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TW201840753A - Ink composition and printed matter - Google Patents

Ink composition and printed matter Download PDF

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TW201840753A
TW201840753A TW107104481A TW107104481A TW201840753A TW 201840753 A TW201840753 A TW 201840753A TW 107104481 A TW107104481 A TW 107104481A TW 107104481 A TW107104481 A TW 107104481A TW 201840753 A TW201840753 A TW 201840753A
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ink composition
water
mass
ink
organic solvent
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TW107104481A
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TWI758407B (en
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水崎透
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日商日信化學工業股份有限公司
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  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract

There is provided an ink composition which contains (A) a non-ionic surface active agent represented by a specific formula, water, (B) a water-soluble organic solvent having a solubility parameter (SP value) of 9.0-12.0, and a colorant, where a content of the component (A) is 0.01-5 mass%. An ink composition has excellent wettability and permeability, and accordingly prevents color bleeding, is excellent in color developing property and image uniformity, and can cope with high-speed printing and high-speed coating. The ink composition exhibits an adequate low contact angle even to a medium such as glossy paper, PP, PET and a PVC film with poor absorbency, and accordingly dots of ink are independent, and the ink composition prevents blurring, has dense printing density and color density of a printed image, and exhibits extremely good printing performance.

Description

油墨組成物及印刷物Ink composition and printed matter

本發明係有關於一種含有非離子性界面活性劑、水、水溶性有機溶劑及著色劑的油墨組成物及印刷物。The present invention relates to an ink composition and a printed matter containing a nonionic surfactant, water, a water-soluble organic solvent, and a coloring agent.

近年來,在印刷業界,基於環保取向等而持續推進油墨的水系化(水/低揮發性水溶性有機溶劑混合系)的發展。就此動向,對於向來以有機溶劑系油墨為主流的蠟光紙、聚丙烯(PP)、聚對苯二甲酸乙二酯(PET)、聚氯乙烯(PVC)膜等吸收性差的介質(記錄媒體)亦同。In recent years, in the printing industry, the development of water-based (water/low-volatility water-soluble organic solvent mixed systems) of inks has been continuously promoted based on environmentally friendly orientation. In this case, a poorly absorbable medium such as wax paper, polypropylene (PP), polyethylene terephthalate (PET), or polyvinyl chloride (PVC) film, which has been dominated by organic solvent-based inks (recording media) ) Same as.

尤其是對於此種吸收性差的介質,在將油墨的一部分有機溶劑替換為水的系統(水/有機溶劑混合系)中,會發生起因於潤濕性不足的印字不良。因此,此種油墨中一般係添加有界面活性劑。In particular, in such a poorly absorbable medium, in a system in which a part of the organic solvent of the ink is replaced with water (water/organic solvent mixed system), printing defects due to insufficient wettability occur. Therefore, a surfactant is generally added to such an ink.

在油墨或水系塗料業界,係廣泛使用聚矽氧系界面活性劑或乙炔二醇系界面活性劑等的非離子性界面活性劑。作為聚矽氧系界面活性劑,已知有改質聚矽氧烷化合物,在專利文獻1~4(日本特開2003-253166號公報、日本特開2013-203910號公報、日本特開2005-23253號公報及日本特開2005-120181號公報)中揭露使用聚醚改質聚矽氧的油墨組成物。In the ink or water-based paint industry, a nonionic surfactant such as a polyoxymethylene surfactant or an acetylene glycol surfactant is widely used. As a polyfluorene-based surfactant, a modified polyoxyalkylene compound is known, and Patent Documents 1 to 4 (Japanese Laid-Open Patent Publication No. 2003-253166, JP-A-2013-203910, JP-A-2005-- An ink composition using polyether modified polyfluorene is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 23-253181.

然而,僅以使用此種聚矽氧系等之界面活性劑的油墨印字於吸收性差的介質,仍常常無法賦予充分的潤濕性,因此便要求解決此問題。 [先前技術文獻] [專利文獻]However, it is often impossible to impart sufficient wettability by printing inks using such a surfactant such as a polyoxygen-based surfactant, and thus it is required to solve the problem. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特開2003-253166號公報   [專利文獻2]日本特開2013-203910號公報   [專利文獻3]日本特開2005-23253號公報   [專利文獻4]日本特開2005-120181號公報[Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-203910 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei. No. 2005-23203 [Patent Document 4] JP-A-2005-120181 Bulletin

[發明所欲解決之課題][Problems to be solved by the invention]

本發明係有鑑於上述實情而完成者,茲以提供一種在印字於蠟光紙、PP、PET、PVC膜等吸收性差的介質時,仍可發揮優良的潤濕性的油墨組成物及將該油墨組成物印刷於記錄媒體的印刷物為目的。 [解決課題之手段]The present invention has been made in view of the above circumstances, and provides an ink composition which can exhibit excellent wettability when printed on a medium having poor absorbability such as wax paper, PP, PET, or PVC film, and The ink composition is printed on a printed matter of a recording medium for the purpose. [Means for solving the problem]

本案發明人為達成上述目的而致力進行研究的結果新發現出用於油墨組成物之有機溶劑的溶解度參數(SP值)與油墨的潤濕性,有一定程度的相關性。亦即,吾人發現出單獨比較有機溶劑時,使用SP值較小的有機溶劑,較有油墨組成物之潤濕性優良的傾向。從而,在水・有機溶劑的混合系油墨組成物中,若使用SP值較小的有機溶劑,則預測可獲得潤濕性優良的油墨組成物。As a result of intensive research to achieve the above object, the inventors of the present invention have newly found that the solubility parameter (SP value) of the organic solvent used for the ink composition and the wettability of the ink have a certain degree of correlation. That is, when it is found that an organic solvent having a small SP value is used for comparison of an organic solvent alone, the wettability of the ink composition tends to be superior. Therefore, when an organic solvent having a small SP value is used in a mixed ink composition of water or an organic solvent, it is predicted that an ink composition excellent in wettability can be obtained.

然而,在上述水・有機溶劑的混合系油墨組成物中,即使添加向來使用的界面活性劑,也無法大幅改善潤濕性。因此,本案發明人進一步進行研究的結果發現,在使用溶解度參數(SP值)為12.0以下之較小值的有機溶劑之水・有機溶劑的混合系油墨組成物中,透過採用最佳之界面活性劑,亦即後述式(1)所示之聚矽氧系非離子性界面活性劑,在印字於蠟光紙、PP、PET、PVC膜等吸收性差的介質時,仍可發揮優良的潤濕性,墨點獨立分布,無浸滲,印字濃度、印字圖像之色濃度極濃,而顯示極良好的印字性能,遂完成本發明。However, in the mixed ink composition of the above water/organic solvent, even if a surfactant which is used in the past is added, the wettability cannot be greatly improved. Therefore, as a result of further research, the inventors of the present invention found that the optimum interfacial activity is adopted in a mixed ink composition of an organic solvent in an organic solvent using a solubility parameter (SP value) of 12.0 or less. The polyfluorene-based nonionic surfactant represented by the following formula (1) can exhibit excellent wetting when printed on a poorly absorbable medium such as wax paper, PP, PET, or PVC film. The ink dots are independently distributed, without impregnation, the printing density, the color density of the printed image are extremely concentrated, and the printing performance is excellent, and the present invention is completed.

從而,本發明係提供一種下述油墨組成物及將該油墨組成物印刷於記錄媒體而成的印刷物。   [1]一種油墨組成物,其特徵為:含有(A)下述式(1)所示之非離子性界面活性劑、水、(B)溶解度參數(SP值)為9.0~12.0的水溶性有機溶劑、與著色劑,上述(A)成分的含量為0.01~5質量%;[式(1)中,m1為10以上之整數,n1為1以上之整數,R1 表示碳數為1~20之烷基、碳數為1~20之含羥基之烷基、碳數為1~20之含羧基之烷基、或下述式(2)所示之基][R2 為氫原子或碳數1~5之烷基,a為0~10的數,b為0~50的數;又,(C2 H4 O)單元及(C3 H6 O)單元不拘其順序,可為隨機或嵌段式]。   [2]如[1]之油墨組成物,其中上述(A)成分之式(1)之R1 的至少1個為上述式(2)所示之基。   [3]如[1]或[2]之油墨組成物,其中上述(A)成分之非離子性界面活性劑,其上述式(1)中的n1為1~5。   [4]如[1]~[3]中任一項之油墨組成物,其中上述(B)成分之水溶性有機溶劑的含量為5~40質量%。   [5]如[1]~[4]中任一項之油墨組成物,其中水與(B)成分之水溶性有機溶劑的比,以質量比計為95:5~60:40。   [6]一種印刷物,其特徵為具有由如上述[1]~[5]中任一項之油墨組成物所形成的印刷部。 [發明之效果]Accordingly, the present invention provides an ink composition described below and a printed matter obtained by printing the ink composition on a recording medium. [1] An ink composition comprising: (A) a nonionic surfactant represented by the following formula (1), water, and (B) a solubility parameter (SP value) of 9.0 to 12.0 The organic solvent and the coloring agent, the content of the component (A) is 0.01 to 5% by mass; In the formula (1), m1 is an integer of 10 or more, n1 is an integer of 1 or more, and R 1 represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group-containing alkyl group having 1 to 20 carbon atoms, and a carbon number of a carboxyl group-containing alkyl group of 1 to 20 or a group represented by the following formula (2)] [R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is a number from 0 to 10, and b is a number from 0 to 50; further, a (C 2 H 4 O) unit and (C 3 H 6 O) Units are in any order, which can be random or blockwise]. [2] The ink composition according to [1], wherein at least one of R 1 of the formula (1) of the component (A) is a group represented by the above formula (2). [3] The ink composition according to [1] or [2], wherein the nonionic surfactant of the component (A) has n1 in the formula (1) of from 1 to 5. [4] The ink composition according to any one of [1] to [3] wherein the content of the water-soluble organic solvent of the component (B) is from 5 to 40% by mass. [5] The ink composition according to any one of [1] to [4] wherein the ratio of water to the water-soluble organic solvent of the component (B) is 95:5 to 60:40 by mass. [6] A printed matter comprising the printing portion formed of the ink composition according to any one of the above [1] to [5]. [Effects of the Invention]

本發明之油墨組成物由於具有優良的潤濕性、滲透性,而無滲色,顯色性、圖像均勻性優異,且亦可因應高速印刷及高速塗敷。又,此油墨組成物由於對蠟光紙、PP、PET、PVC膜等吸收性差的介質仍適度地顯示低接觸角,因此墨點獨立分布,無浸滲,印字濃度、印字圖像之色濃度極濃,而顯示極良好的印字性能。The ink composition of the present invention has excellent wettability and permeability without bleed, excellent color rendering properties, image uniformity, and high-speed printing and high-speed coating. Moreover, since the ink composition exhibits a low contact angle moderately for a medium having poor absorbability such as a glossy paper, a PP, a PET, or a PVC film, the ink dots are independently distributed, and there is no infiltration, a printing density, and a color density of the printed image. Extremely strong, and shows excellent printing performance.

[實施發明之形態][Formation of the Invention]

本發明之油墨組成物係含有作為(A)成分之特定的非離子性界面活性劑、水、作為(B)成分之顯示特定的溶解度參數(SP值)的水溶性有機溶劑、與著色劑。The ink composition of the present invention contains a specific nonionic surfactant as the component (A), water, a water-soluble organic solvent which exhibits a specific solubility parameter (SP value) as the component (B), and a color former.

(A)成分為下述式(1)所示之非離子性界面活性劑: The component (A) is a nonionic surfactant represented by the following formula (1):

上述式(1)中,m1為10以上之整數,n1為1以上之整數,R1 表示碳數1~20之烷基、碳數1~20之含羥基之烷基、碳數1~20之含羧基之烷基、或下述式(2)所示之基。 In the above formula (1), m1 is an integer of 10 or more, n1 is an integer of 1 or more, and R 1 represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group-containing alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to 20 carbon atoms. The carboxyl group-containing alkyl group or a group represented by the following formula (2).

上述式(2)中,R2 為氫原子或碳數1~5之烷基,a為0~10的數,b為0~50的數;又,(C2 H4 O)單元及(C3 H6 O)單元不拘其順序,可為隨機或嵌段式。In the above formula (2), R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is a number of 0 to 10, and b is a number of 0 to 50; further, a (C 2 H 4 O) unit and The C 3 H 6 O) units are in any order and may be random or block.

上述式(1)中,m1為10以上之整數。若使用m1為10以上之整數的上述式(1)之非離子性界面活性劑,作為水溶性有機溶劑使用溶解度參數(SP值)12.0以下者時,會顯示優良的潤濕性。又,上述式(1)中,m1較佳為10~100之整數,更佳為10~60之整數。In the above formula (1), m1 is an integer of 10 or more. When the nonionic surfactant of the above formula (1) in which m1 is an integer of 10 or more is used, when the solubility parameter (SP value) of 12.0 or less is used as the water-soluble organic solvent, excellent wettability is exhibited. Further, in the above formula (1), m1 is preferably an integer of from 10 to 100, more preferably an integer of from 10 to 60.

又,上述式(1)中,n1為1以上之整數,較佳為1~10之整數,更佳為1~5之整數。上述n1的值若偏離上述範圍,則有油墨的潤濕性不足之虞。Further, in the above formula (1), n1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5. If the value of the above n1 deviates from the above range, the wettability of the ink may be insufficient.

作為上述式(1)的R1 ,係以其至少1個,更佳全為式(2)所示之基為佳。此時,作為上述式(1)的R1 ,採用上述式(2)所示之基時,就該式中的a,b值,係以a=1~10,b=1~20,尤為a=1~5,b=1~10為宜。上述a或b值若偏離上述範圍,則有油墨的潤濕性不足之虞。R 1 of the above formula (1) is preferably at least one, more preferably all groups represented by the formula (2). In this case, when R 1 of the above formula (1) is used as the group represented by the above formula (2), the values of a and b in the formula are a = 1 to 10, and b = 1 to 20, particularly a = 1 to 5, and b = 1 to 10 is suitable. If the value of a or b is deviated from the above range, the wettability of the ink may be insufficient.

(A)成分只要是上述式(1)所示者即可,尤以HLB為5~16,更佳為5~8者為佳,其性能未必與HLB有關。The component (A) may be any one represented by the above formula (1), and particularly preferably an HLB of 5 to 16, more preferably 5 to 8, and the performance is not necessarily related to HLB.

於此,HLB(親水基/疏水基平衡「Hydrophile-Lipophile Barance」)係由下述式(3)(格里芬法)所定義。HLB係取0~20的值,該值愈接近0親油性愈高,愈接近20則親水性愈高。 Here, HLB (Hydrophile-Lipophile Barance) is defined by the following formula (3) (Griffin method). HLB is a value of 0 to 20, and the closer the value is to 0, the higher the lipophilicity, and the closer to 20, the higher the hydrophilicity.

進行上述式(1)所示之非離子性界面活性劑的HLB的算出時,就親水性部分而言係屬R1 的(C2 H4 O)單元、羥基、羧基。When the HLB of the nonionic surfactant represented by the above formula (1) is calculated, the hydrophilic portion is a (C 2 H 4 O) unit of R 1 , a hydroxyl group, or a carboxyl group.

(A)成分的含量,在油墨組成物100質量%中為0.01~5.0質量%,較佳為0.05~5.0質量%,更佳為0.1~5.0質量%。(A)成分的含量若超過5.0質量%,則會造成起泡或印刷時的浸滲。The content of the component (A) is 0.01 to 5.0% by mass, preferably 0.05 to 5.0% by mass, and more preferably 0.1 to 5.0% by mass based on 100% by mass of the ink composition. When the content of the component (A) exceeds 5.0% by mass, foaming or impregnation at the time of printing may occur.

又,(A)成分相對於著色劑的含量較佳為0.2~100質量%,更佳為1~100質量%。Further, the content of the component (A) relative to the colorant is preferably from 0.2 to 100% by mass, more preferably from 1 to 100% by mass.

此外,本發明之油墨組成物中係含有水、與作為(B)成分之溶解度參數(SP值)為9.0~12.0的水溶性有機溶劑。Further, the ink composition of the present invention contains water and a water-soluble organic solvent having a solubility parameter (SP value) of the component (B) of 9.0 to 12.0.

本發明之油墨組成物所含的水,可使用例如離子交換水等。水的含量,在油墨組成物100質量%中較佳為55~95質量%,更佳為60~80質量%。As the water contained in the ink composition of the present invention, for example, ion-exchanged water or the like can be used. The content of water is preferably 55 to 95% by mass, more preferably 60 to 80% by mass, based on 100% by mass of the ink composition.

作為(B)成分之水溶性有機溶劑,可舉出碳數5~10之烷基醇類、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、乙二醇單丙基醚、乙二醇單丁基醚、丙酮等,可適宜選擇使用此等的1種或2種以上,惟(B)成分之水溶性有機溶劑,其溶解度參數(SP值)為9.0~12.0。此溶解度參數(SP值)δ係使用Fedors之推算法(R.F.Fedors:Polym. Eng. Sci., 14[2], 147-154(1974))所求得的值。就Fedors之推算法,係依據分子結構,將表1所示值代入下述式(4)來求出SP值δ。此外,表1所示值係摘錄Fedors所提案之值者。於此,ΣEcoh 表示凝聚能(cal/mol),ΣV表示莫耳分子體積(cm3 /mol)。 Examples of the water-soluble organic solvent of the component (B) include alkyl alcohols having 5 to 10 carbon atoms, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, acetone, etc., may be suitably selected from one or more of these, but the water-soluble organic solvent of (B) component, solubility parameter ( The SP value) is 9.0 to 12.0. This solubility parameter (SP value) δ is a value obtained by the Fedors' push algorithm (RFFedors: Polym. Eng. Sci., 14 [2], 147-154 (1974)). The Fedors' push algorithm is based on the molecular structure, and the value shown in Table 1 is substituted into the following formula (4) to find the SP value δ. In addition, the values shown in Table 1 are extracted from the values proposed by Fedors. Here, ΣE coh represents a cohesive energy (cal/mol), and ΣV represents a molar molecular volume (cm 3 /mol).

例如,若為乙二醇單丙基醚,係如下求得。 For example, if it is ethylene glycol monopropyl ether, it is obtained as follows.

從而,此處乙二醇單丙基醚的溶解度參數(SP值)為「11.1」。Therefore, the solubility parameter (SP value) of the ethylene glycol monopropyl ether here is "11.1".

(B)成分之水溶性有機溶劑的溶解度參數(SP值)若超過12.0,有油墨的潤濕性不足之虞;又,小於9.0的話,則油墨的儲存穩定性不良。When the solubility parameter (SP value) of the water-soluble organic solvent of the component (B) exceeds 12.0, the wettability of the ink is insufficient, and if it is less than 9.0, the storage stability of the ink is poor.

(B)成分之水溶性有機溶劑的含量,在油墨組成物100質量%中較佳為5~40質量%,更佳為20~40質量%。The content of the water-soluble organic solvent of the component (B) is preferably from 5 to 40% by mass, more preferably from 20 to 40% by mass, based on 100% by mass of the ink composition.

水與(B)成分之水溶性有機溶劑的含量比,以質量比計較佳為95:5~60:40,更佳為80:20~60:40。此水溶性有機溶劑的含量愈少,愈無需顧慮環保問題而較佳,但過少的話則有油墨組成物的潤濕性不足之虞。The content ratio of water to the water-soluble organic solvent of the component (B) is preferably 95:5 to 60:40, more preferably 80:20 to 60:40 by mass. The smaller the content of the water-soluble organic solvent, the better it is not necessary to worry about environmental protection, but if it is too small, the wettability of the ink composition is insufficient.

本發明之油墨組成物係含有著色劑。作為著色劑,可適宜使用染料、有機顏料、無機顏料。例如,就染料而言,可使用根據色指數分類為酸性染料、直接染料、反應染料、甕染料、硫化染料或食品用色素者,此外亦可使用分類為油溶染料、鹼性染料的著色劑。又,就顏料而言,作為黑色油墨用,可舉出爐黑(Color Black)、燈黑、乙炔黑、槽黑等的碳黑(C.I.顏料黑7)類,具體而言,可舉出例如Ravan 7000、Ravan 5750、Ravan 5250、Ravan 5000、Ravan 3500、Ravan 2000、Ravan 1500、Ravan 1250、Ravan 1200、Ravan 1190ULTRA-II、Ravan 1170、Ravan 1255(以上為COLUMBIA公司製)、Black Pearls L、Regal 400R、Regal 330R、Regal 660R、Mogul L、Monarch 700、Monarch 800、Monarch 880、Monarch 900、Monarch 1000、Monarch 1100、Monarch 1300、Monarch 1400、Valcan XC-72R(以上為CABOT公司製);Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW200、Color Black S150、Color Black S160、Color Black S170、Printex 35、Printex U、Printex V、Printex 140U、Printex 140V、Special Black 6、Special Black 5、Special Black 4A、Special Black 4(以上為Degussa公司製);No.25、No.33、No.40、No.47、No.52、No.900、No.2300、MCF-88、MA600、MA7、MA8、MA100(以上為三菱化學公司製)等、或銅氧化物、鐵氧化物(C.I.顏料黑11)、氧化鈦等的金屬類、苯胺黑(C.I.顏料黑1)等的有機顏料。再者,作為彩色油墨用,可使用C.I.顏料黃1(耐曬黃G)、3、12(雙偶氮黃AAA)、13、14、17、24、34、35、37、42(黃色氧化鐵)、53、55、74、81、83(雙偶氮黃HR)、93、94、95、97、98、100、101、104、108、109、110、117、120、128、138、153、180、C.I.顏料紅1、2、3、5、17、22(耐曬亮猩紅)、23、31、38、48:2(永固紅2B(Ba))、48:2(永固紅2B(Ca))、48:3(永固紅2B(Sr))、48:4(永固紅2B(Mn))、49:1、52:2、53:1、57:1(亮洋紅6B)、60:1、63:1、63:2、64:1、81(玫瑰紅6G色澱)、83、88、101(鐵紅)、104、105、106、108(鎘紅)、112、114、122(喹吖酮洋紅)、123、146、149、166、168、170、172、177、178、179、185、190、193、202、206、209、219、C.I.顏料紫19、23、C.I.顏料橙36、C.I.顏料藍1、2、15(酞菁藍R)、15:1、15:2、15:3(酞菁藍G)、15:4、15:6(酞菁藍E)、16、17:1、56、60、63、C.I.顏料綠1、4、7、8、10、17、18、36等。著色料的摻混量,在油墨組成物100質量%中較佳為0.1~15質量%,更佳為2~10質量%。The ink composition of the present invention contains a colorant. As the colorant, a dye, an organic pigment, or an inorganic pigment can be suitably used. For example, in the case of a dye, an acid dye, a direct dye, a reactive dye, an anthraquinone dye, a sulfur dye, or a food coloring dye can be classified according to a color index, and a coloring agent classified as an oil-soluble dye or a basic dye can also be used. . In addition, as the black ink, examples of the black ink include carbon black (CI pigment black 7) such as color black, lamp black, acetylene black, and channel black, and specific examples thereof include Ravan. 7000, Ravan 5750, Ravan 5250, Ravan 5000, Ravan 3500, Ravan 2000, Ravan 1500, Ravan 1250, Ravan 1200, Ravan 1190 ULTRA-II, Ravan 1170, Ravan 1255 (above COLUMBIA), Black Pearls L, Regal 400R , Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Valcan XC-72R (above CABOT); Color Black FW1 Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Printex 140V, Special Black 6, Special Black 5 , Special Black 4A, Special Black 4 (above, Degussa); No. 25, No. 33, No. 40, No. 47, No. 52, No. 900, No. 2300, MCF-88, MA600, MA7, MA8, MA100 (in The above is an organic pigment such as a metal oxide such as copper oxide, iron oxide (C.I. Pigment Black 11) or titanium oxide, or aniline black (C.I. Pigment Black 1). Further, as the color ink, CI Pigment Yellow 1 (Tanning Yellow G), 3, 12 (Bisazo Yellow AAA), 13, 14, 17, 24, 34, 35, 37, 42 (yellow oxidation) can be used. Iron), 53, 55, 74, 81, 83 (disazo yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 180, CI Pigment Red 1, 2, 3, 5, 17, 22 (light fast red scarlet), 23, 31, 38, 48: 2 (permanent red 2B (Ba)), 48:2 (permanent Red 2B (Ca)), 48:3 (permanent red 2B (Sr)), 48:4 (permanent red 2B (Mn)), 49:1, 52:2, 53:1, 57:1 (bright Magenta 6B), 60:1, 63:1, 63:2, 64:1, 81 (Rose Red 6G Lake), 83, 88, 101 (Iron Red), 104, 105, 106, 108 (cadmium red) , 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219, CI Pigment Violet 19, 23, CI Pigment Orange 36, CI Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15:1, 15:2, 15:3 (phthalocyanine blue G), 15:4, 15:6 ( Phthalocyanine Blue E), 16, 17: 1, 56, 60, 63, CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, and the like. The blending amount of the coloring matter is preferably from 0.1 to 15% by mass, more preferably from 2 to 10% by mass, based on 100% by mass of the ink composition.

本發明之油墨組成物,例如可藉由將上述各成分採用螺旋槳式攪拌機等周知之混合調製方法加以混合而得。又,對於在常溫下為固體的成分,可視需求加熱並予以混合。The ink composition of the present invention can be obtained, for example, by mixing the above-mentioned respective components by a known mixing preparation method such as a propeller type agitator. Further, the components which are solid at normal temperature are heated and mixed as needed.

本發明之油墨組成物中,亦可視需求添加樹脂或其他添加劑。以樹脂來說,其係具有疏水基及親水基的聚合物;較佳的是形成該聚合物之物質的疏水基至少為選自烷基、環烷基或芳基的1種以上。而且,較佳的是親水基至少為羧基、磺酸基、羥基、胺基、或者醯胺基或彼等的鹼。作為形成該等分散聚合物之物質的具體實例,可使用具有雙鍵之丙烯醯基、甲基丙烯醯基、乙烯基或者具有芳基之單體或低聚物類。例如,若對苯乙烯、丙烯酸四氫糠酯、甲基丙烯酸丁酯、(α,2,3或4)-烷基苯乙烯、(α,2,3或4)-烷氧基苯乙烯、3,4-二甲基苯乙烯、α-苯基苯乙烯、二乙烯基苯、乙烯基萘、(甲基)丙烯酸二甲基胺基酯、(甲基)丙烯酸二甲基胺基乙酯、二甲基胺基丙基丙烯醯胺、N,N-二甲基胺基乙基丙烯酸酯、丙烯醯嗎啉、N,N-二甲基丙烯醯胺、N-異丙基丙烯醯胺、N,N-二乙基丙烯醯胺、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸乙基己酯、其他的(甲基)丙烯酸烷基酯、甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基、丙氧基、丁氧基之二乙二醇或聚乙二醇之(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸羥烷基酯、其他含氟、含氯、含矽(甲基)丙烯酸酯、(甲基)丙烯醯胺、馬來酸醯胺、(甲基)丙烯酸等的1官能以外者導入交聯結構時,可使用(單、二、三、四、聚)乙二醇二(甲基)丙烯酸酯、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇及1,10-癸二醇等的(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、甘油(二、三)(甲基)丙烯酸酯、雙酚A或F之環氧乙烷加成物之二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等具有丙烯醯基或甲基丙烯醯基的化合物。In the ink composition of the present invention, a resin or other additives may also be added as needed. In the case of a resin, it is a polymer having a hydrophobic group and a hydrophilic group; preferably, the hydrophobic group of the substance forming the polymer is at least one selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group. Moreover, it is preferred that the hydrophilic group be at least a carboxyl group, a sulfonic acid group, a hydroxyl group, an amine group, or a guanamine group or a base thereof. As a specific example of the substance forming the dispersed polymer, a propylene group having a double bond, a methacryl group, a vinyl group or a monomer or oligomer having an aryl group can be used. For example, if it is styrene, tetrahydrofurfuryl acrylate, butyl methacrylate, (α, 2, 3 or 4)-alkylstyrene, (α, 2, 3 or 4)-alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylaminomethacrylate, dimethylaminoethyl (meth)acrylate , dimethylaminopropyl acrylamide, N,N-dimethylaminoethyl acrylate, propylene morpholine, N,N-dimethyl decylamine, N-isopropyl acrylamide , N,N-diethyl acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethyl hexyl (meth) acrylate, others (A Alkyl acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy, propoxy, butoxy diethylene glycol or polyethylene glycol (meth) acrylate, Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, hydroxyalkyl (meth)acrylate, others Fluorine, chlorine, yttrium (meth) acrylate, (meth) acrylamide, guanamine maleate When a one-membered structure such as (meth)acrylic acid is introduced into a crosslinked structure, (mono, di-, tri-, tetra-, poly) ethylene glycol di(meth)acrylate or 1,4-butanediol can be used. (Meth) acrylate, trimethylolpropane tri(methyl) such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol Acrylate, glycerol (di-, tri) (meth) acrylate, di(meth) acrylate of ethylene oxide adduct of bisphenol A or F, neopentyl glycol di(meth) acrylate, A compound having an acrylonitrile group or a methacryl group, such as pentaerythritol tetra(meth)acrylate or dipentaerythritol hexa(meth)acrylate.

上述樹脂的摻混量不特別限定,在油墨組成物100質量%中較佳為0~30質量%,更佳為0~20質量%。此外,摻混樹脂時,較佳取1質量%以上。The blending amount of the above resin is not particularly limited, and is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, based on 100% by mass of the ink composition. Further, when the resin is blended, it is preferably 1% by mass or more.

作為其他添加劑,可適宜摻混紫外線吸收劑、抗氧化劑、pH調整劑、防腐劑、黏度調整劑等。此等添加劑能以油墨組成物100質量%中的其餘部分來摻混。As other additives, a UV absorber, an antioxidant, a pH adjuster, a preservative, a viscosity adjuster, and the like can be suitably blended. These additives can be blended in the remainder of 100% by mass of the ink composition.

油墨組成物,較佳將黏度(23℃)調製成4mPa・s以下(不含0),藉此可發揮優良的印字特性。The ink composition preferably has a viscosity (23 ° C) of 4 mPa·s or less (excluding 0), thereby exhibiting excellent printing characteristics.

本發明之油墨組成物係藉由作成油墨而塗敷、印刷於記錄媒體,可獲得無滲色,顯色性、圖像均勻性優異,而且無浸滲,印字濃度、印字圖像之色濃度極濃的印刷物。The ink composition of the present invention is applied to a recording medium by printing ink, and can be obtained without bleeding, excellent color rendering property, image uniformity, and without impregnation, printing density, color density of printed image. Extremely rich prints.

作為油墨對記錄媒體的塗敷、印刷方法,可舉出噴墨記錄方式、使用筆等的書寫用具之記錄方式、其他周知之印刷方法。尤其是,本發明之油墨組成物可較佳地使用於噴墨記錄方式,亦可因應高速印刷及高速塗敷。Examples of the method of applying and printing the ink to the recording medium include an ink jet recording method, a recording method using a writing instrument such as a pen, and other known printing methods. In particular, the ink composition of the present invention can be preferably used in an ink jet recording mode, and can also be applied to high speed printing and high speed coating.

再者,本發明之油墨組成物係供印刷於記錄媒體,尤其可適用在塗敷於低吸收性被記錄媒體、非吸收性被記錄媒體。作為低吸收性被記錄媒體,不特別限定,可舉出例如表面設有供容納油性油墨之塗敷層的塗紙。作為塗紙,不特別限定,可舉出例如以銅版紙、塗佈紙、無光像紙為代表之實際印刷紙(actual printing stock)。作為非吸收性被記錄媒體,不特別限定,可舉出例如不具有油墨吸收層之塑膠薄膜、以紙為代表之在基材上塗覆有塑膠者或接著有塑膠薄膜者等。作為此處所稱之塑膠,可舉出聚氯乙烯(PVC)、聚對苯二甲酸乙二酯(PET)、聚碳酸酯、聚苯乙烯、聚胺基甲酸酯、聚乙烯、聚丙烯(PP)等。 [實施例]Further, the ink composition of the present invention is printed on a recording medium, and is particularly preferably applied to a low-absorption recording medium or a non-absorbent recording medium. The low-absorption recording medium is not particularly limited, and for example, a coated paper having a coating layer for containing an oil-based ink on its surface is provided. The coated paper is not particularly limited, and examples thereof include actual printing stock typified by coated paper, coated paper, and matte paper. The non-absorptive recording medium is not particularly limited, and examples thereof include a plastic film which does not have an ink absorbing layer, a case where a plastic is coated on a substrate, or a plastic film, which is represented by paper. Examples of the plastic referred to herein include polyvinyl chloride (PVC), polyethylene terephthalate (PET), polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene ( PP) and so on. [Examples]

以下示出實施例及比較例,對本發明具體地加以說明,惟本發明不限於下述之實施例。The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the examples described below.

[實施例1]   使用式(1)及式(2)中m1=10、n1=3、a=3、b=1、R2 =H的非離子性界面活性劑(A-1)[HLB=5],以表3表示組成製作油墨組成物。[Example 1] A nonionic surfactant (A-1) [HLB] in which m1 = 10, n1 = 3, a = 3, b = 1, and R 2 = H in the formulae (1) and (2) was used. =5], the composition of the ink was produced in Table 3.

將5.0質量%作為黑色顏料的Color Black S170 (Degussa公司製),在以螺旋槳式攪拌機攪拌的同時緩緩地添加於64.5質量%離子交換水中後,添加0.5質量%非離子性界面活性劑(A-1)、30.0質量%乙二醇單丙基醚(SP值:11.1)(B-1),攪拌1小時,而得到黑色(B)油墨組成物。Color Black S170 (manufactured by Degussa Co., Ltd.) containing 5.0% by mass of a black pigment was gradually added to 64.5 mass% of ion-exchanged water while stirring with a propeller mixer, and then 0.5% by mass of a nonionic surfactant (A) was added. -1), 30.0% by mass of ethylene glycol monopropyl ether (SP value: 11.1) (B-1), and stirred for 1 hour to obtain a black (B) ink composition.

又,使用洋紅色顏料(C.I.顏料紅122)、青色顏料(C.I.顏料藍15:3)、黃色顏料(C.I.顏料黃74)替代黑色顏料,根據與上述同樣的方法分別製成洋紅色(M)、青色(C)、黃色(Y)油墨組成物。Further, a magenta pigment (CI pigment red 122), a cyan pigment (CI pigment blue 15:3), and a yellow pigment (CI pigment yellow 74) were used instead of the black pigment, and magenta (M) was produced in the same manner as above. , cyan (C), yellow (Y) ink composition.

對製成的各油墨組成物進行以下評定。將其結果示於表3。The following ink composition was subjected to the following evaluation. The results are shown in Table 3.

(1)印字濃度   就以Seiko Epson製PX-045A,使用黑色油墨印字於OK Topcoat Paper(王子製紙製)的墨點,以Sakura微量密度計PDM-5型(SAKURA SEIKI公司製)測定印字濃度。印字濃度較佳為0.99~1.10,更佳為1.01~1.10。(1) Printing density The ink density of the PX-045A manufactured by Seiko Epson was printed on the OK Topcoat Paper (manufactured by Oji Paper Co., Ltd.) using a black ink, and the printing density was measured by a Sakura microdensity meter PDM-5 type (manufactured by SAKURA SEIKI Co., Ltd.). The printing density is preferably from 0.99 to 1.10, more preferably from 1.01 to 1.10.

(2)點徑   以Seiko Epson製PX-045A,使用黑色油墨印字於OK Topcoat Paper,放大100倍,測定點徑。點徑較佳為200~250μm,更佳為220~240μm。(2) Spot diameter PX-045A manufactured by Seiko Epson was printed on OK Topcoat Paper using black ink, magnified 100 times, and the spot diameter was measured. The spot diameter is preferably from 200 to 250 μm, more preferably from 220 to 240 μm.

(3)印字圖像的色濃度   以Seiko Epson製PX-045A將黑色(B)、洋紅色(M)、青色(C)、黃色(Y)油墨實地印刷於OK Topcoat Paper,以Macbeth濃度計RD-918(Macbeth公司製)進行測定。色濃度較佳為1.30~2.00,更佳為1.40~2.00。(3) Color density of printed image Black (B), magenta (M), cyan (C), and yellow (Y) inks were solid-printed on OK Topcoat Paper using a PX-045A manufactured by Seiko Epson, with a Macbeth concentration meter RD -918 (manufactured by Macbeth Co., Ltd.) was measured. The color density is preferably from 1.30 to 2.00, more preferably from 1.40 to 2.00.

(4)圖像均勻性   以Seiko Epson製PX-045A將黑色(B)、洋紅色(M)、青色(C)、黃色(Y)油墨印字於OK Topcoat Paper。將印字物以電子顯微鏡放大100倍,依以下基準評定平坦性。   ○:幾無濃度差者   △:僅有些微的濃度差者   ×:在墨點內可看見新月形的斑點紋路(4) Image uniformity Black (B), magenta (M), cyan (C), and yellow (Y) inks were printed on OK Topcoat Paper using PX-045A manufactured by Seiko Epson. The printed matter was magnified 100 times with an electron microscope, and flatness was evaluated according to the following criteria. ○: There is no difference in concentration △: Only a slight difference in density ×: A crescent-shaped speckle pattern can be seen in the ink dot

(5)接觸角   使用協和界面科學公司製接觸角計CA-D型測定0.3秒後各種界面活性劑溶液對OK Topcoat Paper、PP、PET、PVC的接觸角值。(5) Contact angle The contact angle value of various surfactant solutions to OK Topcoat Paper, PP, PET, PVC after 0.3 seconds was measured using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd.

[實施例2~11、比較例1~15]   與實施例1相同,以表3~5所示組成製作油墨組成物,並進行評定。其評定結果係一併示於表3(實施例2~11)、表4(比較例1~8)及表5(比較例9~15)。此外,就實施例2~11及比較例1~15,係使用下述(A)非離子性界面活性劑與(B)水溶性有機溶劑。[Examples 2 to 11 and Comparative Examples 1 to 15] In the same manner as in Example 1, the ink compositions were prepared in the compositions shown in Tables 3 to 5, and evaluated. The evaluation results are shown in Table 3 (Examples 2 to 11), Table 4 (Comparative Examples 1 to 8), and Table 5 (Comparative Examples 9 to 15). Further, in Examples 2 to 11 and Comparative Examples 1 to 15, the following (A) nonionic surfactant and (B) water-soluble organic solvent were used.

(A-1):式(1)及式(2)中,m1=10、n1=3、a=3、b=1及R2 =H的非離子性界面活性劑  [HLB=5]   (A-2):式(1)及式(2)中,m1=30、n1=3、a=3、b=8及R2 =CH3 的非離子性界面活性劑  [HLB=5]   (A-3):式(1)及式(2)中,m1=60、n1=3、a=3、b=1及R2 =H的非離子性界面活性劑  [HLB=5]   (A-4):式(1)及式(2)中,m1=1、n1=1、a=3、b=8及R2 =CH3 的非離子性界面活性劑  [HLB=4]   (A-5):式(1)及式(2)中,m1=8、n1=1、a=3、b=8及R2 =CH3 的非離子性界面活性劑  [HLB=4]   (A-6):式(1)及式(2)中,m1=8、n1=3、a=3、b=1及R2 =H的非離子性界面活性劑  [HLB=5]   (A-7):式(1)及式(2)中,m1=0、n1=1、a=1、b=0及R2 =H的非離子性界面活性劑  [HLB=5]   (B-1):乙二醇單丙基醚(SP值:11.1)   (B-2):乙二醇單丁基醚(SP值:10.8)   (B-3):丙酮(SP值:9.1)   (B-4):丙二醇(SP值:15.9)   (B-5):二乙二醇(SP值:15.0)(A-1): in the formulas (1) and (2), a nonionic surfactant having an m1 = 10, n1 = 3, a = 3, b = 1, and R 2 = H [HLB = 5] ( A-2): in the formulas (1) and (2), a nonionic surfactant having a m1 = 30, n1 = 3, a = 3, b = 8, and R 2 = CH 3 [HLB = 5] ( A-3): in the formulas (1) and (2), a nonionic surfactant having a m1 = 60, n1 = 3, a = 3, b = 1, and R 2 = H [HLB = 5] (A -4): in the formulas (1) and (2), a nonionic surfactant having a m1 = 1, n1 = 1, a = 3, b = 8, and R 2 = CH 3 [HLB = 4] (A -5): in the formulas (1) and (2), m1 = 8, n1 = 1, a = 3, b = 8, and R 2 = CH 3 of a nonionic surfactant [HLB = 4] (A -6): in the formulas (1) and (2), m1=8, n1=3, a=3, b=1 and R 2 =H nonionic surfactant [HLB=5] (A- 7): In the formulas (1) and (2), the nonionic surfactants of m1=0, n1=1, a=1, b=0 and R 2 =H [HLB=5] (B-1 ): ethylene glycol monopropyl ether (SP value: 11.1) (B-2): ethylene glycol monobutyl ether (SP value: 10.8) (B-3): acetone (SP value: 9.1) (B- 4): Propylene glycol (SP value: 15.9) (B-5): Diethylene glycol (SP value: 15.0)

Claims (6)

一種油墨組成物,其特徵為:含有(A)下述式(1)所示之非離子性界面活性劑、水、(B)溶解度參數(SP值)為9.0~12.0的水溶性有機溶劑、與著色劑,上述(A)成分的含量為0.01~5質量%;[式(1)中,m1為10以上之整數,n1為1以上之整數,R1 表示碳數1~20之烷基、碳數1~20之含羥基之烷基、碳數1~20之含羧基之烷基、或下述式(2)所示之基][R2 為氫原子或碳數1~5之烷基,a為0~10的數,b為0~50的數;又,(C2 H4 O)單元及(C3 H6 O)單元不拘其順序,可為隨機或嵌段]。An ink composition comprising (A) a nonionic surfactant represented by the following formula (1), water, and (B) a water-soluble organic solvent having a solubility parameter (SP value) of 9.0 to 12.0, With the coloring agent, the content of the component (A) is 0.01 to 5% by mass; In the formula (1), m1 is an integer of 10 or more, n1 is an integer of 1 or more, and R 1 represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group-containing alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to 20 carbon atoms. a carboxyl group-containing alkyl group or a group represented by the following formula (2)] [R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is a number from 0 to 10, and b is a number from 0 to 50; further, a (C 2 H 4 O) unit and (C 3 H 6 O) Units are in any order, which can be random or block]. 如請求項1之油墨組成物,其中上述(A)成分之式(1)之R1 的至少1個為上述式(2)所示之基。The ink composition of claim 1, wherein at least one of R 1 of the formula (1) of the component (A) is a group represented by the above formula (2). 如請求項1或2之油墨組成物,其中上述(A)成分之非離子性界面活性劑,其上述式(1)中的n1為1~5。The ink composition according to claim 1 or 2, wherein the nonionic surfactant of the above component (A) has n1 in the above formula (1) of from 1 to 5. 如請求項1~3中任一項之油墨組成物,其中上述(B)成分之水溶性有機溶劑的含量為5~40質量%。The ink composition according to any one of claims 1 to 3, wherein the content of the water-soluble organic solvent of the component (B) is from 5 to 40% by mass. 如請求項1~4中任一項之油墨組成物,其中水與(B)成分之水溶性有機溶劑的比,以質量比計為95:5~60:40。The ink composition according to any one of claims 1 to 4, wherein a ratio of water to a water-soluble organic solvent of the component (B) is 95:5 to 60:40 by mass. 一種印刷物,其特徵為具有由如請求項1~5中任一項之油墨組成物所形成的印刷部。A printed matter characterized by having a printing portion formed of the ink composition according to any one of claims 1 to 5.
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