JPH05112737A - Photocurable oligomer, resin composition containing same, and its cured article - Google Patents
Photocurable oligomer, resin composition containing same, and its cured articleInfo
- Publication number
- JPH05112737A JPH05112737A JP29961191A JP29961191A JPH05112737A JP H05112737 A JPH05112737 A JP H05112737A JP 29961191 A JP29961191 A JP 29961191A JP 29961191 A JP29961191 A JP 29961191A JP H05112737 A JPH05112737 A JP H05112737A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- oligomer
- resin composition
- ink
- photocurable oligomer
- 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
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規な光硬化性オリゴ
マ−、これを用いた樹脂組成物及びその硬化物に関す
る。さらに詳しくは、紫外線硬化性を有するオリゴマ−
であって、とくに印刷インキ用バインダ−に適する光硬
化性オリゴマ−、これを用いた樹脂組成物及び硬化物に
関する。TECHNICAL FIELD The present invention relates to a novel photocurable oligomer, a resin composition using the same and a cured product thereof. More specifically, an ultraviolet curable oligomer
In particular, the present invention relates to a photocurable oligomer suitable for a binder for printing ink, a resin composition using the same, and a cured product.
【０００２】[0002]
【従来の技術】紫外線硬化型インキは、通常はエポキシ
樹脂とアクリル酸とを反応してえられる不飽和エポキシ
樹脂エステルなどにトリメチロ−ルプロパントリアクリ
レ−トなどの反応性希釈剤、光重合開始剤、および顔料
などを適宜配合して得られる組成物として知られてい
る。この中、不飽和エポキシ樹脂エステル、不飽和ポリ
エステル等はインキ用バインダ−中のオリゴマ−として
位置づけられているが、該オリゴマ−は光沢、顔料分散
性、粘度、印刷適性、硬化速度などのえられるインキ諸
特性に密接に関連するため前記構成成分のなかでもとく
に重要である。2. Description of the Related Art UV curable ink is usually an unsaturated epoxy resin ester obtained by reacting an epoxy resin with acrylic acid, a reactive diluent such as trimethylolpropane triacrylate, and photopolymerization. It is known as a composition obtained by appropriately blending an initiator, a pigment and the like. Among them, unsaturated epoxy resin ester, unsaturated polyester and the like are positioned as oligomers in the binder for inks, and the oligomers have gloss, pigment dispersibility, viscosity, printability, curing speed and the like. It is particularly important among the above constituents because it is closely related to various ink characteristics.
【０００３】[0003]
【発明が解決しようとする課題】近年、紫外線硬化型イ
ンキであっても従来の溶剤型インキと同程度の印刷適性
を有することが要求され、従来の多官能性オリゴマ−で
ある不飽和エポキシ樹脂などでは該要求を充分満足しえ
ない状況にある。In recent years, it has been required that even an ultraviolet curable ink has printability comparable to that of a conventional solvent type ink, and an unsaturated epoxy resin which is a conventional polyfunctional oligomer. However, there is a situation where the demand cannot be sufficiently satisfied.
【０００４】例えば、不飽和エポキシ樹脂として、ビス
フェノ−ルＡのエポキシ樹脂と（メタ）アクリル酸との
反応物が知られているが、これを用いて紫外線硬化型イ
ンキを調製したばあいには印刷適性のうち、殊にインキ
の乳化やミスチング現象が顕著に認められるという欠点
がある。そのため、優れた印刷適性を有する紫外線硬化
性インキを提供しうる新規なオリゴマ−の開発が要望さ
れている。For example, as an unsaturated epoxy resin, a reaction product of an epoxy resin of bisphenol A and (meth) acrylic acid is known, but when an ultraviolet curable ink is prepared using this, a reaction product is prepared. Among the printability, there is a drawback that the emulsification of ink and the misting phenomenon are particularly noticeable. Therefore, there is a demand for the development of a novel oligomer that can provide an ultraviolet curable ink having excellent printability.
【０００５】[0005]
【課題を解決するための手段】本発明は従来技術では解
決しえなかたっ前記課題を解決するためになされたもの
である。本発明者らは、印刷適性のほか、硬化速度、機
上安定性などを考慮して、これら諸性能を満足すること
ができる優れた光硬化性オリゴマ−を開発すべく鋭意研
究を重ねた結果、ロジン成分を側鎖に有する特定のオリ
ゴマ−を用いることにより、前記課題を解決しうること
を見出した。即ち、本発明は、 １．式（１）で表される化合物The present invention has been made to solve the above-mentioned problems, which cannot be solved by the prior art. As a result of intensive studies to develop an excellent photocurable oligomer capable of satisfying these various performances, in consideration of the printability, the curing speed, the on-machine stability, etc. It has been found that the above problems can be solved by using a specific oligomer having a rosin component in the side chain. That is, the present invention is: Compound represented by formula (1)
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】（式中Ｒ、Ｈ又はＣＨ3 である。）とロジ
ンとの反応物である光硬化性オリゴマ−、 ２．第１項記載の光硬化性オリゴマ−を含有することを
特徴とする樹脂組成物、 ３．第２項記載の樹脂組成物の硬化物、に関する。1. A photocurable oligomer which is a reaction product of (in the formula, R, H or CH 3 ) with rosin, 2. A resin composition containing the photocurable oligomer according to item 1. A cured product of the resin composition according to item 2.
【０００８】本発明の新規な光硬化性オリゴマ−は、前
記式（１）で表される化合物とロジンとを反応させるこ
とにより得ることができる。式（１）で表される化合物
の具体例としては、The novel photocurable oligomer of the present invention can be obtained by reacting the compound represented by the above formula (1) with rosin. Specific examples of the compound represented by the formula (1) include:
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】を挙げることができる。ロジン類は、得ら
れるインキの紫外線硬化速度、光硬化性オリゴマ−の色
調などを考慮して決定され、通常は水素化ロジン、不均
化ロジンなどの共役二重結合を安定化処理したロジンが
適当である。例えば、荒川化学工業（株）製、商品名、
ハイペ−ル（水添ロジン）、ＫＲ−６１０（無色ロジ
ン）等を挙げることができる。The following can be mentioned. The rosin is determined in consideration of the ultraviolet curing speed of the obtained ink, the color tone of the photocurable oligomer, etc., and is usually a rosin obtained by stabilizing the conjugated double bond such as hydrogenated rosin and disproportionated rosin. Appropriate. For example, Arakawa Chemical Co., Ltd. product name,
Examples include high pale (hydrogenated rosin) and KR-610 (colorless rosin).
【００１２】式（１）で表される化合物とロジンとの反
応は、ロジン類のカルボキシル基の１当量に対して式
（１）で表される化合物を好ましくは約０．９〜１．５
当量、特に好ましくは約０．９５〜１．１当量となる比
で行う。反応を促進させるために触媒（例えば、トリエ
チルアミン、ベンジルジメチルアミン、メチルトリエチ
ルアンモニウムクロライド、トリフェニルフォスフィン
等）を使用することが好ましく、該触媒の使用量は、反
応原料混合物に対して好ましくは０．１〜１０重量％、
特に好ましくは０．３〜５重量％である。反応中の重合
を防止するために、重合防止剤（例えば、メトキノン、
ハイドロキノン、フェノチアジン等）を使用するのが好
ましく、その使用量は、反応原料混合物に対して好まし
くは０．０１〜１重量％、特に好ましくは０．０５〜
０．５重量％である。反応温度は好ましくは６０〜１５
０℃、特に好ましくは８０〜１２０℃である。又、反応
時間は好ましくは５〜６０時間、特に好ましくは１０〜
５０時間である。In the reaction of the compound represented by the formula (1) with rosin, the compound represented by the formula (1) is preferably about 0.9 to 1.5 relative to 1 equivalent of the carboxyl group of the rosin.
Equivalents, particularly preferably in a ratio of about 0.95 to 1.1 equivalents. It is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylphosphine, etc.) to accelerate the reaction, and the amount of the catalyst used is preferably 0 with respect to the reaction raw material mixture. 1 to 10% by weight,
It is particularly preferably 0.3 to 5% by weight. In order to prevent polymerization during the reaction, a polymerization inhibitor (for example, methoquinone,
Hydroquinone, phenothiazine, etc.) is preferably used, and the amount thereof is preferably 0.01 to 1% by weight, particularly preferably 0.05 to 1% by weight based on the reaction raw material mixture.
It is 0.5% by weight. The reaction temperature is preferably 60-15
The temperature is 0 ° C, particularly preferably 80 to 120 ° C. The reaction time is preferably 5 to 60 hours, particularly preferably 10 to
50 hours.
【００１３】本発明の樹脂組成物は光硬化性オリゴマ−
が高粘度な為に必要に応じて粘度降下を目的として反応
性希釈剤を本発明の光硬化性オリゴマ−１００重量部に
対して通常２０〜７００重量部の範囲で使用する。該反
応性希釈剤としては、２−ヒドロキシエチル（メタ）ア
クリレ−ト、トリプロピレングリコ−ルジ（メタ）アク
リレ−ト、ヒドロキシピバリン酸ネオペンチルグリコ−
ルジ（メタ）アクリレ−ト、ビスフェノ−ルＡテトラエ
トキシジ（メタ）アクリレ−ト、ビスフェノ−ルＦテト
ラエトキシジ（メタ）アクリレ−ト、トリメチロ−ルプ
ロパントリ（メタ）アクリレ−ト、トリメチロ−ルプロ
パントリプロポキシトリ（メタ）アクリレ−ト、ジトリ
メチロ−ルプロパンテトラ（メタ）アクリレ−ト、トリ
シクロデカンジメチロ−ルジ（メタ）アクリレ−ト、ジ
ペンタエリスリト−ルヘキサ及びペンタ（メタ）アクリ
レ−ト等を挙げることができる。これら反応性希釈剤を
１種もしくは２種以上用いることができる。The resin composition of the present invention is a photocurable oligomer.
Since it has a high viscosity, a reactive diluent is usually used in the range of 20 to 700 parts by weight based on 100 parts by weight of the photocurable oligomer of the present invention for the purpose of decreasing the viscosity. Examples of the reactive diluent include 2-hydroxyethyl (meth) acrylate, tripropylene glycol di (meth) acrylate, and neopentylglycol hydroxypivalate.
Di (meth) acrylate, bisphenol A tetraethoxydi (meth) acrylate, bisphenol F tetraethoxydi (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane Tripropoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tricyclodecanedimethyldi (meth) acrylate, dipentaerythritol hexa and penta (meth) acrylate Etc. can be mentioned. One or more of these reactive diluents can be used.
【００１４】本発明の樹脂組成物を印刷、インキ用バイ
ンダ−として使用する場合には、更に必要に応じて、フ
ァストエロ−、ベンジジンエロ−、レ−キレッド４Ｒ、
レ−キレッドＣ、ブリリアントカ−ミン６Ｂ、フタロシ
アニンブル−、チタン白、カ−ボンブラック等の顔料
を、本発明の樹脂組成物中、通常５０重量％以下で分散
して使用することができる。さらに、アルミナ、ケイ素
等の体質顔料を分散して使用してもよい。また、紫外線
の様な比較的低エネルギ−の活性エネルギ−線を硬化エ
ネルギ−線として利用する際には、ベンゾフェノン、チ
オキサントン、ベンゾインエチルエ−テル、２−メチル
−１−〔４−（メチルチオ）フェニル〕−２−モルフォ
リノ−プロパン−１−オン、ジエトキシアセトフェノ
ン、２−ヒドロキシ−２−メチル−１−フェニルプロパ
ン−１−オン等の光重合開始剤を樹脂組成物中通常０．
５〜２０重量％、さらに必要に応じて脂肪族あるいは芳
香族アミンあるいは４，４−ビスジエチルアミノベンゾ
フェノン等を樹脂組成物中０．１〜１０重量％、促進剤
として使用することが好ましい。When the resin composition of the present invention is used as a binder for printing or ink, if necessary, Fastello-, Benzine-ello, Lake Red 4R,
Pigments such as Rekilled C, Brilliant Carmine 6B, Phthalocyanine Blue, Titanium White, Carbon Black and the like can be dispersed in the resin composition of the present invention in an amount of usually 50% by weight or less and used. Further, an extender pigment such as alumina or silicon may be dispersed and used. Further, when utilizing a relatively low energy active energy ray such as ultraviolet ray as a curing energy ray, benzophenone, thioxanthone, benzoinethyl ether, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like are usually added to the resin composition in an amount of 0.
It is preferable to use 5 to 20% by weight, and if necessary, an aliphatic or aromatic amine or 4,4-bisdiethylaminobenzophenone in the resin composition in an amount of 0.1 to 10% by weight as an accelerator.
【００１５】さらに、本発明の樹脂組成物として、本発
明の光硬化性オリゴマ−の他に、従来より知られている
エポキシ（メタ）アクリレ−ト、ウレタン（メタ）アク
リレ−ト等を一部併用することもできる。本発明の樹脂
組成物はさらに前記反応希釈剤等をさらに加えて低粘度
化すること等によって塗料、接着剤、ソルダ−レジス
ト、オ−バ−プリントワニス等として使用することがで
き、さらに成形物用材料として使用することもできる。
本発明の樹脂組成物は各成分を均一に混合することによ
り得ることができる。本発明の樹脂組成物の硬化物は常
法により紫外線又は電子線を照射して硬化させることに
より得ることができる。Further, as the resin composition of the present invention, in addition to the photocurable oligomer of the present invention, a part of conventionally known epoxy (meth) acrylate, urethane (meth) acrylate, etc. is used. It can also be used together. The resin composition of the present invention can be used as a paint, an adhesive, a solder resist, an overprint varnish, etc. by further adding the reaction diluent or the like to lower the viscosity, and a molded product. It can also be used as a material.
The resin composition of the present invention can be obtained by uniformly mixing the components. The cured product of the resin composition of the present invention can be obtained by irradiating an ultraviolet ray or an electron beam to cure the resin composition by a conventional method.
【００１６】[0016]
【実施例】以下実施例によって本発明をさらに詳細に説
明する。実施例中、部は重量部を示す。 実施例１ 無色ロジン（荒川化学工業（株）製、ＫＲ−６１０、不
均化ロジン、酸価（mgKOH/g)１７０）２００部、前記式
（２）の化合物１１５部、メチルトリエチルアンモニウ
ムクロライド１．１４部及びメトキノン０．３部を仕込
み、９５℃に昇温し、９５℃で反応を行う。反応混合液
の酸価（mgkOH/g)が５以下になるまで反応を行い（約２
５時間）本発明の光硬化性オリゴマ−（生成物Ａ）を得
た。得られた生成物Ａは、常温で固体で淡黄色透明であ
った。得られた生成物の高分解能核磁気共鳴（ＮＭＲ）
により測定を行った結果を下記に示す。The present invention will be described in more detail with reference to the following examples. In the examples, “part” means “part by weight”. Example 1 200 parts of colorless rosin (manufactured by Arakawa Chemical Industry Co., Ltd., KR-610, disproportionated rosin, acid value (mgKOH / g) 170), 115 parts of the compound of the formula (2), methyltriethylammonium chloride 1 14 parts and methoquinone 0.3 parts are charged, the temperature is raised to 95 ° C., and the reaction is carried out at 95 ° C. React until the acid value (mgkOH / g) of the reaction mixture becomes 5 or less (about 2
5 hours) A photocurable oligomer of the present invention (Product A) was obtained. The obtained product A was solid at room temperature and was light yellow and transparent. High resolution nuclear magnetic resonance (NMR) of the obtained product
The results of measurement by are shown below.
【００１７】 Ｎｏ． ＰＰＭ Ｎｏ． ＰＰＭ １ １６６．２２０ ９ １２４．２５１ ２ １６６．１６０ １０ １２４．０３２ ３ １４６．７１３ １１ ７７．４８４ ４ １４５．７３３ １２ ７７．０６１ ５ １３０．７１２ １３ ７６．６３６ ６ １２８．４１９ １４ ７２．９１３ ７ １２８．３１０ １５ ７２．８３２ ８ １２７．００１ １６ ７１．９８９ Ｎｏ． ＰＰＭ Ｎｏ． ＰＰＭ １７ ７１．７０７ ４５ ３６．８７２ １８ ７１．６６２ ４６ ３６．７４１ １９ ６８．３５２ ４７ ３６．６９５ ２０ ６８．１８１ ４８ ３６．５５５ ２１ ６８．０４０ ４９ ３６．３４６ ２２ ６７．４９３ ５０ ３６．２４３ ２３ ６７．２７４ ５１ ３５．３９０ ２４ ６７．２２５ ５２ ３４．４３４ ２５ ６７．１３８ ５３ ３３．４５４ ２６ ６７．０７０ ５４ ３３．３３８ ２７ ６７．０２８ ５５ ３３．０９２ ２８ ５６．２６０ ５６ ３２．８０８ ２９ ４９．９８９ ５７ ３２．６１１ ３０ ４７．７８５ ５８ ３２．１２５ ３１ ４７．７１３ ５９ ３２．０２１ ３２ ４６．５２１ ６０ ３１．８３９ ３３ ４５．１１４ ６１ ３１．７９０ ３４ ４４．２２４ ６２ ３１．７３８ ３５ ４３．６６１ ６３ ３０．８００ ３６ ４０．４６２ ６４ ３０．７２４ ３７ ４０．３７９ ６５ ３０．３５５ ３８ ３８．４２３ ６６ ２９．８３２ ３９ ３８．２２６ ６７ ２８．７８５ ４０ ３８．１３７ ６８ ２８．７０９ ４１ ３７．９７０ ６９ ２８．６３５ ４２ ３７．１６７ ７０ ２７．８３４ ４３ ３７．０５３ ７１ ２７．１３１ ４４ ３７．０１４ ７２ ２６．０８７ No. PPM No. PPM 1 166.220 9 124.251 2 166.160 10 124.032 3 146.713 11 77.484 4 145.733 12 77.061 5 130.712 13 76.636 6 128.419 14 72.9137 128.310 15 72.832 8 127.001 16 71.989 No. PPM No. PPM 17 71.707 45 36.872 18 71.662 46 36.741 19 68.352 47 36.695 20 68.181 48 36.555 21 68.040 49 36.346 22 67.493 50 36.243 23 67.274 51 35.390 24 67.225 52 34.434 25 67.138 53 33.454 26 67.070 54 33.338 27 67.0028 55 33.092 28 56.260 56 32.808 29 49. 989 57 32.611 30 47.785 58 32.125 31 47.713 59 32.021 32 46.521 60 31.839 33 45.114 61 31.790 34 44.224 62 31.738 35 43.661 63 30.800 6 40.462 64 30.724 37 40.379 65 30.355 38 38.423 66 29.832 39 38.226 67 28.785 40 38.137 68 68.709 9 41 37.970 69 69 28.635 42 37 .167 70 27.834 43 37.053 71 27.131 44 37.014 72 26.087
【００１８】なお、上記の測定は、基準物質としてテト
ラメチルシランを用いて溶媒は重クロロホルムを用いて
プロトンデカップリング法で行った。The above measurement was carried out by a proton decoupling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.
【００１９】実施例２ 無色ロジン（荒川化学工業（株）製、ＫＲ−６１０、不
均化ロジン、酸価（mgKOH/g)１７０）２００部、前記式
（３）の化合物１２４部、トリフェニルホスフィン１．
１６部及びメトキノン０．３２部を仕込み、９５℃で反
応を行い（約２５時間）本発明の光硬化性オリゴマ−
（生成物Ｂ）を得た。生成物Ｂは常温で固体で、淡黄色
透明であった。 Ｎ．Ｍ．Ｒ．の測定結果Example 2 200 parts of colorless rosin (manufactured by Arakawa Chemical Industry Co., Ltd., KR-610, disproportionated rosin, acid value (mgKOH / g) 170), 124 parts of the compound of the formula (3), triphenyl Phosphine 1.
16 parts and 0.32 part of methquinone were charged and reacted at 95 ° C. (about 25 hours). The photocurable oligomer of the present invention.
(Product B) was obtained. The product B was solid at room temperature and was light yellow and transparent. N. M. R. Measurement result
【００２０】 Ｎｏ． ＰＰＭ Ｎｏ． ＰＰＭ １ １７８．３５８ ２０ ７７．０５４ ２ １７８．０００ ２１ ７６．６３１ ３ １６７．４８３ ２２ ７２．９５０ ４ １６７．４１８ ２３ ７２．８７４ ５ １６７．３６９ ２４ ７２．４９８ ６ １４６．７０６ ２５ ７１．９９６ ７ １４５．７４７ ２６ ７１．９０１ ８ １３７．４９９ ２７ ７１．７３３ ９ １３６．３５８ ２８ ６８．４２８ １０ １３６．３２４ ２９ ６８．２１５ １１ １３６．２６８ ３０ ６７．５９６ １２ １３４．５０８ ３１ ６７．５２６ １３ １２７．０１８ ３２ ６７．３４２ １４ １２５．９４４ ３３ ６７．２７８ １５ １２５．６１３ ３４ ６７．２１０ １６ １２５．４７３ ３５ ６７．１３６ １７ １２４．２６９ ３６ ５６．８４３ １８ １２４．０３２ ３７ ５６．３００ １９ ７７．４７７ ３８ ５６．２３０ Ｎｏ． ＰＰＭ Ｎｏ． ＰＰＭ ３９ ５０．１０５ ６６ ３６．２４８ ４０ ５０．０２３ ６７ ３５．５９２ ４１ ４８．０６２ ６８ ３５．３９０ ４２ ４７．７８９ ６９ ３４．４３７ ４３ ４７．７１３ ７０ ３３．４５８ ４４ ４６．５５９ ７１ ３３．３４３ ４５ ４６．５１０ ７２ ３３．０９８ ４６ ４５．１７２ ７３ ３２．８１３ ４７ ４５．０７４ ７４ ３２．６２１ ４８ ４４．２２６ ７５ ３２．２７０ ４９ ４３．６７３ ７６ ３２．１８８ ５０ ４３．６４６ ７７ ３２．１１２ ５１ ４０．４６２ ７８ ３２．０３６ ５２ ４０．３７４ ７９ ３１．８６６ ５３ ３８．５４６ ８０ ３１．７９３ ５４ ３８．４０８ ８１ ３０．８４４ ５５ ３８．２１１ ８２ ３０．７９０ ５６ ３８．１５２ ８３ ３０．３８２ ５７ ３７．９７３ ８４ ２９．８３４ ５８ ３７．１５０ ８５ ２８．８２１ ５９ ３７．０５９ ８６ ２８．７２８ ６０ ３７．０１４ ８７ ２８．４７０ ６１ ３６．９４０ ８８ ２７．９９９ ６２ ３６．７３２ ８９ ２７．８８３ ６３ ３６．６５３ ９０ ２７．１８８ ６４ ３６．５５８ ９１ ２６．０９２ ６５ ３６．３４９ ９２ ２５．４０１ No. PPM No. PPM 1 178.358 20 77.054 2 178.000 21 76.631 3 167.483 22 72.950 4 167.418 23 72.874 5 167.369 24 72.498 6 146.706 625 71.9967. 145.747 26 71.901 8 137.499 27 71.733 9 136.358 28 68.428 10 136.324 29 68.215 11 136.268 30 67.596 12 134.508 31 67.526 13 127. 018 32 67.342 14 125.944 33 67.278 15 125.613 34 67.210 16 125.473 35 67.136 17 124.269 36 56.843 18 124.032 37 56.300 19 77.477 8 56.230 No. PPM No. PPM 39 50.105 66 36.248 40 50.023 67 35.592 41 48.062 68 35.390 42 47.789 69 34.437 43 47.713 70 33.458 44 46.559 71 33.343 45 46.510 72 33.098 46 45.172 73 32.813 47 45.074 74 32.621 48 44.226 75 32.270 49 43.673 76 32.188 50 43.646 77 32.112 51 40. 462 78 32.036 52 40.374 79 31.866 53 38.546 80 31.793 54 38.408 81 30.844 55 38.211 82 30.790 56 38.152 83 30.382 57 37.973 84 29.834 8 37.150 85 28.821 59 37.059 86 28.728 60 37.014 87 28.470 61 36.940 88 27.999 62 36.7732 89 27.8883 63 36.653 90 27.188 64 36 .558 91 26.092 65 36.349 92 25.401
【００２１】応用実施例１〜５、比較例１ 表１に示す様な組成比（数値は重量部を示す。）にて３
本ロ−ルミルを用いて混練し、調整し印刷インキ用樹脂
組成物を得た。そして該組成物のインキ性能評価を行っ
た。Application Examples 1 to 5 and Comparative Example 1 3 with a composition ratio (numerical values indicate parts by weight) as shown in Table 1.
Kneading and adjustment were carried out using the present roll mill to obtain a resin composition for printing ink. Then, the ink performance of the composition was evaluated.
【００２２】インキ性能評価方法 硬化性（硬化時間）：インキ０．６ｇをＲＩテスタ−
（（株）明製作所製）を用いてカルトン紙に展色し、直
ちに８０W/cm、高圧水銀ランプで１０cmの距離から紫外
線を照射した後、ＲＩテスタ−により両面特ア−ト紙を
圧着し、インキが付着しなくなるまで要した照射時間
（秒）を硬化時間として求める。 原インキおよび乳化インキの光沢：上記でえられた硬化
後の印刷物の光沢（原インキ光沢）を肉眼観察して評価
する。Ink performance evaluation method Curability (curing time): 0.6 g of ink was added to RI tester.
(Manufactured by Akira Seisakusho Co., Ltd.) was used to develop color on the carton paper, and immediately irradiated with ultraviolet light from a distance of 10 cm with a high pressure mercury lamp at 80 W / cm, and then double-sided special art paper was pressure bonded with an RI tester. The curing time is the irradiation time (seconds) required until the ink does not adhere. Gloss of original ink and emulsified ink: The gloss of the cured print obtained above (original ink gloss) is visually observed and evaluated.
【００２３】またインキ０．６ｇと湿し水とをＲＩテス
タ−で乳化させ水切りした後、カルトン紙に展色し、原
インキ光沢の測定時と同一条件で硬化し、硬化後の印刷
面の光沢を乳化インキの光沢とし、同様に肉眼で観察し
下記の基準により評価する。 ◎ ： 非常に良好（印刷面が平滑であり、非常に艶が
ある。） ○ ： 良好（印刷面に艶がある） △ ： ○と×の中間 × ： 不良（印刷面に艶がなく、光を当ても反射しな
い）Further, 0.6 g of ink and fountain solution were emulsified with an RI tester, drained, and then spread on a carton paper, and cured under the same conditions as when measuring the gloss of the original ink. The gloss is taken as the gloss of the emulsified ink and similarly observed with the naked eye and evaluated according to the following criteria. ◎: Very good (printing surface is smooth and very glossy) ○: Good (printing surface is glossy) △: Intermediate between ○ and × ×: Poor (printing surface is not glossy and light Even if you hit it, it will not reflect)
【００２４】 ミスチング ： インコメ−タ−のロ−ルの前に紙を置
きインキが付着したロ−ルを１２００回転させてインキ
をミスチングさせ、紙面に飛散したインキの状態を肉眼
で観察し下記の基準で評価する。 ○ ： 少ない（使用適当） × ： 多い（使用不適当） 洗浄性 ： インキの付着したインコメ−タ−のロ−ル
の灯油による洗浄性を評価する。 ブロンジング：ＲＩテスタ−を用いてカルトン紙に展色
し、１時間室温で放置した後、硬化性試験と同様な条件
で紫外線を０．５秒照射して硬化させ、肉眼で観察して
下記の基準により評価する。 ○ ： 展色直後硬化した試料と比較し、同等の色調 × ： 顔料とビヒクルの分離がみられ、反射光が金色
を呈する。Misting: The paper is placed in front of the roll of the incom- puter, the roll to which the ink is attached is rotated 1200 times to misting the ink, and the state of the ink scattered on the paper surface is observed with the naked eye. Evaluate according to the standard. ◯: Small (suitable for use) ×: Large (unsuitable for use) Detergency: Evaluate the detergency of kerosene on the roll of the incommer with ink. Bronzing: The color was applied to the carton paper by using an RI tester, left at room temperature for 1 hour, and then irradiated with ultraviolet rays for 0.5 seconds under the same conditions as in the curability test to be cured. Evaluate according to the standard. ◯: Equivalent color tone compared to the sample cured immediately after color development ×: Separation of pigment and vehicle is observed, and reflected light is gold.
【００２５】 表１ 実施例 比較例 １ ２ ３ ４ ５ １ ２ 生成物Ａ 40 30 50 35 45 生成物Ｂ 5 5 5 KAYARAD R-114 ＊１ 40 36 〃 FM-300 ＊２ 29 29 29 T-1420 ＊３ 34 33 TMPTA ＊４ 19 19 イルガキュア−907 ＊５ ６ ６ ６ ６ ６ ６ ６ KAYACURE DETX ＊６ １ １ １ １ １ １ １ カ−ミン６Ｂ ＊７ 24 24 24 24 24 24 24 硬化時間（秒） 0.4 0.3 0.4 0.5 0.4 0.3 0.3 原インキ光沢 ◎ ◎ ◎ ◎ ◎ ○ ○ 乳化インキ光沢 ◎ ◎ ◎ ◎ ◎ △ △ ミスチング ○ ○ ○ ○ ○ × × 洗浄性 良好 良好 良好 良好 良好 不良 不良 ブロンジンク ○ ○ ○ ○ ○ × ×Table 1 Example Comparative Example 1 2 3 4 5 1 2 Product A 40 30 50 35 45 Product B 5 5 5 KAYARAD R-114 * 1 40 36 〃 FM-300 * 2 29 29 29 T-1420 * 3 34 33 TMPTA * 4 19 19 Irgacure-907 * 5 6 6 6 6 6 6 6 6 KAYACURE DETX * 6 1 1 1 1 1 1 1 1 1 Carmin 6B * 7 24 24 24 24 24 24 24 Curing time (seconds) 0.4 0.3 0.4 0.5 0.4 0.3 0.3 Raw ink gloss ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ Emulsion ink gloss ◎ ◎ ◎ ◎ ◎ ◎ △ △ Misting ○ ○ ○ ○ ○ × × Good cleaning good Good good Good bad Bad × ×
【００２６】注 ＊１ KAYARAD R-114 ：油化シエル
エポキシ（株）製 エピコ−ト828 のアクリル酸エステル化物。 ＊２ KAYARAD FM-300：ビスフェノ−ルＡのテトラエ
トキシジアクリレ−ト、日本化薬（株）製 ＊３ KAYARAD T-1420：ジトリメチロ−ルプロパンテ
トラアクリレ−ト 日本化薬（株）製 ＊４ KAYARAD TMPTA ：トリメチロ−ルプロパントリ
アクリレ−ト、日本化薬（株）製 ＊５ イルガキュア−907 ：チバ・ガイギ−社製、光
重合開始剤。 ＊６ KAYACURE DETX ：日本化薬（株）製、光重合開
始剤。 ＊７ カ−ミン６Ｂ：アゾ系紅顔料。Note * 1 KAYARAD R-114: An acrylic acid esterified product of Epicort 828 manufactured by Yuka Shell Epoxy Co., Ltd. * 2 KAYARAD FM-300: Bisphenol A tetraethoxy diacrylate, manufactured by Nippon Kayaku Co., Ltd. * 3 KAYARAD T-1420: Ditrimethylol propane tetraacrylate manufactured by Nippon Kayaku Co., Ltd. * 4 KAYARAD TMPTA: Trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd. * 5 Irgacure-907: Photopolymerization initiator manufactured by Ciba-Geigy. * 6 KAYACURE DETX: Photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd. * 7 Carmine 6B: Azo red pigment.
【００２７】表から明らかなように、本発明の樹脂組成
物は光沢、印刷適性（ミスチング、洗浄性、ブロンジン
グ等）に優れている。As is apparent from the table, the resin composition of the present invention is excellent in gloss and printability (misting, cleaning, bronzing, etc.).
【００２８】[0028]
【発明の効果】本発明の光硬化性オリゴマ−は、その光
硬化性を利用することにより広範囲な用途に適用するこ
とができ、特に印刷インキ用バインダ−として使用した
場合には、得られた印刷インキの光沢、顔料分散性、印
刷適性などの点で従来の溶剤型印刷インキと比較して優
れた利点を有する。INDUSTRIAL APPLICABILITY The photocurable oligomer of the present invention can be applied to a wide range of applications by utilizing its photocurability, and it was obtained when it was used as a binder for printing ink. It has advantages over conventional solvent-based printing inks in terms of gloss, pigment dispersibility, printability, etc. of printing inks.
Claims (3)
物である光硬化性オリゴマ−。1. A compound represented by the formula (1): (In the formula, R is H or CH 3. ) A photocurable oligomer which is a reaction product of rosin.
することを特徴とする樹脂組成物。2. A resin composition containing the photocurable oligomer according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29961191A JPH05112737A (en) | 1991-10-21 | 1991-10-21 | Photocurable oligomer, resin composition containing same, and its cured article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29961191A JPH05112737A (en) | 1991-10-21 | 1991-10-21 | Photocurable oligomer, resin composition containing same, and its cured article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05112737A true JPH05112737A (en) | 1993-05-07 |
Family
ID=17874870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29961191A Pending JPH05112737A (en) | 1991-10-21 | 1991-10-21 | Photocurable oligomer, resin composition containing same, and its cured article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05112737A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010091498A (en) * | 2008-10-10 | 2010-04-22 | Toyo Seiki Seisakusho:Kk | Apparatus for washing roll of inkometer and method for washing roll |
-
1991
- 1991-10-21 JP JP29961191A patent/JPH05112737A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010091498A (en) * | 2008-10-10 | 2010-04-22 | Toyo Seiki Seisakusho:Kk | Apparatus for washing roll of inkometer and method for washing roll |
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