201124482 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種活性能量射線硬化型喷黑油黑組成 物、及適於熱成型之附有圖樣之熱可塑性樹脂片材。 【先前技術】 習知，成型用附有圖樣之熱可塑性樹脂片材係藉由於薄犋 或片材狀之塑膠基材上，應用例如凹版印刷或絲網印刷手段 #，使用版進行圖樣印刷而製造。然而，於專利文獻1中^ 載’其存在有以下問題：即便於大批次生產之情形時，每個 成型品之版費所佔之比例極小’於如成型品樣品生產之d h 次生產之情形時，每個成型品所佔之版費會變大，作為、 正式生產（大批次）之初期投資，廠商之成本負擔會變得過 大。 另一方面，印刷圖樣之方法已知有喷墨方式，亦提出有Ά 劑糸、水糸之油墨組成物，但作為印刷基材，通常限於σ At 吸收某種程度之溶劑或水之種類之基材，例如在將丙稀酸系 • 樹脂片材或聚碳酸酯樹脂片材等能夠成型之熱可塑性樹月旨 片材作為印刷基材之情形時，便需要設置受容層等之步驟。 對於能夠成型之熱可塑性樹脂片材能夠某種程度地密接 之活性能量射線硬化型油墨組成物係記載於專利文獻2〜 專利文獻4中，但存在於硬化後之熱成型加工時由於彎曲或 拉伸等步驟而使所形成之圖樣等產生龜裂或白化之問題。 099140501 3 201124482 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開2〇〇1_247694號公報 專利文獻2 :日本專利特開2〇〇夂56232號公報 專利文獻3·日本專利特開2〇〇8_7687號公報 專利文獻4:日本專利特開2〇〇8194〇8號公報 【發明内容】 (發明所欲解決之問題） 本發明之課題在於提供一種尤其是於無處理層之情況下 亦可直接列印、密接性優異之活性能量射線硬化型喷墨油墨 、、且成物進而本％明之課題在於提供一種附有圖樣之熱可 塑性樹脂片材’其係藉由該油墨組成物而將圖樣列印於熱可 塑性樹脂材上並硬化而成者，該Μ材即便進行熱成型，亦 不會產生龜裂或白化現象’無損圖樣外觀。 (解決問題之手段） 本發明之活性能量射線硬化.型喷墨油墨組成物至少含 有：自乙婦基己内醯胺、（曱基)丙烯酸作、及（甲基)丙稀 酸異旨中選擇之1種或2種以上之單官能單體(Α);下述 通式（1)所不之雙酚Α環氧烷改質物之二（曱基）丙烯酸酯體 (B);自（甲基）丙烯酸2_經基·3_苯氧基丙_、（甲基）丙稀酸 4-第二丁基己§旨、（曱基）丙烯酸苯氧基乙g旨中選擇之】種 或2種以上之單體(C);及活性能量射線聚合起始劑⑼。 099140501 4 201124482 Η匕i] 通式（l) =CK-, R1 R2 /r^ __s R2 R ‘ ：=c—^i4"OCH2CH t° 飞 // o-f^Q^o-j^c-c (式中，R1表示氫或曱基，R2表示氫、曱基或/乙基，R3 表示-CH2-或-C(CH3)2-基，此外，m+n表示6〜30之整數） 較佳為單官能單體(A)為乙烯基己内醯胺、（甲基）丙烯酸 苄酯、及（曱基）丙烯酸異葙酯之混合單體，本發明之活性能 量射線硬化型喷墨油墨組成物於油墨組成物中分別以50質 量％〜90質量％之比例含有該混合單體，以0.5質量％〜10 質量％之比例含有二（曱基）丙烯酸酯體(B)，以0.5質量％〜 30質量％之比例含有單體(C)，以5質量％〜15質量％之比 例含有活性能量射線聚合起始劑(D)。 本發明之活性能量射線硬化型喷墨油墨組成物較佳為進 一步含有有色材料。 本發明之附有圖樣之熱可塑性樹脂片材係將活性能量射 線硬化型喷墨油墨組成物列印於熱可塑性樹脂片材上，進行 活性能量射線硬化以形成圖樣而獲得者；該活性能量射線硬 化型喷墨油墨組成物至少含有：自乙烯基己内醯胺、（曱基) 丙烯酸苄酯、及（甲基）丙烯酸異搐酯中選擇之1種或2種以 上之單官能單體(A);上述通式（1)所示之雙酚A環氧烷改質 物之二（曱基）丙烯酸酯體(B);自（甲基）丙烯酸2-羥基-3-苯氧 099140501 5 201124482 基丙酉曰、（甲基）丙烯酸4_第三丁基環己酷、（甲基)丙稀酸苯 氧基乙S旨中選擇之1種或2種以上之單體(Q ;活性能量射 線聚合起始劑(D);及有色材料。 於150C之環i兄下、以應變速度％ 進行延伸時之 本啦明之附有圖樣之熱可塑性樹脂片材之較佳拉伸斷裂點 應變為150%以上。 ， 上述熱可塑性樹脂片材較佳為自丙烯酸系樹脂片材、聚礙 酸醋樹脂片材、聚氣乙埽樹脂片材、娜樹脂片材、及聚 苯乙烯樹脂片材中選擇。 再者於本心a月中’於（甲基）丙稀酸醋之情形時，係指甲 基丙烯酸酯或丙烯酸酯。 (發明效果） 本發明之錄能讀線硬化㈣墨記錄用油墨組成物能 夠於丙烯酸樹脂片材或聚碳酸酯樹脂片材等熱可塑性樹脂 片材上，尤其疋於無處理層之情況下直接進行列印。本發明 之附有圖樣之熱可塑性樹脂片材不會由於熱成型引起之白 化現象而損及圖樣外觀。因此，本發明之附有圖樣之熱可塑 性樹脂片材即便於如成型品樣品般以小批次進行生產，圖樣 之製作實質上亦無需版費，而減輕初期投資之負擔。 【實施方式】 本發明之活性能量射線硬化型喷墨記錄用油墨組成物（以 下，亦稱為油墨組成物)含有以下成分作為必須成分：作為 099140501 6 201124482 具有乙烯性不飽和雙鍵之化合物之自乙烯基己内醯胺、（甲 基）丙烯酸苄酯、（曱基）丙烯酸異萡酯中選擇之1種或2種以 上之單官能單體(A);上述通式（1)所示之雙酚A環氧烷改質 物之二（曱基）丙烯酸酯體(B);及自（曱基）丙烯酸2-羥基-3-苯氧基丙酯、（甲基）丙烯酸4-第三丁基環己酯、（曱基）丙烯 酸苯氧基乙酯中選擇之1種或2種以上之單體(C)。 單官能單體（A)為自乙烯基己内醯胺、（甲基）丙烯酸苄 酯、（曱基）丙烯酸異萡酯中選擇之1種或2種以上，含有其 之目的在於提昇對於熱可塑性樹脂片材之列印性及密接 性。構成適於熱成型之熱可塑性樹脂片材之樹脂之具體例為 聚甲基丙烯酸甲酯（PMMA)、聚碳酸酯（PC)、丙烯腈-丁二烯 -苯乙烯樹脂(ABS樹脂）、聚氯乙烯樹脂。包含任一種樹脂 之片材之列印性及密接性均優異。為獲得具有廣泛使用性之 油墨組成物，而適當組合乙烯基己内醯胺、（曱基）丙烯酸苄 酯及（曱基）丙烯酸異萡酯之3種單官能單體。於組合使用3 種單官能單體之情形時，較佳為於油墨組成物中以1〇質量 %〜40質量％之比例含有乙烯基己内醯胺，以0.5質量％〜 30質量％之比例含有（曱基）丙烯酸苄酯，以10質量％〜60 質量％之比例含有（曱基）丙烯酸異萡酯，3種單官能單體之 較佳總含量相對於油墨組成物為50質量％〜90質量％。若 該總含量少於50質量％，則有如下之虞：油墨組成物之列 印性及密接性下降，失去其廣泛使用性，藉由油墨組成物形 099140501 7 201124482 成圖樣之附有圖樣之熱可塑性樹脂η从 树月曰片材之拉伸斷裂點應變 變低，其加工性產生問題。對成型用蚪女㈤此 丁取1用附有圖樣之熱可塑性樹 脂片材而言’熱延伸性為重要的，於 於150C之％境下、以應 變速度50 mm/min進行延伸時之該附有圖叙熱可塑性樹 脂片材之較佳伸斷裂點應變(以下，稱為拉伸應變量)為 15〇%〜400%。若錄伸應變量過低，咖有圖樣之熱可塑 性樹脂片材之加工性變差。 其次’上述通式⑴㈣m環魏改f物之二斤基) 丙雜體⑻(以下’稱為二(甲基)丙烯酸醋體⑽可作為 與各種單體之交雜成分而辭塗賴度，並且提昇油墨組 成物對各録材之，陳及密接性，可在㈣及藉由油墨組 成物而形成圖樣之附有圖樣之熱可塑性樹脂片材之拉伸後 的外觀之情況下提高拉伸應變量。歧之二（甲基）丙稀酸醋 體W於油墨組成物中較佳為含有Q5〜i5質量％，更佳為含 有1〜1〇質量％。若該二（甲基）丙稀酸酯體⑻之含量過多， 則有如下之虞··油墨組成物之形卩性及密接性下降，失去其 廣泛使用性’藉由油墨組成物而形成圖樣之附有圖樣之熱可 f性樹脂片材之拉伸斷裂點應變變低，其加卫性產生問題。 右一（甲基）内烯酸醋體⑻之E〇加成量未達^莫耳，則有油 墨=成^形卩性及密接性下降之虞。2官能之丙烯酸胺基BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable black ink black composition and a thermographic resin sheet with a pattern suitable for thermoforming. [Prior Art] It is known that a thermoplastic resin sheet with a pattern attached is formed by pattern printing using a plate, for example, by gravure printing or screen printing means on a thin plastic substrate or a sheet-like plastic substrate. Manufacturing. However, in Patent Document 1, it has the following problem: even in the case of large-scale production, the proportion of the cost per molding product is extremely small, as in the case of dh production such as the production of a molded article. At the time of the introduction, the cost of each molded product will become large, and as the initial investment in formal production (large batch), the cost burden of the manufacturer will become excessive. On the other hand, a method of printing a pattern is known as an ink jet method, and an ink composition of a bismuth agent or a hydrazine is also proposed. However, as a printing substrate, it is usually limited to σ At to absorb a certain degree of solvent or water. In the case of a substrate, for example, when a thermoplastic resin sheet which can be molded such as an acrylic resin sheet or a polycarbonate resin sheet is used as a printing substrate, a step of providing a receiving layer or the like is required. The active energy ray-curable ink composition which can be adhered to some extent to the thermoplastic resin sheet which can be formed is described in Patent Document 2 to Patent Document 4, but is bent or pulled during thermoforming after hardening. Stretching and other steps cause problems such as cracking or whitening of the formed pattern. [Patent Document 1] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. An active energy ray-curable inkjet ink which can be directly printed and has excellent adhesion, and the object of the invention is to provide a thermoplastic resin sheet with a pattern which is to be formed by the ink composition. The pattern is printed on the thermoplastic resin material and hardened. Even if the material is thermoformed, it will not cause cracking or whitening phenomenon. (Means for Solving the Problem) The active energy ray hardening type inkjet ink composition of the present invention contains at least: from the group of ethyl phthalamide, (mercapto) acrylic acid, and (meth) acrylic acid One or two or more kinds of monofunctional monomers (Α) selected; the bis(indenyl) acrylate body (B) of the bisphenol fluorene oxide modified product of the following formula (1); Methyl)acrylic acid 2_ylidyl-3-phenoxypropyl-, (meth)acrylic acid 4-second butyl hexyl, (fluorenyl) phenoxy acrylate Or two or more kinds of monomers (C); and an active energy ray polymerization initiator (9). 099140501 4 201124482 Η匕i] General formula (l) = CK-, R1 R2 /r^ __s R2 R ' :=c—^i4"OCH2CH t° fly ///of^Q^oj^cc (in the formula, R1 Represents hydrogen or a fluorenyl group, R2 represents hydrogen, fluorenyl or /ethyl, R3 represents -CH2- or -C(CH3)2- group, and m+n represents an integer of from 6 to 30. Preferably, a monofunctional single The body (A) is a mixed monomer of vinyl caprolactam, benzyl (meth)acrylate, and isodecyl (mercapto)acrylate, and the active energy ray-curable inkjet ink composition of the present invention is composed of ink. The mixed monomer is contained in an amount of 50% by mass to 90% by mass, and the bis(indenyl)acrylate body (B) is contained in an amount of 0.5% by mass to 10% by mass, and is 0.5% by mass to 30% by mass. The ratio contains the monomer (C), and the active energy ray polymerization initiator (D) is contained in a proportion of 5 mass% to 15 mass%. The active energy ray-curable inkjet ink composition of the present invention preferably further contains a colored material. The patterned thermoplastic resin sheet of the present invention is obtained by printing an active energy ray-curable inkjet ink composition on a thermoplastic resin sheet and performing active energy ray hardening to form a pattern; the active energy ray The curable inkjet ink composition contains at least one or more monofunctional monomers selected from the group consisting of vinyl caprolactam, benzyl (meth) acrylate, and isodecyl (meth) acrylate ( A); a bis(indenyl) acrylate body of the bisphenol A alkylene oxide modified substance represented by the above formula (1); (B); from 2-(hydroxy)acrylic acid 2-hydroxy-3-phenyloxy 099140501 5 201124482 One or two or more monomers selected from the group consisting of propylene ketone, (meth)acrylic acid 4_t-butylcyclohexanyl, (meth)acrylic acid phenoxy ethane S (Q; active energy) The radiation polymerization initiator (D); and the colored material. The preferred tensile fracture point strain of the thermoplastic resin sheet with the pattern attached to the strain at the strain rate % under the 150C ring 150% or more. The above thermoplastic resin sheet is preferably a sheet from an acrylic resin sheet. It is selected from the sheet of acid vinegar resin, the sheet of gas-filled acetarene resin, the sheet of enamel resin, and the sheet of polystyrene resin. In addition, in the case of "the (meth) acrylate vinegar in the heart of the month The invention relates to a methacrylic acid ester or an acrylate. (Effect of the invention) The ink-recording line hardening (IV) ink composition for ink recording of the present invention can be used for a thermoplastic resin sheet such as an acrylic resin sheet or a polycarbonate resin sheet. In the above, the printing is directly carried out in the case of no treatment layer. The thermoplastic resin sheet with the pattern of the present invention does not impair the appearance of the pattern due to whitening caused by thermoforming. Therefore, the present invention is attached. The patterned thermoplastic resin sheet is produced in a small batch as in the case of a molded article, and the production of the pattern substantially does not require a plate fee, thereby reducing the burden of initial investment. [Embodiment] The active energy ray-curing type of the present invention The ink composition for inkjet recording (hereinafter also referred to as an ink composition) contains the following components as essential components: as a compound having an ethylenically unsaturated double bond as 099140501 6 201124482 One or two or more kinds of monofunctional monomers (A) selected from the group consisting of vinyl caprolactam, benzyl (meth)acrylate, and isodecyl (mercapto)acrylate; represented by the above formula (1) Bis(A) acrylate acrylate (B); and 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-(meth) acrylate 4-third One or two or more monomers (C) selected from butylcyclohexyl ester and phenoxyethyl (meth) acrylate. Monofunctional monomer (A) is self-vinyl caprolactam, (A) One or two or more selected from the group consisting of benzyl acrylate and isodecyl acrylate, and the purpose thereof is to improve the printability and adhesion to the thermoplastic resin sheet. Specific examples of the resin of the thermoplastic resin sheet are polymethyl methacrylate (PMMA), polycarbonate (PC), acrylonitrile-butadiene-styrene resin (ABS resin), and polyvinyl chloride resin. The sheet containing any of the resins is excellent in printability and adhesion. In order to obtain an ink composition having wide applicability, three kinds of monofunctional monomers of vinyl caprolactam, benzyl (meth) acrylate and isodecyl (mercapto) acrylate are appropriately combined. When three kinds of monofunctional monomers are used in combination, it is preferred to contain vinyl caprolactam in a ratio of from 1% by mass to 40% by mass in the ink composition, and the ratio is from 0.5% by mass to 30% by mass. Benzyl (meth) acrylate is contained, and isodecyl acrylate is contained in a proportion of 10% by mass to 60% by mass, and the total content of the three monofunctional monomers is 50% by mass based on the ink composition. 90% by mass. If the total content is less than 50% by mass, there is a defect that the printing property and the adhesion of the ink composition are lowered, and the wide-use property is lost, and the pattern of the ink composition is 099140501 7 201124482. The thermoplastic resin η has a low strain at the tensile breaking point of the sapphire sheet, and has a problem in workability. For the forming prostitute (5), the ferrule 1 is made of a thermoplastic resin sheet with a pattern, and the thermal extensibility is important. When the strain is 50 mm/min, the elongation is performed at a strain rate of 50 mm/min. The preferred tensile breaking point strain (hereinafter, referred to as tensile strain) of the thermoplastic resin sheet attached is shown to be 15% to 400%. If the recording strain is too low, the processability of the hot plastic resin sheet having a pattern is deteriorated. Next, 'the above formula (1) (four) m ring Wei modified f ji ji ji) propylene (8) (hereinafter referred to as bis (meth) acrylate vinegar (10) can be used as a cross-linking component with various monomers, Further, the ink composition is improved in adhesion to each of the recording materials, and the stretching can be improved in the case of (4) and the stretched appearance of the patterned thermoplastic resin sheet formed by the ink composition. The amount of the di(meth)acrylic acid vinegar W in the ink composition preferably contains Q5 to i5 mass%, more preferably 1 to 1 mass%. If the di(meth)propyl group When the content of the dilute acid ester (8) is too large, the following is the case where the ink composition is inferior in shape and adhesion, and the wide-ranging property is lost, and the heat of the pattern formed by the ink composition is attached. The strain at the tensile break point of the resin sheet becomes low, and the susceptibility of the resin sheet is problematic. The amount of E 〇 addition of the right (methyl) olefinic vinegar body (8) is less than that of the molar, then there is ink = Cheng ^ A decrease in shape and adhesion. A 2-functional acrylate group
盥涌、等一（甲基）丙烯酸酯可作為二（P基）丙烯酸酯體(B) ”式⑴所不者併用。若二（甲基）丙烯酸S旨體並非雙酚A 099140501 201124482 %氧烧改質物’而係新戍·一醇之環氧炫改質物’則可提高於 由油墨組成物而形成圖樣之附有圖樣之熱可塑性樹脂片材 之拉伸應變量，但該附有圖樣之熱可塑性樹脂片材拉伸後產 生白化專現象。藉由油墨組成物而形成圖樣之附有圖樣之熱 可塑性樹脂片材必須熱成型性優異而不產生延伸後之白化 現象。 一（曱基）丙烯酸酯體(B)為上述通式（1)所示之雙齡a環氧 烷改質物，環氧烷之加成莫耳數(m+n)為6〜3〇，較佳為⑺ 莫耳一（曱基）丙細酸醋體(B)之具體例為雙g分a之環 氧烧(EO)1〇莫耳加成改質物（共榮社化學製）、雙紛a之 E〇2〇莫耳加成改質物（新中村化學工業公司製）、雙酚a之 EO30莫耳加成改質物(新中村化學工業公司製）。 第二稀酸2’基苯氧基丙醋、(甲基Μ烯酸4- 2種以I:。：(甲基)兩烯酸苯氧基乙醋中選擇之1種或 早體(C)可提昇油墨組成物對各種_基材之列 印性及密触，並且以較之躲㈣触。^ 油墨組錢*較佳為含有i〜3。質量%，更佳為人二〜7; 質量％。㈣含量過多’則藉由油墨組成物:3〜 有圖樣之射難_旨料之 彡®樣之附 對各種_基材之科性及龍打降降，组成物 本發明之㈣組成物可含有習知之油 常使用之無機顏料赤亡^由墨組成物中通 “科或有機綱作為衫㈣(顏 099140501 〆’ 9 201124482 具體例為碳黑、鎘紅、鉬紅、鉻黃、鎘黃、鈦黃、 鉻綠、鈦㈣、群青藍、普魯士藍、錄藍、二叫比洛并/ 洛、葱酿、苯并味销、葱射、偶氮系顏料、敗青比 系顏料、異系顏料、二辦系顏^陰丹 士林糸顏料、B顏料、派瑞酮系顏料、硫彀藍系顏料 駄 3同糸顏料、金屬錯合物顏料。 顏料一次粒子之較佳體籍i|L的私^ ^ 顆積千均粒㈣用雷射散射所 之值為50〜20G nm。於顏料之平均粒徑未達％她 時’會由於粒徑變小而產生耐光性下降。另—方面，於^過 200 nm之情形時，難以維持分散之安定性，易於產生顏料 之沉殿。顏料係視需要而進行添加，其相對於油墨組成物之 含量較佳為3G質量％以下，更佳為25 f量％以下 2 20質量％以下。 、為 本發明之油墨組成物可含有高分子分散劑作為分散劑4 分子分散劑之主鏈包括聚酯系、聚丙烯酸系、聚胺基甲酸阿 酯系、聚胺系、聚己内酯系等，高分子分散劑具有胺基二乙 基、砜基、羥基等極性基作為侧鏈。較佳之高分子分散、羧 聚醋糸分散劑’其具體例為曰本Lubrizol公司製造' 「SOLSPERSE33000」、「SOLSPERSE32000 J Λ 「SOLSPERSE24000」；BYK Chemie 公司製造之 「DisperBYK168」；Ajinomoto Fine-Techno 公司製造之 「Ajisper PB821」。高分子分散劑以相對於顏料1質量份車交 099140501 10 201124482 佳為0.03質量份〜5質量份、更佳為0.05質量份〜5質量份 之比例添加。高分子分散劑於油墨組成物中較佳為含有〇1 質量％〜30質量％，更佳為含有〇·5質量％〜20質量％。 其次，對於本發明之活性能量射線硬化型噴墨記錄用油墨 組成物所含有之光聚合起始劑進行説明。本發明中之活性能 量射線係表示電子射線、紫外線、紅外線等自由基、陽離子、 陰離子等可成為聚合反應之誘因的能量射線。光聚合起始劑 之具體例為屬於醯基氧化膦之雙(2,4,6-三曱基苯甲醯基)_苯 基-氧化膦(1^&〇1^819、（：比3】&卩&11公司製）、雙(2,6-二甲氧 基苯曱醯基)-2,4,4-三曱基-戊基苯基氧化膦、2,4,6-三曱基苯 曱醯基-二苯基-氧化膦(Darocur TPO : Ciba Japan公司製； Lucirin TPO : BASF 公司製）。 用作光聚合起始劑之α -羥基酮之具體例為2-羥基 -1-{4-[4-(2-經基-2-甲基-丙酸基)-节基]-苯基}-2-曱基-丙烧 -卜酮（Irgacure 127、Ciba Japan公司製）、2-經基-4’-經基乙氧 基-2-曱基苯丙酮(Irgacure 2959、Ciba Japan 公司製）。 用作光聚合起始劑之α -胺基烷基苯酮之具體例為2-苄基 -2-二甲基胺基_1-(4-嗎啉基苯基)-丁酮-l(Irgacure 369、Ciba Japan公司製）。 用作光聚合起始劑之苯基酮之具體例為1 -環己基苯基酮 (Irgacure 184、Ciba Japan 公司製）。 本發明之活性能量射線硬化型噴墨記錄用油墨組成物可 099140501 11 201124482 含有表面調整劑。表面調整劑之具體例為聚醚改質二甲基聚 石夕氧烧末端丙烯酸酯化物(TegoRao2300、degussa公司製）。 表面調整劑相對於油墨組成物之較佳含有比例為0.1〜0.3 質量％。 本發明之活性能量射線硬化型喷墨油墨組成物此外可含 有塑化劑、紫外線抑制劑、光安定化劑、抗氧化劑等各種添 加劑。 本發明之活性能量射線硬化型喷墨油墨組成物係將顏料 與單體、顏料分散劑一同藉由砂磨機等通常之分散機進行分 散而製造。預先製作顏料高濃度之濃縮液，將該濃縮液以單 體加以稀釋。藉由通常之分散機可進行充分之分散，而調製 安定性優異之油墨。將油墨利用孔徑較佳為3以下、更 佳為1//以下之過濾器進行過遽。 本發明之活性能量射線硬化型喷墨油墨組成物於4〇ΐ之 較佳黏度為5〜2〇 mPa · s。於該黏度過低之情形時，高頻 喷頭之吐出之追隨性下降。另一方面，於該黏度過高之情形 時，即便將藉由加熱而使黏度下降之機構組裴入噴頭中，亦 會產生吐出下降，吐出之安定性變得不良，無法完全吐出油 墨組成物。 將本發明之活性能量射線硬化型噴墨油墨組成物供給至 喷墨記錄方式用印表機之列印頭，自該列印頭吐出至基材 上，其後照射紫外線、電子射線等活性能量射線，使其於印 099140501 12 201124482 刷媒體上迅速地硬化。 作為活性能直射線之紫外線之光源之具體例為高壓水銀 燈、金屬商素燈、低壓水銀燈、超高壓水銀燈、紫外線雷射、 太陽光。於電子射線為活性能量射線之情形時，通常照射 300 eV以下之能量之電子射線，但本發明之活性能量射線 硬化型喷墨油墨組成物以1〜5 Mrad之照射量即可瞬時硬 化。 藉由本發明之活性能量射線硬化型喷墨油墨組成物而形 成圖樣之較佳印刷基材為丙烯酸系樹脂製、聚碳酸酯樹脂 製、聚苯乙燦樹脂製、聚氣乙稀樹脂製等包含油墨非吸收性 樹脂之印刷基材。該等印刷基材由後述之密接性試驗可知， 係顯示出優異之密接性。 以下，列舉貫施例來具體地說明本發明，但本發明並不特 別限定於實施例。再者，實施例中之「份」表示「質量份」。 [實施例] [實施例1] [分散體之製備] 將下述表中之比例之高分子分散劑（SOLSPERSE33000、 曰本Lubrizol公司製）溶解於丙烯酸苄酯（viscoat# 160、大 阪有機化學工業公司製）中，接著添加下述表中之比例之黃 色顏料(E4GN-GT、Lanxess公司製）’藉由塗料振盪器進行 分散而使顏料粒徑（中徑）成為200 nm以下，獲得分散體。 099140501 13 201124482 粒徑係以HOLIBA公司製造之「LB-55〇」測定。 將表1及表2所示之原料除分散體以外依序進行混合，一 面加溫至50°C —面攪拌1小時，確認無溶解殘留，恢復至 室溫後’添加分散體進行攪拌。其後，利用薄膜過渡器進行 過遽’製作實施例1之油墨。 [實施例2〜5、比較例1〜比較例4] 實施例2〜5、比較例2〜比較例4，係使用表1及表2所 示之顏料、分散劑，與實施例1同樣地製作分散體，除此以 外，係利用與實施例1相同之方式製作各油墨。再者，比較 例1中之分散體係使用丙烯酸苯氧基乙酯代替實施例丨之丙 烯酸苄酯而同樣地製作’除此以外，係利用與實施例丨相同 之方式製作比較例1之油墨。 將獲得之各油墨利用棒式塗佈機#8以平均膜厚達到 /zm之方式展色於各基材上。其後，使用高壓水銀燈 (HAL250NL) ’ 以累計光量· 112.63 mJ/cm2(UV-351)、波峰 照度：I34.43 mW/cm2(uv-35i)、輸出：8〇 w/cm、搬送速 度m/mhl之條件使其硬化。結果根據下述評估方法進 行判斷。 ⑴黏度 油墨之黏度係基於JIS K71m，使用B型黏度計於4代 進行測定。 (2)密接性 099140501 14 201124482 如ASTM D3359所規定，將玻璃紙膠帶黏貼於將硬化後 之塗膜以1 mm間隔交叉切割為1〇〇格之部分，充分地密接 後，將玻璃紙膠帶以90度剝離，根據此時塗膜對基材之密 接程度而判斷密接性。判斷基準如下所述。 5B :無剝離。 4B :有未達5%之剝離。 3B :有5%以上而未達15%之剝離。 2B :有15%以上而未達35%之剝離。 1B :有35%以上而未達65%之剝離。 0B :有65%以上之剝離。 (3) 拉伸應變量 將各油墨組成物利用棒式塗佈機#8以平均膜厚達到18 μ m之方式塗佈於PMMA基材(厚度2 mm、Acrylite EX、 二菱麗％公司製）上，製作附有圖樣之熱可塑性樹脂片材。 將δ亥附有圖樣之熱可塑性樹脂片材利用衝壓機公 司製）連同基材一起衝壓成條狀，板據K7U3，利用 T—UCT-IT ; ORIENTEC公司製）將獲得之試片加敎至 15叱，以應變速度5G mm/min連同基材—起進行拉伸試 驗。塗膜之破SfH緒以目視確認_表面破裂時之伸長成 為百分比(％)而進行測定。 (4) 延伸後外觀 藉由目視絲據下絲準評估卩时圖狀熱可塑性樹脂 099140501 15 201124482 片材之延伸後外觀。 A :無白化 B :稍白化 C :明顯白化 表1〜4中之1)〜28)如下所述。 1) : E4GN-GT(Lanxess 公司製） 2) : CINQUASIA MAGENTA RT-355D(Ciba Japan 公 3) : LIONOLBLUEFG7400G(東洋油墨製造公 3^·) 1製） 4) : CARBON BLACK #MA-14(三菱化學公 d 5) : CFR6121EC(大日精化公司製） 6) : V-CAP/RC(ISP Japan 公司製） 7) : Viscoat# 160(大阪有機化學工業公司製） 8) : Light Acrylate IBXA(共榮社化學公司製） 9) : NK Ester 702A(新中村化學工業公司製） 10) : Laromer TBCH(BASF 公司製） 11) : Light Acrylate PO-A(共榮社化學公司製） 12) : Light Acrylate BP-10ΕΑ(共榮社化學公幻製） 13) : NKEsterA-BPE-20(新中村化學工業公幻製） 14) : NK Ester A-BPE-30(新中村化學工業公豸製） 15) : Light Acrylate BP_4EA(共榮社化學公豸製） 16) : SR9045(SARTOMER 公司製） 17) : CN996(SARTOMER 公司製） 099140501 16 201124482 18) : Irgacure 184(1-環己基苯基酮、Ciba Japan 公司製） 19) : Lucirin TPO(二苯基_(2,4,6_三曱基苯甲醯基）氧化 膦、BASF公司製） 20) : Irgacure 369(2-苄基-2二曱基胺基-1-(4-嗎琳基苯基) 丁酮-1、Ciba Japan 公司製） 21) : DisperBYK168(BYK Chemie 公司製） 22) : SOLSPERSE33000(曰本 Lubrizol 公司製） 23) : TegoRad 2300(degussa 公司製） 24) : Acrylite EX(三菱麗陽公司製、膜厚2.0 mm) 25) :聚碳酸醋板(Takiron公司製、膜厚2.0 mm) 26) : Carbo Glass Twin Carbo 9034-30(AGC 旭石肖子公司 製、膜厚4.0 mm) 27) : ABS 板 Natural(Takiron 公司製、膜厚 2.0 mm) 28) : S640(Takiron 公司製、膜厚 2.0 mm) 表1及2中之數值之單位為質量％，表面調整劑之添加率 為相對於油墨組成物之添加率。 099140501 17 201124482 [表i] 實施例 實施例 實施例 實施例 實施例 1 2 3 4 5 ΡΥ 150° 3.6 - - - - PV 19. PR 2022) - 4.0 - - - PB 15:43) - - 2.4 - - 碳黑4) - - - 2.1 - PR 1775) - - - - 3.6 N-乙烯基己内醯胺6) 20.0 20. 0 20. 0 20.0 20. 0 丙烯酸苄醋7) 12.6 14.4 11.2 12.6 12.0 丙烯酸異萡酯8> 43.0 28.0 34.0 27.2 20.0 丙烯酸2-羥基-3-苯氧基丙酯9) - 20.0 15.0 20.0 - 丙烯酸4-第三丁基環己酯⑼ - - - - 19.8 丙烯酸苯氧基乙酯n) 5.0 - - - - 雙酚A二丙烯酸酯(EO10莫耳改質）12) - 4.0 - - - 雙酚A二丙烯酸酯(EO20莫耳改質）13) 6.0 - - - 4.0 雙酚A二丙烯酸酯(E〇3〇莫耳改質）14) - - 6.0 7.0 - 雙酚A二丙烯酸酯(E04莫耳改質）15) - - - - - 新戊二醇二丙烯酸酯(PO改質）16) - - - - - 2-官能丙烯酸胺基甲酸乙酯17> - - - - 5.0 Irgacure 18418) 2.0 2.0 2.5 2.5 2.5 Lucirin ΤΡ019) 2.0 3.0 2.0 2.0 2.0 Irgacure 3 6 920) 4.0 3.0 4.5 4.5 4.5 DisperBYK 1682° - - 2.4 2.1 6.6 SOLSPERSE 3300022) 1.8 1.6 - - - TegoRad 230023) 0.2 0.2 0.2 0.2 0.2 18 099140501 201124482 [表2] 比較例 1 比較例 2 比較例 3 比較例 4 ΡΥ 150υ - - - - PV 19. PR 2022) 4.0 4.0 4.0 4.0 PB 15:43) - - - - 碳黑4) - - - - PR 1775) - - - - N-乙烯基己内醯胺6) - 20. 0 20. 0 20. 0 丙稀酸节醋7) - 14.4 14.4 14.4 丙烯酸異葙酯8) - 32.0 28.0 28.0 丙烯酸2-羥基-3-苯氧基丙酯9) 20.0 20.0 20.0 20.0 丙烯酸4-第三丁基環己酯lfl) - - - - 丙烯酸苯氧基乙酯n) 62.4 - - - 雙酚A二丙烯酸酯(EO10莫耳改質）|2) 4.0 - - - 雙酚A二丙烯酸酯(EO20莫耳改質）13) - - - - 雙酚A二丙烯酸酯(EO30莫耳改質）|4) - - - - 雙酚A二丙烯酸酯(E04莫耳改質）15> - - - 4.0 新戊二醇二丙烯酸酯(PO改質）16) - - 4.0 - 2-官能丙烯酸胺基甲酸乙酯17) - - - - Irgacure 18418) 2.0 2.0 2.0 I 2.0 Lucirin ΤΡ019) 3.0 3.0 3.0 3.0 Irgacure 36920)- 3. 0 3. 0 3. 0 3.0 DisperBYK 16821) - - - - SOLSPERSE 3 3 0 0 022) 1.6 1.6 1.6 1.6 TegoRad 230023) 0.2 0.2 0.2 0.2 19 099140501 201124482 [表3]A turbid, iso-(meth) acrylate can be used as a di(P-based) acrylate body (B) "(1). If the bis(meth)acrylic acid S is not a bisphenol A 099140501 201124482% oxygen Burning the modified substance 'and the new epoxy resin modified by the alcohol' can improve the tensile strain of the patterned thermoplastic resin sheet formed by the ink composition, but the pattern is attached. The thermoplastic resin sheet is stretched to produce a whitening phenomenon. The thermoplastic resin sheet with a pattern formed by the ink composition is excellent in thermoformability without causing whitening after stretching. The acrylate body (B) is a two-year-old alkylene oxide modified product represented by the above formula (1), and the molar number (m+n) of the alkylene oxide is 6 to 3 Å, preferably (7). A specific example of a molar (A) thiocyanate (B) is an epoxy burned (EO) 1 〇 Moer addition modified product (manufactured by Kyoeisha Chemical Co., Ltd.) E〇2〇Moer Addition Modified (made by Shin-Nakamura Chemical Industry Co., Ltd.), EO30 Moer Addition of Bisphenol A (Xinzhongcun Chemical Industry Co., Ltd.) The second dilute acid 2' phenoxy propyl vinegar, (methyl 4-decenoic acid 4- 2 kinds of I:: (meth) enoic acid phenoxy vinegar selected one or early body (C) can improve the printing and contact of the ink composition on various _substrate, and to hide (four) touch. ^ Ink group money * preferably contains i ~ 3. mass%, better for people two ~7; mass %. (4) excessive content 'by ink composition: 3~ there is a pattern of difficult to shoot _ the purpose of the 彡 样 样 样 样 _ _ _ _ _ _ _ _ _ _ _ _ _ 基材 基材(4) The composition of the invention may contain an inorganic pigment which is commonly used in conventional oils, and is red-brown. The composition of the ink is passed through the "organic or organic class as a shirt (4) (Yan 099140501 〆' 9 201124482 specific examples are carbon black, cadmium red, molybdenum red , chrome yellow, cadmium yellow, titanium yellow, chrome green, titanium (four), ultramarine blue, Prussian blue, recorded blue, two called biluo / Luo, onion, benzo flavor, onion, azo pigment, defeat Cyan pigments, meta-pigments, two-lined yin yin yin yin pigment, B pigment, pyridone pigment, sulphur indigo pigment 駄 3 糸 pigment, metal complex pigment. The preferred body of the child i|L is a private ^ ^ product of a thousand particles (4) with a laser scattering value of 50~20G nm. When the average particle size of the pigment is less than %, she will become smaller due to the smaller particle size. In addition, when the temperature is over 200 nm, it is difficult to maintain the stability of dispersion, and it is easy to produce a sink of pigment. The pigment is added as needed, and the content of the ink composition is relatively higher than that of the ink composition. It is preferably 3 G% by mass or less, more preferably 25 f% by weight or less and 2 20% by mass or less. The ink composition of the present invention may contain a polymer dispersant as a dispersing agent. The main chain of the molecular dispersing agent includes a polyester system. A polyacrylic acid type, a polyurethane type, a polyamine type, a polycaprolactone type, etc., and a polymer dispersing agent has a polar group, such as an amino-ethyl group, a sulfone group, and a hydroxyl group, as a side chain. A preferred example of polymer dispersing and carboxypolyacetate dispersing agent is 'SOLSPERSE 33000', 'SOLSPERSE 32000 J Λ 'SOLSPERSE 24000', and 'Disper BYK 168' manufactured by BYK Chemie; manufactured by Ajinomoto Fine-Techno "Ajisper PB821". The polymer dispersant is added in a ratio of 0.03 parts by mass to 5 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, per part by mass of the pigment, 099140501 10 201124482. The polymer dispersant preferably contains 〇1% by mass to 30% by mass, more preferably 〇55% by mass to 20% by mass, based on the ink composition. Next, the photopolymerization initiator contained in the active energy ray-curable inkjet recording ink composition of the present invention will be described. The active energy ray system in the present invention is an energy ray which can cause a polymerization reaction, such as an electron beam, an ultraviolet ray, or an infrared ray, such as a radical, a cation or an anion. A specific example of the photopolymerization initiator is bis(2,4,6-trimercaptobenzylidene)-phenyl-phosphine oxide belonging to fluorenylphosphine oxide (1^&〇1^819, (: ratio 3]&卩&11 company), bis(2,6-dimethoxybenzoinyl)-2,4,4-tridecyl-pentylphenylphosphine oxide, 2,4,6 - Trimethyl phenyl fluorenyl-diphenyl-phosphine oxide (Darocur TPO: manufactured by Ciba Japan Co., Ltd.; Lucirin TPO: manufactured by BASF Corporation). Specific examples of α-hydroxyketone used as a photopolymerization initiator are 2- Hydroxy-1-{4-[4-(2-transyl-2-methyl-propionyl)-]]phenyl]-2-indenyl-propanone-propanone (Irgacure 127, Ciba Japan) Company, 2-Phosyl-4'-transethoxyethoxy-2-mercaptopropiophenone (Irgacure 2959, manufactured by Ciba Japan Co., Ltd.). α-Aminoalkylphenone used as a photopolymerization initiator A specific example is 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (Irgacure 369, manufactured by Ciba Japan Co., Ltd.). A specific example of the phenyl ketone is 1-cyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.). The active energy ray-curable inkjet recording ink composition of the present invention can be 0991. 40501 11 201124482 A surface conditioning agent is contained. A specific example of the surface conditioning agent is a polyether modified dimethyl polysulfide oxyalkylated terminal acrylate (TegoRao 2300, manufactured by Degussa Co., Ltd.). The surface conditioning agent is preferred over the ink composition. The active energy ray-curable inkjet ink composition of the present invention may further contain various additives such as a plasticizer, an ultraviolet inhibitor, a light stabilizer, an antioxidant, etc. The active energy ray of the present invention. The curable inkjet ink composition is produced by dispersing a pigment together with a monomer or a pigment dispersant by a usual disperser such as a sand mill. A concentrate having a high concentration of a pigment is prepared in advance, and the concentrate is subjected to a monomer. The ink can be sufficiently dispersed by a usual dispersing machine to prepare an ink excellent in stability. The ink is dried by a filter having a pore diameter of preferably 3 or less, more preferably 1// or less. The energy ray-curable inkjet ink composition has a preferred viscosity of 5 〇 2 〇 mPa · s at 4 Torr. When the viscosity is too low, the high frequency nozzle On the other hand, when the viscosity is too high, even if the mechanism group which reduces the viscosity by heating is thrown into the head, the discharge is lowered, and the stability of the discharge is poor. The ink composition of the inkjet recording type inkjet ink of the present invention is supplied to the head of the inkjet recording type printer, and is discharged from the printing head onto the substrate, and then irradiated with ultraviolet rays. Active energy rays such as electron beams are rapidly hardened on the printing medium of 099140501 12 201124482. Specific examples of the light source of the ultraviolet rays which are active direct rays are a high pressure mercury lamp, a metal commercial lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet laser, and sunlight. In the case where the electron beam is an active energy ray, an electron beam of an energy of 300 eV or less is usually irradiated, but the active energy ray-curable inkjet ink composition of the present invention can be instantaneously hardened by an irradiation amount of 1 to 5 Mrad. A preferred printing substrate formed by the active energy ray-curable inkjet ink composition of the present invention is made of acrylic resin, polycarbonate resin, polystyrene resin, or polyethylene resin. Printing substrate for ink non-absorbent resin. These printed substrates were found to have excellent adhesion by the adhesion test described later. Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not particularly limited to the examples. Further, the "parts" in the examples mean "parts by mass". [Examples] [Example 1] [Preparation of dispersion] The polymer dispersant (SOLSPERSE 33000, manufactured by Sakamoto Lubrizol Co., Ltd.) in the following table was dissolved in benzyl acrylate (viscoat #160, Osaka Organic Chemical Industry) In the company's product, a yellow pigment (E4GN-GT, manufactured by Lanxess Co., Ltd.) in the following table was added to disperse by a paint shaker to have a pigment particle diameter (medium diameter) of 200 nm or less to obtain a dispersion. . 099140501 13 201124482 The particle size is measured by "LB-55" manufactured by HOLIBA. The materials shown in Tables 1 and 2 were mixed in this order except for the dispersion, and the mixture was heated to 50 ° C on the surface, and the mixture was stirred for 1 hour, and it was confirmed that there was no dissolution residue. After returning to room temperature, the dispersion was added and stirred. Thereafter, the ink of Example 1 was produced by using a film transitioner. [Examples 2 to 5, Comparative Example 1 to Comparative Example 4] Examples 2 to 5 and Comparative Examples 2 to 4 were the same as in Example 1 except that the pigments and dispersants shown in Tables 1 and 2 were used. Each of the inks was produced in the same manner as in Example 1 except that the dispersion was produced. Further, in the dispersion system of Comparative Example 1, the ink of Comparative Example 1 was produced in the same manner as in Example 使用 except that phenoxyethyl acrylate was used instead of benzyl acrylate of the Example. Each of the obtained inks was developed on each substrate by a bar coater #8 so that the average film thickness reached /zm. Thereafter, a high-pressure mercury lamp (HAL250NL) was used to accumulate light amount: 112.63 mJ/cm2 (UV-351), peak illuminance: I34.43 mW/cm2 (uv-35i), output: 8 〇w/cm, and transport speed m The condition of /mhl hardens it. The results were judged according to the following evaluation methods. (1) Viscosity The viscosity of the ink was measured based on JIS K71m using a B-type viscometer in 4th generation. (2) Adhesiveness 099140501 14 201124482 Adhesive cellophane tape is adhered to the hardened film at a 1 mm interval to a portion of 1 inch as specified in ASTM D3359. After sufficient adhesion, the cellophane tape is 90 degrees. Peeling was performed, and the adhesion was judged based on the degree of adhesion of the coating film to the substrate at this time. The judgment criteria are as follows. 5B: No peeling. 4B: There is a peel of less than 5%. 3B: There are more than 5% and less than 15% of the divestiture. 2B: There are more than 15% and less than 35% of the divestiture. 1B: There are more than 35% and less than 65% of the stripping. 0B: There are more than 65% of the stripping. (3) Tensile strain amount Each ink composition was applied to a PMMA substrate by a bar coater #8 with an average film thickness of 18 μm (thickness 2 mm, Acrylite EX, manufactured by Ericsson Co., Ltd.) On the other hand, a thermoplastic resin sheet with a pattern attached thereto was produced. The thermoplastic resin sheet with the pattern attached to δHai was punched into strips together with the substrate, and the obtained test piece was twisted according to K7U3, using T-UCT-IT; manufactured by ORIENTEC Co., Ltd.) 15 叱, tensile test was carried out at a strain rate of 5 G mm/min together with the substrate. The SfH of the coating film was visually confirmed to determine the elongation at the time of surface cracking as a percentage (%). (4) Appearance after extension The visual thermoplastic resin is evaluated by visual inspection according to the wire. 099140501 15 201124482 The appearance of the sheet after extension. A: no whitening B: slightly whitened C: marked whitening 1) to 28) in Tables 1 to 4) are as follows. 1) : E4GN-GT (manufactured by Lanxess) 2) : CINQUASIA MAGENTA RT-355D (Ciba Japan 3) : LIONOLBLUEFG7400G (Toyo Ink Manufacturing Co., Ltd. 3) · 4) : CARBON BLACK #MA-14 (Mitsubishi Chemical public d 5) : CFR6121EC (made by Daisei Seiki Co., Ltd.) 6) : V-CAP/RC (made by ISP Japan) 7) : Viscoat # 160 (made by Osaka Organic Chemical Industry Co., Ltd.) 8) : Light Acrylate IBXA 9): NK Ester 702A (manufactured by Shin-Nakamura Chemical Co., Ltd.) 10) : Laromer TBCH (manufactured by BASF Corporation) 11) : Light Acrylate PO-A (manufactured by Kyoeisha Chemical Co., Ltd.) 12) : Light Acrylate BP-10ΕΑ (Chongrongshe Chemical Puppet System) 13) : NKEsterA-BPE-20 (Xinzhongcun Chemical Industry Public System) 14) : NK Ester A-BPE-30 (Xinzhongcun Chemical Industry Corporation) 15 ) : Light Acrylate BP_4EA (Kyoeisha Chemical Co., Ltd.) 16) : SR9045 (manufactured by SARTOMER Co., Ltd.) 17) : CN996 (manufactured by SARTOMER Co., Ltd.) 099140501 16 201124482 18) : Irgacure 184 (1-cyclohexyl phenyl ketone, Ciba) Japan company) 19) : Lucirin TPO (diphenyl-(2,4,6-trimethyl benzhydryl) phosphine oxide, manufactured by BASF) 20) : Irgacur e 369(2-benzyl-2didecylamino-1-(4-morphinylphenyl)butanone-1, manufactured by Ciba Japan Co., Ltd.) 21) : DisperBYK168 (manufactured by BYK Chemie) 22) : SOLSPERSE33000 (manufactured by Sakamoto Lubrizol Co., Ltd.) 23) : TegoRad 2300 (manufactured by Degussa Co., Ltd.) 24) : Acrylite EX (manufactured by Mitsubishi Rayon Co., Ltd., film thickness: 2.0 mm) 25): Polycarbonate plate (manufactured by Takiron Co., Ltd., film thickness: 2.0 mm) 26) : Carbo Glass Twin Carbo 9034-30 (AGC manufactured by Asahi Shikoko Co., Ltd., film thickness: 4.0 mm) 27) : ABS plate Natural (manufactured by Takiron Co., Ltd., film thickness: 2.0 mm) 28) : S640 (manufactured by Takiron Co., Ltd.) Thickness 2.0 mm) The units of the values in Tables 1 and 2 are % by mass, and the addition ratio of the surface conditioner is relative to the addition ratio of the ink composition. 099140501 17 201124482 [Table i] EXAMPLES EXAMPLES EXAMPLES Example 1 2 3 4 5 ΡΥ 150° 3.6 - - - - PV 19. PR 2022) - 4.0 - - - PB 15:43) - - 2.4 - - Carbon black 4) - - - 2.1 - PR 1775) - - - - 3.6 N-vinyl caprolactam 6) 20.0 20. 0 20. 0 20.0 20. 0 Benzyl acrylate 7) 12.6 14.4 11.2 12.6 12.0 Acrylic acid Isodecyl ester 8 > 43.0 28.0 34.0 27.2 20.0 2-Hydroxy-3-phenoxypropyl acrylate 9) - 20.0 15.0 20.0 - 4-tert-butylcyclohexyl acrylate (9) - - - - 19.8 Phenoxyethyl acrylate Ester n) 5.0 - - - - Bisphenol A diacrylate (EO10 Moer modified) 12) - 4.0 - - - Bisphenol A diacrylate (EO20 Moer modified) 13) 6.0 - - - 4.0 Bisphenol A diacrylate (E〇3〇 Moer modified) 14) - - 6.0 7.0 - Bisphenol A diacrylate (E04 Moer modified) 15) - - - - - Neopentyl glycol diacrylate (PO Modified) 16) - - - - - 2-functional urethane amide 17> - - - - 5.0 Irgacure 18418) 2.0 2.0 2.5 2.5 2.5 Lucirin ΤΡ019) 2.0 3.0 2.0 2.0 2.0 Irgacure 3 6 920) 4.0 3.0 4.5 4.5 4.5 DisperBYK 1682° - - 2.4 2 .1 6.6 SOLSPERSE 3300022) 1.8 1.6 - - - TegoRad 230023) 0.2 0.2 0.2 0.2 0.2 18 099140501 201124482 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ΡΥ 150 υ - - - - PV 19. PR 2022) 4.0 4.0 4.0 4.0 PB 15:43) - - - - Carbon black 4) - - - - PR 1775) - - - - N-vinyl caprolactam 6) - 20. 0 20. 0 20. 0 Acetate Acid vinegar 7) - 14.4 14.4 14.4 Isodecyl acrylate 8) - 32.0 28.0 28.0 2-hydroxy-3-phenoxypropyl acrylate 9) 20.0 20.0 20.0 20.0 4-tert-butylcyclohexyl acrylate lfl) - - - Phenoxyethyl acrylate n) 62.4 - - - Bisphenol A diacrylate (EO10 Moer modified)|2) 4.0 - - - Bisphenol A diacrylate (EO20 Moer) 13) - - - - Bisphenol A diacrylate (EO30 Moer modified)|4) - - - - Bisphenol A diacrylate (E04 Moer modified) 15> - - - 4.0 Neopentyl glycol diacrylate (PO modified) 16) - - 4.0 - 2-functional ethyl urethane 17) - - - - Irgacure 18418) 2.0 2.0 2.0 I 2.0 Lucirin ΤΡ019) 3.0 3.0 3.0 3.0 Irgacure 36920)- 3. 0 3. 0 3. 0 3.0 DisperBYK 16821) - - - - SOLSPERSE 3 3 0 0 022) 1.6 1.6 1.6 1.6 TegoRad 230023) 0.2 0.2 0.2 0.2 19 099140501 201124482 [Table 3]
實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 黏度（mPa · s/40°C) 11.90 11.96 11.52 11.60 11.44 PMMA24)密接性 5B . 5B 5B 5B 5B PC25)密接性 5B ，5B 5B 5B 5B PC26)密接性 5B 5B 5B 5B 5B ABS27)密接性 5B 5;B 5B 5B 5B 硬質氣乙烯28)密接性 5B 5B 5B 5B 5B 150°C拉伸試驗應變量（％) 239.4 199.5 302.5 248.9 199.5 150°C拉伸試驗後外觀 B B A B AExample 1 Example 2 Example 3 Example 4 Example 5 Viscosity (mPa · s / 40 ° C) 11.90 11.96 11.52 11.60 11.44 PMMA24) Adhesion 5B . 5B 5B 5B 5B PC25) Adhesion 5B , 5B 5B 5B 5B PC26) Adhesiveness 5B 5B 5B 5B 5B ABS27) Adhesiveness 5B 5; B 5B 5B 5B Hard gas ethylene 28) Adhesion 5B 5B 5B 5B 5B 150 ° C tensile test strain (%) 239.4 199.5 302.5 248.9 199.5 150° Appearance BBABA after C tensile test
[表4][Table 4]
比較例.1 比較例2 比較例3 比較例4 黏度（mPa . s/40°C) 16.36 10.14 11.64 11.78 PMMA24)密接性 4B 3B 5B 3B PC25)密接性 1B 5B 5B 3B PC26)密接性 1B 3B 4B 5B ABS27)密接性 5B 5B 5B 5B 硬質氣乙烯28)密接性 0B 4B 5B 3B 150°C拉伸試驗應變量（％) 72.2 378.9 327.8 138.5 150°C拉伸試驗後外觀 A B C BComparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Viscosity (mPa.s/40 °C) 16.36 10.14 11.64 11.78 PMMA24) Adhesion 4B 3B 5B 3B PC25) Adhesion 1B 5B 5B 3B PC26) Adhesion 1B 3B 4B 5B ABS27) Adhesiveness 5B 5B 5B 5B Hard gas ethylene 28) Adhesion 0B 4B 5B 3B 150 ° C tensile test strain (%) 72.2 378.9 327.8 138.5 150 ° C tensile test appearance ABCB
[產業上之可利用性] 本發明之活性能量射線硬化型喷墨油墨組成物對各種可 成型之熱可塑性樹脂片材之列印性及密接性優異，本發明之 活性能量射線硬化型喷墨油墨組成物為具有廣泛使用性之 油墨組成物。本發明之附有圖樣之熱可塑性樹脂片材即便進 行熱成型，亦可於無損圖樣外觀之情況下成型。 099140501 20[Industrial Applicability] The active energy ray-curable inkjet ink composition of the present invention is excellent in printability and adhesion to various formable thermoplastic resin sheets, and the active energy ray-curable inkjet of the present invention The ink composition is an ink composition having wide applicability. The patterned thermoplastic resin sheet of the present invention can be molded without deteriorating the appearance of the pattern even if it is thermoformed. 099140501 20