量部である。
顔料としては次のものを用いた。
・CB:カーボンブラック顔料、チバ・ジャパン社製:MICROLITH Black C−K)
・Blue:チバ・ジャパン社製:MICROLITH Blue 4G−K
また、モノマーとしては、前述した(A−2)〜(A−4)、(A−10)、(A−12)、下記(B−1)〜(B−6)、及び(D−1)の化合物を用い、光塩基発生剤としては、下記(C−1)、(C−2)の化合物を用い、光ラジカル重合開始剤としては、下記(C−3)、(C−4)の化合物を用いた。
Examples 1-8, Comparative Examples 1-2
Actinic ray curable compositions were prepared by mixing and stirring materials having the composition ratios shown in the columns of Examples and Comparative Examples in Table 1. In Examples 5 and 6 and Comparative Example 2, a pigment was further added and mixed and stirred to prepare an actinic ray curable inkjet ink. The numbers in parentheses in the table are parts by weight.
The following pigments were used.
CB: carbon black pigment, manufactured by Ciba Japan Co., Ltd .: MICROLITH Black CK)
・ Blue: Ciba Japan Co., Ltd .: MICROLITH Blue 4G-K
Moreover, as a monomer, (A-2)-(A-4), (A-10), (A-12), the following (B-1)-(B-6), and (D-1) mentioned above are mentioned. ), The following (C-1) and (C-2) compounds are used as photobase generators, and the following (C-3) and (C-4) are used as photoradical polymerization initiators. The following compounds were used.
実施例及び比較例の各インクをスライドガラスに塗布した後、水銀ランプ(HOYA−SCHOTT製:EX−250、25mW/cm2)により光照射を行い、硬化性を評価した。比較評価は表面タック性により行った。表面タック(粘つき)は、測定後のサンプルを指触することにより行った。結果を表1に示す。 After each ink of Examples and Comparative Examples was applied to a slide glass, light irradiation was performed with a mercury lamp (manufactured by HOYA-SCHOTT: EX-250, 25 mW / cm 2 ) to evaluate curability. The comparative evaluation was performed based on the surface tackiness. The surface tack (stickiness) was performed by touching the sample after measurement with a finger. The results are shown in Table 1.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011179578A JP5842459B2 (en) | 2011-08-19 | 2011-08-19 | Actinic ray curable composition and actinic ray curable ink jet ink |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011179578A JP5842459B2 (en) | 2011-08-19 | 2011-08-19 | Actinic ray curable composition and actinic ray curable ink jet ink |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013040307A JP2013040307A (en) | 2013-02-28 |
JP5842459B2 true JP5842459B2 (en) | 2016-01-13 |
Family
ID=47888986
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011179578A Expired - Fee Related JP5842459B2 (en) | 2011-08-19 | 2011-08-19 | Actinic ray curable composition and actinic ray curable ink jet ink |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5842459B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6252977B2 (en) * | 2013-10-23 | 2017-12-27 | 株式会社リコー | Actinic ray curable composition, actinic ray curable inkjet ink composition and actinic ray curable adhesive composition using the same |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0273811A (en) * | 1988-09-08 | 1990-03-13 | Hitachi Chem Co Ltd | Acrylate salt-cyclohexenone copolymer, intermediate thereof, production thereof, builder and cleanser composition |
JPH0753499A (en) * | 1993-08-11 | 1995-02-28 | Aibaitsu Kk | Bis-(((2-nitro-4,5-dimethoxybenzyl)oxy) carbonyl)isophoronediamine and its usage |
JP2002328475A (en) * | 2001-02-19 | 2002-11-15 | Sumitomo Chem Co Ltd | Chemical amplification type positive resist composition |
JP2005213471A (en) * | 2004-02-02 | 2005-08-11 | Nippon Soda Co Ltd | New polymer |
WO2006008251A2 (en) * | 2004-07-21 | 2006-01-26 | Ciba Specialty Chemicals Holding Inc. | Process for the photoactivation and use of a catalyst by an inverted two-stage procedure |
JP2006328297A (en) * | 2005-05-30 | 2006-12-07 | Konica Minolta Medical & Graphic Inc | Active ray-curable composition and active ray-curable ink-jet ink composition, method for image formation using the same and ink-jet printer using the same |
JP2009128588A (en) * | 2007-11-22 | 2009-06-11 | Konica Minolta Opto Inc | Method of manufacturing optical compensation film, optical compensation film, polarizing plate and liquid crystal display device |
KR101475573B1 (en) * | 2009-06-08 | 2014-12-22 | 산요가세이고교 가부시키가이샤 | Photosensitive composition |
JP5862021B2 (en) * | 2010-03-05 | 2016-02-16 | 株式会社リコー | Actinic ray curable ink composition, actinic ray curable inkjet ink composition and printing method thereof |
-
2011
- 2011-08-19 JP JP2011179578A patent/JP5842459B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2013040307A (en) | 2013-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5844416B2 (en) | Method for producing photocured product of photosensitive composition | |
JP6183642B2 (en) | Actinic ray curable composition, actinic ray curable ink composition for inkjet printing using the same, and actinic ray curable adhesive composition | |
JP4667145B2 (en) | Photocurable resin composition and resin composition for plastics comprising the same | |
JP5940259B2 (en) | Photosensitive composition | |
JP6008166B2 (en) | Actinic ray curable composition, actinic ray curable ink composition for inkjet printing, actinic ray curable adhesive composition and method for stabilizing actinic ray curable composition | |
JP2008527130A5 (en) | ||
JP2012167271A (en) | Photosensitive composition | |
TWI496833B (en) | Cation polymeric resin, cation polymeric resin composition and cured article thereof | |
JP2012167262A (en) | Photosensitive composition | |
JP5517112B2 (en) | Photocurable resin composition and its use | |
JP2012158745A (en) | Polymerizable compound for inkjet printing ink, and ink composition | |
JP2003212975A (en) | Curable composition | |
JP2012168526A (en) | Photosensitive composition | |
JP5842459B2 (en) | Actinic ray curable composition and actinic ray curable ink jet ink | |
JP2013040306A (en) | Active ray-curable composition and active ray-curable inkjet ink | |
JP7114725B2 (en) | Radiation-curable gravure printing ink | |
JP2014105305A (en) | Curable composition, actinic ray-curable inkjet composition and actinic ray-curable adhesive composition | |
JP6252977B2 (en) | Actinic ray curable composition, actinic ray curable inkjet ink composition and actinic ray curable adhesive composition using the same | |
JP2012167263A (en) | Microwave curable composition | |
JP5490588B2 (en) | Polymerizable compound and ink composition for ink jet printing ink | |
JP6639403B2 (en) | Active energy ray curable composition | |
JP2013216775A (en) | Active ray curable composition, and active ray curable ink for inkjet | |
JP2012167266A (en) | Photosensitive composition | |
JP6071104B2 (en) | Actinic ray curable composition, actinic ray curable inkjet composition, and actinic ray curable adhesive composition | |
JP4560672B2 (en) | Curable resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140711 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141222 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150106 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150212 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150728 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150917 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20151020 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20151102 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 5842459 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
LAPS | Cancellation because of no payment of annual fees |