TWI712656B - Ink composition and ink set for photocurable inkjet recording - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
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Abstract
本發明之光硬化型噴墨記錄用墨水組成物，其係用於單一路徑方式噴墨裝置，
其係含有聚合性化合物與光聚合起始劑，
其中聚合性化合物係包含以通式(I)：
Description
本發明係有關光硬化型噴墨記錄用墨水組成物及墨水套組。The present invention relates to a photocurable ink composition and ink set for inkjet recording.
噴墨記錄用墨水組成物，可列舉例如藉由照射如紫外線之活性能量線，使塗佈膜硬化形成圖像的墨水組成物、及對記錄媒體滲透，以乾燥等除去溶劑，形成圖像的墨水組成物(以下，有時前者記載為光硬化型噴墨記錄用墨水組成物，後者記載為溶劑型噴墨記錄用墨水組成物)。光硬化型噴墨記錄用墨水組成物係藉由光照射形成聚合物，且乾燥性優異，故一般而言，相較於溶劑型噴墨記錄用墨水組成物，形成之圖像為塗膜強度優異，對設計圖像之轉印性優異，且具有適於高速印刷之優點。 [先前技術文獻] [專利文獻]The ink composition for inkjet recording includes, for example, an ink composition that hardens a coating film to form an image by irradiating active energy rays such as ultraviolet rays, and an ink composition that penetrates the recording medium and removes the solvent by drying to form an image. Ink composition (hereinafter, the former may be described as an ink composition for photocurable inkjet recording, and the latter may be described as an ink composition for solvent inkjet recording). The photo-curable ink composition for inkjet recording forms a polymer by light irradiation and has excellent drying properties. Therefore, in general, compared to solvent-based ink composition for inkjet recording, the formed image is the strength of the coating film Excellent, excellent transfer of design images, and has the advantages of being suitable for high-speed printing. [Prior Technical Literature] [Patent Literature]
[專利文獻1]特開2010-209198號公報[Patent Document 1] JP 2010-209198 A
對於光硬化型噴墨記錄用墨水組成物，為了得到轉印性更優異的圖像，而要求噴墨頭之噴嘴不會產生阻塞，安定的吐出墨水液滴的性質(吐出安定性)。吐出安定性，特別是高速印刷時被要求之重要的特性。For the photocurable ink composition for inkjet recording, in order to obtain an image with better transferability, it is required that the nozzles of the inkjet head should not be clogged and that the ink droplets can be discharged stably (discharge stability). Discharge stability, especially an important characteristic required for high-speed printing.
光硬化型噴墨記錄用墨水組成物，通常包含光聚合起始劑與具有乙烯性雙鍵之聚合性化合物，故具有臭氣、皮膚刺激等。專利文獻1記載越是硬化性優異之光硬化型噴墨記錄用墨水組成物，越具有皮膚刺激性。期望全部滿足這種墨水組成物之吐出安定性、安全性、塗膜之密著性及塗膜強度之4種特性。The photocurable ink composition for inkjet recording usually contains a photopolymerization initiator and a polymerizable compound having an ethylenic double bond, so it has odor and skin irritation. Patent Document 1 describes that the more excellent the curability of the photocurable ink composition for inkjet recording, the more skin irritation is. It is expected that all four characteristics of this ink composition, such as discharge stability, safety, coating film adhesion, and coating film strength, are satisfied.
本發明係有鑑於上述課題而完成者，本發明之目的係提供具有優異之安全性及高速印刷中之優異的吐出安定性，可形成密著性及強度優異之塗膜的光硬化型噴墨記錄用墨水組成物。又，本發明之另外之目的係提供包含這種光硬化型噴墨記錄用墨水組成物的墨水套組。 The present invention was completed in view of the above-mentioned problems. The object of the present invention is to provide a photocurable inkjet that has excellent safety and excellent discharge stability in high-speed printing, and can form a coating film with excellent adhesion and strength. Ink composition for recording. Moreover, another object of the present invention is to provide an ink set containing such a photocurable ink composition for inkjet recording.
本發明人等，精心檢討的結果而完成本發明。
亦即，本發明係提供以下的態樣者。
[1]一種光硬化型噴墨記錄用墨水組成物，其係用於單一路徑方式之噴墨記錄裝置的光硬化型噴墨記錄用墨水組成物，
其係含有聚合性化合物與光聚合起始劑，
前述聚合性化合物係包含：
以下述通式(I)：
依據本發明時，可提供具有優異安全性及高速印刷時之優異的吐出安定性，且可形成密著性及強度優異之塗膜的光硬化型噴墨記錄用墨水組成物。又，依據本發明時，可提供包含這種光硬化型噴墨記錄用墨水組成物的墨水套組。 [實施發明之形態]According to the present invention, it is possible to provide a photocurable inkjet recording ink composition that has excellent safety and excellent discharge stability during high-speed printing, and can form a coating film with excellent adhesion and strength. Furthermore, according to the present invention, an ink set containing such a photocurable ink composition for inkjet recording can be provided. [The form of implementing the invention]
以下，詳細說明本發明之實施形態。又，本說明書中，丙烯醯基及甲基丙烯醯基有稱為「(甲基)丙烯醯基」的情形。又，化合物名之後附上「系」，有涵蓋化合物及其衍生物的情形。化合物名之後附上「系」表示聚合物名時，意指聚合物之重複單位為來自化合物或其衍生物，或來自化合物或其衍生物之重複單位在聚合後，施予了化學修飾等的聚合物。Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the acryl group and the methacryl group may be referred to as "(meth)acryl group". In addition, "series" is appended to the compound name, which may cover the compound and its derivatives. When the compound name is appended with "system" to indicate the name of the polymer, it means that the repeating unit of the polymer is derived from the compound or its derivative, or the repeating unit from the compound or its derivative is chemically modified after polymerization. polymer.
＜光硬化型噴墨記錄用墨水組成物＞ 本發明之實施形態之噴墨記錄用墨水組成物(以下有時稱為墨水組成物)係使用於單一路徑(single pass)方式的噴墨記錄裝置。墨水組成物係含有聚合性化合物與光聚合起始劑。聚合性化合物係包含含乙烯醚基(甲基)丙烯酸酯類、單官能單體及多官能單體。含乙烯醚基(甲基)丙烯酸酯類係以通式(I)表示。單官能單體係選自由丙烯醯胺系單體及單官能(甲基)丙烯酸單體所組成之群組之至少1種。單官能單體之含有率為1質量%以上9質量%以下。多官能(甲基)丙烯酸單體之含有率為5質量%以上50質量%以下。單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃以上，多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃以上。<Photocurable ink composition for inkjet recording> The ink composition for inkjet recording (hereinafter sometimes referred to as the ink composition) according to the embodiment of the present invention is used in a single pass type inkjet recording device. The ink composition system contains a polymerizable compound and a photopolymerization initiator. The polymerizable compound includes vinyl ether group-containing (meth)acrylates, monofunctional monomers, and multifunctional monomers. The vinyl ether group-containing (meth)acrylates are represented by the general formula (I). The monofunctional monosystem is at least one selected from the group consisting of acrylamide monomers and monofunctional (meth)acrylic monomers. The content of the monofunctional monomer is 1% by mass to 9% by mass. The content rate of the polyfunctional (meth)acrylic monomer is 5% by mass to 50% by mass. The glass transition temperature of the polymer of monofunctional (meth)acrylic monomer is 30°C or higher, and the glass transition temperature of the polymer of polyfunctional (meth)acrylic monomer is 30°C or higher.
[1.單一路徑方式] 單一路徑方式之噴墨記錄裝置具備覆蓋對記錄媒體之搬送方向垂直方向之記錄媒體全域的線性噴頭(Line head)。此噴墨記錄裝置係對於固定之線性噴頭，使記錄媒體在搬送方向僅使移動一次，與此移動連動，由線性噴頭之噴嘴吐出墨水液滴的動作，在記錄媒體上形成圖像。因此，單一路徑方式之噴墨記錄裝置可高速印刷，可提高生產性。吐出方式係以壓電方式為佳。[1. Single path method] The single-path type inkjet recording device is equipped with a line head covering the entire area of the recording medium in the direction perpendicular to the conveying direction of the recording medium. In this inkjet recording device, for a fixed linear nozzle, the recording medium is moved only once in the conveying direction. In conjunction with this movement, the nozzles of the linear nozzle eject ink droplets to form an image on the recording medium. Therefore, the single-path type inkjet recording device can print at high speed, which can improve productivity. The spitting method is preferably piezoelectric.
[2.光聚合起始劑] 本說明書中，光聚合起始劑係吸收活性能量線，使光聚合反應(連鏈聚合反應)開始。光聚合起始劑，可列舉例如醯基氧化磷系化合物、烷基苯酮系化合物、及噻噸酮系化合物。[2. Photopolymerization initiator] In this specification, the photopolymerization initiator absorbs active energy rays to start the photopolymerization reaction (chain polymerization reaction). The photopolymerization initiator includes, for example, an oxyphosphorus-based compound, an alkylphenone-based compound, and a thioxanthone-based compound.
醯基氧化磷系化合物，可列舉例如2,4,6-三甲基苯甲醯基-二苯基-氧化膦(phosphine oxide)及雙(2,4,6-三甲基苯甲醯基)-苯基氧化磷。醯基氧化磷系化合物之市售品，可列舉例如BASF公司製「IRGACURE(註冊商標)TPO」及「IRGACURE(註冊商標)819」。Phosphorus oxide compounds include, for example, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzyl )-Phenyl phosphorus oxide. Examples of commercially available products of the phosphonium oxide-based compound include "IRGACURE (registered trademark) TPO" and "IRGACURE (registered trademark) 819" manufactured by BASF Corporation.
烷基苯酮系化合物，可列舉例如2,2-二甲氧基-1,2-二苯基乙烷-1-酮及2-甲基-1[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮。烷基苯酮系化合物之市售品，可列舉BASF公司製「IRGACURE(註冊商標)651」及「IRGACURE (註冊商標)907」。Examples of alkylphenone compounds include 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1[4-(methylthio)phenyl] -2-morpholinopropan-1-one. Commercial products of alkylphenone compounds include "IRGACURE (registered trademark) 651" and "IRGACURE (registered trademark) 907" manufactured by BASF Corporation.
噻噸酮系化合物，可列舉例如噻噸酮、2,4-二甲基噻噸酮、2-氯噻噸酮、2-乙基噻噸酮及1-氯-4-丙氧基噻噸酮。The thioxanthone-based compound includes, for example, thioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, and 1-chloro-4-propoxythioxanthone ketone.
光聚合起始劑之含量，就使效率佳進行光聚合反應的觀點，相對於墨水組成物100質量份，以5質量份以上25質量份以下為佳，更佳為10質量份以上20質量份以下。The content of the photopolymerization initiator, from the viewpoint of enabling efficient photopolymerization, is preferably 5 parts by mass or more and 25 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass relative to 100 parts by mass of the ink composition the following.
[3.聚合性化合物] 本說明書中，聚合性化合物係藉由聚合反應可形成聚合物的化合物。聚合性化合物係包含通式(I)表示之含乙烯醚基(甲基)丙烯酸酯類與選自由丙烯醯胺系單體及單官能(甲基)丙烯酸單體所組成之群組之至少1種的單官能單體及多官能(甲基)丙烯酸單體。單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃以上。多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃以上。 又，聚合性化合物之含有率係在全墨水組成物中，以60～85質量%為佳。[3. Polymeric compound] In this specification, a polymerizable compound is a compound that can form a polymer by a polymerization reaction. The polymerizable compound includes vinyl ether group-containing (meth)acrylates represented by general formula (I) and at least 1 selected from the group consisting of acrylamide monomers and monofunctional (meth)acrylic monomers Kinds of monofunctional monomers and multifunctional (meth)acrylic monomers. The glass transition temperature of the monofunctional (meth)acrylic monomer polymer is 30°C or higher. The glass transition temperature of the polyfunctional (meth)acrylic monomer polymer is 30°C or higher. In addition, the content rate of the polymerizable compound in the entire ink composition is preferably 60 to 85% by mass.
(3-1.含乙烯醚基(甲基)丙烯酸酯類)
含乙烯醚基(甲基)丙烯酸酯類係以通式(I)：
碳原子數2以上20以下之2價有機殘基，可列舉例如碳原子數2以上20以下之伸烷基、碳原子數3以上20以下之伸環烷基及碳原子數6以上10以下之2價芳香族基。碳原子數2以上20以下之2價有機殘基也可被取代。Divalent organic residues with 2 to 20 carbon atoms include, for example, alkylenes with 2 to 20 carbon atoms, cycloalkylenes with 3 to 20 carbon atoms, and those with 6 to 10 carbon atoms. Divalent aromatic group. Divalent organic residues having 2 to 20 carbon atoms may also be substituted.
碳原子數2以上20以下之伸烷基係直鏈或支鏈且非取代。碳原子數2以上20以下之伸烷基，可列舉例如伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基( undecylene)及伸十六烷基。碳原子數2以上20以下之伸烷基係以碳原子數2以上9以下之伸烷基為佳，更佳為碳原子數1以上8以下之氧代伸烷基、被氧原子2個以上4個以下之任一取代之碳原子數9以上15以下之伸烷基及碳原子數2以上6以下之伸烷基。The alkylene group having 2 to 20 carbon atoms is straight or branched and unsubstituted. The alkylene groups having 2 to 20 carbon atoms include, for example, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylylene, decylene, extending undecyl (undecylene) and extending hexadecyl. The alkylene having 2 to 20 carbon atoms is preferably an alkylene having 2 to 9 carbon atoms, more preferably an oxoalkylene having 1 to 8 carbon atoms, and 2 or more oxygen atoms Any one of 4 or less substituted alkylene groups having 9 to 15 carbon atoms and alkylene groups having 2 to 6 carbon atoms.
碳原子數2以上9以下之伸烷基係直鏈或支鏈且非取代。碳原子數2以上9以下之烷基，可列舉例如伸乙基、伸丙基、伸丁基、伸戊基、伸己基、伸庚基、伸辛基及伸壬基。The alkylene group having 2 to 9 carbon atoms is linear or branched and unsubstituted. Examples of alkyl groups having 2 to 9 carbon atoms include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and nonylylene.
碳原子數1以上8以下之氧代伸烷基係直鏈或支鏈，且非取代。碳原子數1以上8以下之氧代伸烷基係碳原子數2以上9以下之伸烷基中之1個-CH2 -被-O-取代之取代基。The oxoalkylene group having 1 to 8 carbon atoms is linear or branched, and is not substituted. The oxoalkylene having 1 to 8 carbon atoms is a substituent in which one -CH 2 -is substituted by -O- in an alkylene having 2 to 9 carbon atoms.
碳原子數9以上15以下之伸烷基係直鏈或支鏈，且非取代。碳原子數9以上15以下之伸烷基，可列舉例如伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十三烷基、伸十四烷基、伸十四烷基及伸十五烷基。Alkylene groups with 9 to 15 carbon atoms are straight or branched, and unsubstituted. The alkylene groups having 9 to 15 carbon atoms include, for example, nonylylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, and tetradecylene. Alkyl and pentadecyl.
碳原子數2以上6以下之伸烷基係直鏈或支鏈，且非取代。碳原子數2以上6以下之伸烷基，可列舉例如伸乙基、伸丙基、伸丁基、伸戊基及伸己基。Alkylene groups having 2 to 6 carbon atoms are straight or branched, and are not substituted. Examples of alkylene groups having 2 to 6 carbon atoms include ethylene, propylene, butylene, pentylene, and hexylene.
碳原子數3以上20以下之伸環烷基係環狀且非取代。碳原子數3以上20以下之伸環烷基，可列舉例如伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環壬基、伸環癸基、伸環十一烷基、及伸環十六烷基。碳原子數3以上20以下之伸環烷基，也可為可被複數之碳原子數1以上3以下之烷基取代之碳原子數3以上20以下之伸環烷基。碳原子數1以上3以下之烷基係直鏈或支鏈且非取代。碳原子數1以上3以下之烷基，可列舉例如甲基、乙基、丙基及異丙基。The cycloalkylene group having 3 to 20 carbon atoms is cyclic and unsubstituted. The cycloalkylene groups having 3 to 20 carbon atoms include, for example, cycloalkylene, cyclobutylene, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, Cyclodecylene, cycloundecyl, and cyclohexadecyl. The cycloalkylene group having 3 to 20 carbon atoms may also be a cycloalkylene group having 3 to 20 carbon atoms that may be substituted by a plurality of alkyl groups having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is linear or branched and unsubstituted. Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl, and isopropyl.
碳原子數6以上10以下之2價芳香族基係環狀且非取代。碳原子數6以上10以下之2價芳香族基，可列舉例如伸苯基及伸萘基。碳原子數6以上10以下之2價芳香族基，也可為可被複數之碳原子數1以上3以下之烷基取代之碳原子數6以上10以下之2價芳香族基。The divalent aromatic group having 6 to 10 carbon atoms is cyclic and unsubstituted. Examples of divalent aromatic groups having 6 or more and 10 carbon atoms include phenylene and naphthylene. The divalent aromatic group having 6 or more and 10 or less carbon atoms may also be a divalent aromatic group having 6 or more and 10 or less carbon atoms which may be substituted by a plurality of alkyl groups having 1 or more and 3 carbon atoms.
碳原子數1以上11以下之1價有機殘基，可列舉例如碳原子數1以上10以下之烷基、碳原子數3以上10以下之環烷基及碳原子數6以上10以下之1價芳香族基。Monovalent organic residues with 1 to 11 carbon atoms include, for example, alkyl groups with 1 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, and monovalent organic residues with 6 to 10 carbon atoms. Aromatic group.
碳原子數1以上10以下之烷基係直鏈或支鏈，且非取代。碳原子數1以上10以下之烷基，可列舉例如甲基、乙基、丙基、異丙基、n-丁基、sec-丁基、tert-丁基、戊基、異戊基、新戊基、己基、庚基、辛基、壬基、及癸基。碳原子數1以上10以下之烷基係以碳原子數1以上3以下之烷基為佳，更佳為可被苯基取代之碳原子數1以上3以下之烷基，又更佳為甲基、乙基及苄基。可被取代之碳原子數6以上10以下之1價芳香族基，較佳為苯基。碳原子數1以上3以下之烷基係與碳原子數3以上20以下之伸環烷基中之碳原子數1以上3以下之烷基同義。 The alkyl group having 1 to 10 carbon atoms is linear or branched, and is not substituted. Alkyl groups having 1 to 10 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, and new Pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms which may be substituted by a phenyl group, and still more preferably a methyl group Group, ethyl and benzyl. The monovalent aromatic group having 6 to 10 carbon atoms which may be substituted is preferably a phenyl group. The alkyl group having 1 to 3 carbon atoms has the same meaning as the alkyl group having 1 to 3 carbon atoms in the cycloalkylene having 3 to 20 carbon atoms.
碳原子數3以上10以下之環烷基為環狀且非取代。碳原子數3以上10以下之環烷基，可列舉例如環丁基、環戊基、環己基、環庚基、及環辛基。 The cycloalkyl group having 3 to 10 carbon atoms is cyclic and unsubstituted. The cycloalkyl group having 3 to 10 carbon atoms includes, for example, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.
碳原子數6以上10以下之1價芳香族基為環狀且非取代。碳原子數6以上10以下之1價芳香族基，可列舉例如苯基及萘基。 The monovalent aromatic group having 6 to 10 carbon atoms is cyclic and unsubstituted. Examples of monovalent aromatic groups having 6 or more and 10 carbon atoms include phenyl and naphthyl.
(甲基)丙烯酸酯類(I)，可列舉例如(甲基)丙烯酸乙烯氧基烷酯、(甲基)丙烯酸乙烯氧基環烷酯、(甲基)丙烯酸烷基乙烯氧基烷酯、(甲基)丙烯酸乙烯氧基烷基環烷基烷酯、(甲基)丙烯酸乙烯氧基烷基芳基烷酯、(甲基)丙烯酸乙烯氧基烷氧基烷酯、(甲基)丙烯酸乙烯氧基烷氧基烷氧基烷酯及(甲基)丙烯酸乙烯氧基烷氧基烷氧基烷氧基烷酯。此等之(甲基)丙烯酸酯類(I)可單獨使用1種，亦可組合2種以上來使用。 The (meth)acrylates (I) include, for example, vinyloxyalkyl (meth)acrylate, vinyloxycycloalkyl (meth)acrylate, alkyl vinyloxyalkyl (meth)acrylate, Vinyloxyalkylcycloalkylalkyl (meth)acrylate, vinyloxyalkylarylalkyl (meth)acrylate, vinyloxyalkoxyalkyl (meth)acrylate, (meth)acrylic acid Vinyloxyalkoxyalkoxyalkyl ester and vinyloxyalkoxyalkoxyalkoxyalkyl (meth)acrylate. These (meth)acrylates (I) may be used individually by 1 type, and may be used in combination of 2 or more types.
(甲基)丙烯酸乙烯氧基烷酯，可列舉例如(甲基)丙烯酸2-乙烯氧基乙酯、(甲基)丙烯酸2-乙烯氧基丙酯、(甲基)丙烯酸4-乙烯氧基丁酯、及(甲基)丙烯酸2-乙烯氧基丁酯。 Vinyloxyalkyl (meth)acrylate, for example 2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxy (meth)acrylate Butyl ester, and 2-vinyloxybutyl (meth)acrylate.
(甲基)丙烯酸乙烯氧基環烷酯，可列舉例如(甲基)丙烯酸乙烯氧基環己酯。 (Meth)acrylic acid vinyloxy cycloalkyl ester, for example, (meth)acrylic acid vinyloxy cyclohexyl ester can be mentioned.
(甲基)丙烯酸烷基乙烯氧基烷酯，可列舉例如(甲基)丙烯酸2-甲基-3-乙烯氧基丙酯、及(甲基)丙烯酸1-甲基-2-乙烯氧基丙酯。 (Meth)acrylic acid alkyl vinyloxyalkyl ester, for example, (meth)acrylic acid 2-methyl-3-vinyloxypropyl ester, and (meth)acrylic acid 1-methyl-2-vinyloxy Propyl ester.
(甲基)丙烯酸乙烯氧基烷基環烷基烷酯，可列舉例如(甲基)丙烯酸3-乙烯氧基甲基環己基甲酯。 (Meth)acrylic acid vinyloxyalkylcycloalkylalkylester, for example, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate can be mentioned.
(甲基)丙烯酸乙烯氧基烷基芳基烷酯，可列舉例如(甲基)丙烯酸p-乙烯氧基甲基苯基甲酯。 (Meth)acrylic acid vinyloxy alkyl aryl alkyl ester, for example, (meth)acrylic acid p-vinyloxy methyl phenyl methyl ester can be mentioned.
(甲基)丙烯酸乙烯氧基烷氧基烷酯，可列舉例如丙烯酸2-(2-乙烯氧基乙氧基)乙酯(VEEA)、甲基丙烯酸2-(2-乙烯氧基乙氧基)乙酯(VEEM)、(甲基)丙烯酸2-(乙烯氧基異丙氧基)丙酯、及(甲基)丙烯酸2-(乙烯氧基異丙氧基)異丙酯。 (Meth) acrylate vinyloxy alkoxy alkyl esters, for example, 2-(2-vinyloxyethoxy) ethyl acrylate (VEEA), 2-(2-vinyloxyethoxy methacrylate) ) Ethyl (VEEM), 2-(vinyloxyisopropoxy)propyl (meth)acrylate, and 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate.
(甲基)丙烯酸乙烯氧基烷氧基烷氧基烷酯，可列舉例如(甲基)丙烯酸乙烯氧基乙氧基乙氧基乙酯。 (Meth)acrylic acid vinyloxy alkoxy alkoxy alkyl ester, for example, (meth)acrylic acid vinyloxy ethoxy ethoxy ethyl ester can be mentioned.
(甲基)丙烯酸乙烯氧基烷氧基烷氧基烷氧基烷酯，可列舉例如(甲基)丙烯酸乙烯氧基乙氧基乙氧基乙氧基乙酯。 (Meth)acrylic acid vinyloxy alkoxy alkoxy alkoxy alkyl ester, for example, (meth)acrylic acid vinyloxy ethoxy ethoxy ethoxy ethyl ester can be mentioned.
此等(甲基)丙烯酸酯類(I)之中，低黏度，且臭氣低，可抑制對皮膚刺激，引火點高，且反應性及硬化性優異，藉由硬化形成之塗膜之密著性優異，故較佳為(甲基)丙烯酸2-(2-乙烯氧基乙氧基)乙酯。 Among these (meth)acrylates (I), the viscosity is low, and the odor is low, which can inhibit skin irritation, has a high ignition point, and is excellent in reactivity and hardening. The dense coating formed by hardening Since it is excellent in tackiness, it is preferably 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.
(甲基)丙烯酸酯類(I)之含有率，就可使墨水低黏度化，提高反應性、塗膜強度及密著性的觀點，在墨水組成物，較佳為20質量%以上60質量%以下，更佳為20質量%以上50質量%以下，又更佳為30質量%以上50質量%以下，特佳為35質量%以上50質量%以下，非常特佳為35質量%以上45質量%以下。The content of (meth)acrylates (I) can lower the viscosity of the ink and improve the reactivity, coating film strength and adhesion. In the ink composition, it is preferably 20% by mass or more and 60% by mass. % Or less, more preferably 20 mass% or more and 50 mass% or less, still more preferably 30 mass% or more and 50 mass% or less, particularly preferably 35 mass% or more and 50 mass% or less, very particularly preferably 35 mass% or more and 45 mass% %the following.
(3-2.單官能單體) 本說明書中，單官能單體係1分子中具有1個聚合性的部分(例如乙烯性雙鍵)。單官能單體係選自由丙烯醯胺系單體及單官能(甲基)丙烯酸單體所組成之群組之至少1種。單官能單體之含有率係在墨水組成物中，為1質量%以上9質量%以下。單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg為30℃以上。單官能單體係黏度比較低，且單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg比較高。因此，墨水組成物係以1質量%以上9質量%以下之含有率包含單官能單體時，可提供對(甲基)丙烯酸酯類(I)及多官能(甲基)丙烯酸單體，作為稀釋劑產生機能，吐出安定性及安全性優異，且可形成強度優異之塗膜，亦即，平衡良好兼具3個特性的墨水組成物。單官能單體之含有率，就更提高上述3個特性的觀點，在墨水組成物，較佳為7質量%以上9質量%以下，更佳為5質量%以上9質量%以下。(3-2. Monofunctional monomer) In this specification, a monofunctional monosystem has one polymerizable part (for example, an ethylenic double bond) in one molecule. The monofunctional monosystem is at least one selected from the group consisting of acrylamide monomers and monofunctional (meth)acrylic monomers. The content of the monofunctional monomer in the ink composition is 1% by mass to 9% by mass. The glass transition temperature Tg of the monofunctional (meth)acrylic monomer polymer is 30°C or higher. The monofunctional monosystem has relatively low viscosity, and the glass transition temperature Tg of the monofunctional (meth)acrylic monomer polymer is relatively high. Therefore, when the ink composition contains a monofunctional monomer at a content rate of 1% by mass to 9% by mass, it can provide (meth)acrylates (I) and polyfunctional (meth)acrylic monomers as The thinner produces an ink composition that has excellent discharge stability and safety, and can form a coating film with excellent strength, that is, a well-balanced ink composition with three characteristics. From the viewpoint of further improving the above three characteristics, the content of the monofunctional monomer is preferably 7 mass% to 9 mass% in the ink composition, and more preferably 5 mass% to 9 mass%.
皮膚第一次刺激指數(Primary Irritation Index：PII值)係表示皮膚刺激性之物性值。PII值越大表示對皮膚之刺激性越強，使用上要注意的化合物。Primary Irritation Index (PII value) is a physical property value indicating skin irritation. The larger the PII value, the stronger the irritation to the skin. Please pay attention to the compound.
(3-2-1.丙烯醯胺系單體) 丙烯醯胺系單體，可列舉例如二甲基丙烯醯胺、二乙基丙烯醯胺、2-羥基乙基丙烯醯胺、二甲基胺基丙基丙烯醯胺、及丙烯醯基嗎啉(ACMO)。此等之丙烯醯胺系單體之中，以具有環狀結構(更具體而言，脂環式結構或雜環式結構等)之丙烯醯胺系單體為佳，更佳為丙烯醯基嗎啉。(3-2-1. Acrylic amide monomer) The acrylamide monomers include, for example, dimethyl acrylamide, diethyl acrylamide, 2-hydroxyethyl acrylamide, dimethylaminopropyl acrylamide, and acryl morpholine (ACMO). Among these acrylamide-based monomers, acrylamide-based monomers having a cyclic structure (more specifically, alicyclic structure or heterocyclic structure, etc.) are preferred, and acrylamide-based monomers are more preferred. Morpholine.
(3-2-2.單官能(甲基)丙烯酸單體) 單官能(甲基)丙烯酸單體，可列舉例如具有鏈狀結構或環狀結構之單官能(甲基)丙烯酸單體。在此，具有鏈狀結構之單官能(甲基)丙烯酸單體，其分子結構中不具有環式結構，而具有直鏈結構或支鏈結構。具有環狀結構之單官能(甲基)丙烯酸單體，其分子結構中具有環狀結構，也可再具有鏈狀結構。(3-2-2. Monofunctional (meth)acrylic monomer) The monofunctional (meth)acrylic monomer includes, for example, a monofunctional (meth)acrylic monomer having a chain structure or a cyclic structure. Here, the monofunctional (meth)acrylic monomer having a chain structure does not have a cyclic structure in its molecular structure, but has a linear structure or a branched structure. The monofunctional (meth)acrylic monomer having a cyclic structure has a cyclic structure in its molecular structure, and may also have a chain structure.
單官能(甲基)丙烯酸單體，就具有該單官能(甲基)丙烯酸單體之聚合物為30℃以上之玻璃轉移溫度的觀點，以具有環狀結構為佳。具有環狀結構之單官能(甲基)丙烯酸單體，可列舉例如單環之脂環式(甲基)丙烯酸酯、複環之脂環式(甲基)丙烯酸酯、及雜環式(甲基)丙烯酸酯。單環之脂環式(甲基)丙烯酸酯，可列舉例如環烷基(甲基)丙烯酸酯(更具體而言，3,3,5-三甲基環己基丙烯酸酯(TMCHA)等)。複環之脂環式(甲基)丙烯酸酯，可列舉例如丙烯酸異冰片酯(IBOA)、異莰基甲基丙烯酸酯、降莰基(甲基)丙烯酸酯、金剛烷基(甲基)丙烯酸酯及二環戊基(甲基)丙烯酸酯。雜環式(甲基)丙烯酸酯，可列舉例如環狀三羥甲基丙烷縮甲醛丙烯酸酯(CTFA)。此等之單官能(甲基)丙烯酸單體，可單獨使用1種，亦可組合2種以上來使用。The monofunctional (meth)acrylic monomer preferably has a cyclic structure from the viewpoint that the polymer having the monofunctional (meth)acrylic monomer has a glass transition temperature of 30°C or higher. Monofunctional (meth)acrylic monomers having a cyclic structure include, for example, monocyclic alicyclic (meth)acrylates, bicyclic alicyclic (meth)acrylates, and heterocyclic (meth)acrylates.基)acrylate. Monocyclic alicyclic (meth)acrylates include, for example, cycloalkyl (meth)acrylates (more specifically, 3,3,5-trimethylcyclohexylacrylate (TMCHA), etc.). Bicyclic alicyclic (meth)acrylates, for example, isobornyl acrylate (IBOA), isobornyl methacrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylic acid Esters and dicyclopentyl (meth)acrylate. Examples of heterocyclic (meth)acrylates include cyclic trimethylolpropane formal acrylate (CTFA). These monofunctional (meth)acrylic monomers may be used alone or in combination of two or more kinds.
此等之單官能(甲基)丙烯酸單體之中，以選自由丙烯酸異冰片酯(IBOA)、3,3,5-三甲基環己基丙烯酸酯(TMCHA)、及環狀三羥甲基丙烷縮甲醛丙烯酸酯(CTFA)及異莰基甲基丙烯酸酯所組成之群組之至少1種為佳，更佳為選自由丙烯酸異冰片酯(IBOA)、3,3,5-三甲基環己基丙烯酸酯(TMCHA)及環狀三羥甲基丙烷縮甲醛丙烯酸酯(CTFA)所組成之群組之至少1種。Among these monofunctional (meth)acrylic monomers, they are selected from isobornyl acrylate (IBOA), 3,3,5-trimethylcyclohexyl acrylate (TMCHA), and cyclic trimethylol At least one of the group consisting of propane formal acrylate (CTFA) and isobornyl methacrylate is preferred, more preferably selected from isobornyl acrylate (IBOA), 3,3,5-trimethyl At least one of the group consisting of cyclohexyl acrylate (TMCHA) and cyclic trimethylolpropane formal acrylate (CTFA).
單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg，就提高塗膜強度的觀點，為30℃以上。單官能(甲基)丙烯酸單體之玻璃轉移溫度，就維持優異之塗膜強度，同時提高吐出安定性及安全性的觀點，更佳為30℃以上90℃以下，更佳為40℃以上90℃以下。又，本說明書中，單官能(甲基)丙烯酸單體之聚合物係指單官能(甲基)丙烯酸單體單獨進行聚合的聚合物。亦即，意味該聚合物實質上由來自1種單官能(甲基)丙烯酸單體之重複單位所成者。聚合物實質上由來自1種單官能(甲基)丙烯酸單體之重複單位所成係指對於構成聚合物之全重複單位，來自1種單官能(甲基)丙烯酸單體之重複單位為99莫耳%以上。The glass transition temperature Tg of the polymer of the monofunctional (meth)acrylic monomer is 30°C or higher from the viewpoint of improving the strength of the coating film. The glass transition temperature of monofunctional (meth)acrylic monomer maintains excellent coating film strength while improving discharge stability and safety. It is more preferably 30°C or higher and 90°C or lower, and more preferably 40°C or higher and 90°C or higher. Below ℃. In addition, in this specification, the polymer of a monofunctional (meth)acrylic monomer means a polymer in which a monofunctional (meth)acrylic monomer is polymerized alone. That is, it means that the polymer is essentially composed of repeating units derived from one monofunctional (meth)acrylic monomer. The polymer is essentially composed of repeating units derived from a monofunctional (meth)acrylic monomer. It means that the repeating units of a single monofunctional (meth)acrylic monomer are 99 More than mol%.
(3-3.多官能(甲基)丙烯酸單體) 本說明書中，多官能(甲基)丙烯酸單體係1分子中具有2個以上聚合性之部分(例如乙烯性雙鍵)。多官能(甲基)丙烯酸單體，可列舉二官能(甲基)丙烯酸單體、三官能(甲基)丙烯酸單體、四官能(甲基)丙烯酸單體及五官能(甲基)丙烯酸單體。多官能(甲基)丙烯酸單體，也可具有鏈狀結構或脂環式結構。在此，具有鏈狀結構之多官能(甲基)丙烯酸單體，其分子結構中不具有環式結構，而具有直鏈結構或支鏈結構。具有脂環式結構之多官能(甲基)丙烯酸單體，其分子結構中具有脂環式結構，也可再具有鏈狀結構。(3-3. Multifunctional (meth)acrylic monomer) In this specification, the polyfunctional (meth)acrylic acid single system has two or more polymerizable parts (for example, ethylenic double bonds) in one molecule. Multifunctional (meth)acrylic monomers, including difunctional (meth)acrylic monomers, trifunctional (meth)acrylic monomers, tetrafunctional (meth)acrylic monomers, and pentafunctional (meth)acrylic monomers body. The polyfunctional (meth)acrylic monomer may have a chain structure or an alicyclic structure. Here, the multifunctional (meth)acrylic monomer having a chain structure does not have a cyclic structure in its molecular structure, but has a linear structure or a branched structure. A polyfunctional (meth)acrylic monomer with an alicyclic structure has an alicyclic structure in its molecular structure, and may also have a chain structure.
多官能(甲基)丙烯酸單體，就具有該多官能(甲基)丙烯酸單體之聚合物為30℃以上的玻璃轉移溫度，且提高墨水組成物之安全性的觀點，較佳為二官能(甲基)丙烯酸單體，更佳為包含具有鏈狀結構之二官能(甲基)丙烯酸單體與具有脂環式結構之二官能(甲基)丙烯酸單體，又更佳為僅包含具有鏈狀結構之二官能(甲基)丙烯酸單體。The polyfunctional (meth)acrylic monomer is preferably bifunctional from the viewpoint that the polymer having the polyfunctional (meth)acrylic monomer has a glass transition temperature of 30°C or higher and improves the safety of the ink composition The (meth)acrylic monomer, more preferably includes a bifunctional (meth)acrylic monomer with a chain structure and a difunctional (meth)acrylic monomer with an alicyclic structure, and more preferably only includes Chain structure of bifunctional (meth)acrylic monomer.
具有鏈狀結構之二官能(甲基)丙烯酸單體，可列舉例如烷二醇二丙烯酸酯(更具體而言，甲基-1,5-戊二醇二丙烯酸酯(MPDDA)、1,9-壬二醇二丙烯酸酯(1,9ND-A)、及1,10-癸二醇二丙烯酸酯(DDDA)等)、聚伸烷二醇二丙烯酸酯(更具體而言，二丙二醇二丙烯酸酯(DPGDA)及三丙二醇二丙烯酸酯(TPGDA)等)及其他之二丙烯酸酯(更具體而言，新戊二醇羥基新戊酸酯二丙烯酸酯(HPNDA)及新戊二醇環氧丙烷二丙烯酸酯(NPGPODA)等)。具有此等鏈狀結構之多官能(甲基)丙烯酸單體，可單獨使用1種，亦可組合2種以上來使用。The bifunctional (meth)acrylic monomer having a chain structure includes, for example, alkanediol diacrylate (more specifically, methyl-1,5-pentanediol diacrylate (MPDDA), 1,9 -Nonanediol diacrylate (1,9ND-A), 1,10-decanediol diacrylate (DDDA), etc.), polyalkylene glycol diacrylate (more specifically, dipropylene glycol diacrylate) Ester (DPGDA) and tripropylene glycol diacrylate (TPGDA), etc.) and other diacrylates (more specifically, neopentyl glycol hydroxypivalate diacrylate (HPNDA) and neopentyl glycol propylene oxide Diacrylate (NPGPODA) etc.). The polyfunctional (meth)acrylic monomer having such a chain structure may be used alone or in combination of two or more kinds.
具有環狀結構之二官能(甲基)丙烯酸單體，可列舉例如二環戊基二丙烯酸酯(DCPDA)。Examples of the bifunctional (meth)acrylic monomer having a cyclic structure include dicyclopentyl diacrylate (DCPDA).
二官能以外之多官能(甲基)丙烯酸單體，可列舉例如丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙三醇丙氧基三(甲基)丙烯酸酯或季戊四醇三(甲基)丙烯酸酯之三官能(甲基)丙烯酸單體、如季戊四醇四(甲基)丙烯酸酯之四官能(甲基)丙烯酸單體及如二季戊四羥基五(甲基)丙烯酸酯之五官能(甲基)丙烯酸單體。Polyfunctional (meth)acrylic monomers other than difunctional include, for example, propoxylated trimethylolpropane tri(meth)acrylate, glycerol propoxy tri(meth)acrylate, or pentaerythritol tri (Meth) acrylate trifunctional (meth)acrylic monomer, such as pentaerythritol tetra(meth)acrylate tetrafunctional (meth)acrylic monomer and such as dipentaerythritol penta(meth)acrylate Pentafunctional (meth)acrylic monomer.
此等之多官能(甲基)丙烯酸單體之中，較佳為二環戊基二丙烯酸酯(DCPDA)、甲基-1,5-戊二醇二丙烯酸酯(MPDDA)、二丙二醇二丙烯酸酯(DPGDA)、新戊二醇羥基新戊酸酯二丙烯酸酯(HPNDA)、1,10-癸二醇二丙烯酸酯(DDDA)、三丙二醇二丙烯酸酯(TPGDA)、新戊二醇環氧丙烷二丙烯酸酯(NPGPODA)及1,9-壬二醇二丙烯酸酯(1,9ND-A)，更佳為選自由二丙二醇二丙烯酸酯(DPGDA)、新戊二醇羥基新戊酸酯二丙烯酸酯(HPNDA)、1,9-壬二醇二丙烯酸酯(1,9ND-A)、三丙二醇二丙烯酸酯(TPGDA)、及新戊二醇環氧丙烷二丙烯酸酯(NPGPODA)所組成之群組之至少1種。Among these multifunctional (meth)acrylic monomers, dicyclopentyl diacrylate (DCPDA), methyl-1,5-pentanediol diacrylate (MPDDA), and dipropylene glycol diacrylate are preferred. Ester (DPGDA), neopentyl glycol hydroxypivalate diacrylate (HPNDA), 1,10-decanediol diacrylate (DDDA), tripropylene glycol diacrylate (TPGDA), neopentyl glycol epoxy Propane diacrylate (NPGPODA) and 1,9-nonanediol diacrylate (1,9ND-A), more preferably selected from dipropylene glycol diacrylate (DPGDA), neopentyl glycol hydroxypivalate diacrylate Acrylate (HPNDA), 1,9-nonanediol diacrylate (1,9ND-A), tripropylene glycol diacrylate (TPGDA), and neopentyl glycol propylene oxide diacrylate (NPGPODA) At least one type of group.
多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg，就提高塗膜強度的觀點為30℃以上。多官能(甲基)丙烯酸單體之玻璃轉移溫度Tg，就維持優異之塗膜強度，同時提高吐出安定性及安全性之觀點，較佳為30℃以上200℃以下，更佳為30℃以上150℃以下。又，本說明書中，多官能(甲基)丙烯酸單體之聚合物係指多官能(甲基)丙烯酸單體以單獨進行聚合的聚合物。亦即，意味該聚合物實質上來自1種多官能(甲基)丙烯酸單體之重複單位所成。聚合物實質上來自1種多官能(甲基)丙烯酸單體之重複單位所成係指對於構成聚合物之全重複單位，來自1種多官能(甲基)丙烯酸單體之重複單位為99莫耳%以上。The glass transition temperature Tg of the polymer of the polyfunctional (meth)acrylic monomer is 30°C or higher from the viewpoint of improving the strength of the coating film. The glass transition temperature Tg of the polyfunctional (meth)acrylic monomer maintains excellent coating film strength while improving discharge stability and safety. It is preferably 30°C or more and 200°C or less, more preferably 30°C or more Below 150°C. In addition, in this specification, the polymer of the polyfunctional (meth)acrylic monomer refers to a polymer in which the polyfunctional (meth)acrylic monomer is polymerized separately. That is, it means that the polymer is substantially derived from a repeating unit of a polyfunctional (meth)acrylic monomer. The polymer is essentially derived from the repeating unit of a polyfunctional (meth)acrylic monomer, which means that the repeating unit from a polyfunctional (meth)acrylic monomer is 99 mo Ear% or more.
多官能(甲基)丙烯酸單體之含有率，就提高墨水組成物之吐出安定性及安全性，且提高塗膜強度的觀點，在墨水組成物中，為5質量%以上50質量%，較佳為10質量%以上40質量%以下。多官能(甲基)丙烯酸單體之含有率，當墨水組成物包含作為顏料之白色顏料時，較佳為5質量%以上20質量%以下，更佳為10質量%以上15質量%以下。又，多官能(甲基)丙烯酸單體之含有率係當墨水組成物包含作為顏料之白色以外的顏料(更具體而言，青色(cyan)、洋紅色(magenta)、黃色、或黑色之顏料等)時，較佳為25質量%以上50質量%以下，更佳為30質量%以上45質量%以下，較佳為30質量%以上40質量%以下。The content rate of the polyfunctional (meth)acrylic monomer improves the discharge stability and safety of the ink composition, and improves the strength of the coating film. In the ink composition, it is 5% by mass to 50% by mass, which is more Preferably it is 10 mass% or more and 40 mass% or less. When the ink composition contains a white pigment as a pigment, the content of the polyfunctional (meth)acrylic monomer is preferably from 5 mass% to 20 mass%, and more preferably from 10 mass% to 15 mass%. In addition, the content of the polyfunctional (meth)acrylic monomer is when the ink composition contains a pigment other than white as a pigment (more specifically, cyan, magenta, yellow, or black pigments) Etc.), preferably 25% by mass to 50% by mass, more preferably 30% by mass to 45% by mass, and more preferably 30% by mass to 40% by mass.
[4.其他之成分] 墨水組成物，除了聚合性化合物及光聚合起始劑外，必要時，也可進一步含有任意的成分。任意的成分，可列舉例如界面活性劑(表面張力調整劑)、著色材、聚合抑制劑、分散劑、有機溶劑、固定性(fixity)樹脂、平坦劑、消泡劑、抗氧化劑、pH調整劑、電荷賦予劑、殺菌劑、防腐劑、防臭劑、電荷調整劑、濕潤劑、及紫外線吸收劑。此等之任意的成分，可單獨使用1種，也可組合2種以上使用。[4. Other ingredients] In addition to the polymerizable compound and the photopolymerization initiator, the ink composition may further contain optional components if necessary. Optional components include, for example, surfactants (surface tension adjusters), coloring materials, polymerization inhibitors, dispersants, organic solvents, fixity resins, leveling agents, defoamers, antioxidants, and pH adjusters , Charge imparting agent, bactericide, preservative, deodorant, charge regulator, wetting agent, and ultraviolet absorber. These optional components may be used alone or in combination of two or more kinds.
(4-1.界面活性劑) 為了調整記錄媒體及/或噴墨頭對噴嘴基板之墨水之潤濕性之目的，墨水組成物也可包含界面活性劑。界面活性劑，可列舉例如聚矽氧系化合物。聚矽氧系化合物，例如具有二甲基矽氧烷結構之聚矽氧系化合物為佳，更佳為聚醚改質聚二甲基矽氧烷。界面活性劑之市售品，可列舉例如BYK-Chemie公司製「BYK-350、352、354、355、358N、361N、381N、381、392、BYK-300、302、306、307、310、315、320、322、323、325、330、331、333、337、340、344、348、370、375、377、378、355、356、357、390、UV3500、UV3510及UV3570」、Tegokemi公司製「Tegorad-2100、2200、2250、2500、及2700」、及Evonik Degussa公司製「TEGO(註冊商標)Glide 100、110、130、403、406、410、411、415、432、435、440、450、及482」等，但是不限定於此。此等界面活性劑，可單獨使用1種，亦可組合2種以上來使用。界面活性劑就維持良好相溶性的觀點，使用2種以上為佳。藉由使用2種以上的界面活性劑，即使長期間保存墨水組成物的情形，因維持良好的相溶性，故墨水組成物可在記錄媒體上充分地潤濕擴展，可保持顏料特徵之廣顏色再現性的緣故。(4-1. Surfactant) For the purpose of adjusting the wettability of the recording medium and/or inkjet head to the ink of the nozzle substrate, the ink composition may also include a surfactant. Surfactants include, for example, silicone compounds. Polysiloxane compounds, for example, polysiloxane compounds having a dimethylsiloxane structure are preferred, and polyether-modified polydimethylsiloxane is more preferred. Commercial products of surfactants include BYK-350, 352, 354, 355, 358N, 361N, 381N, 381, 392, BYK-300, 302, 306, 307, 310, 315 manufactured by BYK-Chemie, for example , 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 348, 370, 375, 377, 378, 355, 356, 357, 390, UV3500, UV3510 and UV3570", made by Tegokemi Tegorad-2100, 2200, 2250, 2500, and 2700", and "TEGO (registered trademark) Glide 100, 110, 130, 403, 406, 410, 411, 415, 432, 435, 440, 450, And 482", but not limited to this. These surfactants may be used alone or in combination of two or more kinds. Surfactants are preferably used in two or more types from the viewpoint of maintaining good compatibility. By using two or more surfactants, even when the ink composition is stored for a long period of time, the ink composition maintains good compatibility, so the ink composition can be fully wetted and spread on the recording medium, and the wide color characteristic of the pigment can be maintained For the sake of reproducibility.
界面活性劑之含量，就提高對記錄媒體之本發明之墨水組成物之潤濕性的觀點，相對於墨水組成物100質量份，較佳為0.01質量份以上5質量份以下，更佳為0.05質量份以上3質量份以下，又更佳為0.5質量份以上2質量份以下。The content of the surfactant, from the viewpoint of improving the wettability of the ink composition of the present invention to the recording medium, is preferably 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass relative to 100 parts by mass of the ink composition Parts by mass or more and 3 parts by mass or less, more preferably 0.5 parts by mass or more and 2 parts by mass or less.
(4-2.聚合抑制劑) 為了控制光聚合反應進行之目的，墨水組成物也可包含聚合抑制劑。聚合抑制劑，可列舉例如對苯二酚系化合物、兒茶酚系化合物、及酚系化合物。對苯二酚系化合物，可列舉例如對苯二酚、甲基對苯二酚、對苯二酚單甲醚、tert-丁基對苯二酚、及二tert-丁基對苯二酚。兒茶酚系化合物，可列舉例如兒茶酚、甲基兒茶酚、及tert-丁基兒茶酚。酚系化合物，可列舉例如苯酚、3,5-二tert-丁基-4-羥基甲苯(丁基羥基甲苯(BHT))、甲酚及氫醌單甲醚。(4-2. Polymerization inhibitor) For the purpose of controlling the progress of the photopolymerization reaction, the ink composition may also contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone-based compounds, catechol-based compounds, and phenol-based compounds. Hydroquinone compounds include, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, and ditert-butylhydroquinone. Examples of catechol-based compounds include catechol, methylcatechol, and tert-butylcatechol. Examples of phenolic compounds include phenol, 3,5-ditert-butyl-4-hydroxytoluene (butylhydroxytoluene (BHT)), cresol, and hydroquinone monomethyl ether.
聚合抑制劑之含量，就兼具本發明之墨水組成物之保存安定性及單一路徑方式之硬化性的觀點，相對於墨水組成物100質量份，較佳為0.05質量份以上5質量份以下，更佳為0.20質量份以上2質量份以下，又更佳為0.1質量份以上1質量份以下。The content of the polymerization inhibitor, from the viewpoint of having both the storage stability of the ink composition of the present invention and the curability of a single path method, is preferably 0.05 parts by mass to 5 parts by mass relative to 100 parts by mass of the ink composition, It is more preferably not less than 0.20 part by mass and not more than 2 parts by mass, and still more preferably not less than 0.1 part by mass and not more than 1 part by mass.
(4-3.著色材) 作為著色材，可列舉例如顏料及染料。就提高形成之圖像之耐候性的觀點，較佳為顏料(更具體而言，有機顏料及無機顏料等)。(4-3. Coloring material) Examples of the coloring material include pigments and dyes. From the viewpoint of improving the weather resistance of the formed image, pigments (more specifically, organic pigments, inorganic pigments, etc.) are preferred.
作為黑色之著色材，可列舉例如碳黑。黑色之著色材之市售品，可列舉例如東海碳公司製之tokablack；三菱化學公司製之HCF、MCF、RCF、LFF、SCF；Degussa-Hüls公司製之彩色黑、special black、printex；Columbia公司製之raven；cabot公司製之Monarch、Regal。Examples of black coloring materials include carbon black. Commercial products of black color materials include, for example, tokablack manufactured by Tokai Carbon; HCF, MCF, RCF, LFF, SCF manufactured by Mitsubishi Chemical Corporation; colored black, special black, printex manufactured by Degussa-Hüls; Columbia Corporation Raven of the system; Monarch and Regal of the Cabot Company.
作為青色的著色材，可列舉例如銅酞菁化合物、蒽醌化合物、及鹼染料色澱化合物。青色之著色材，可列舉例如C.I.顏料藍(1、7、15、15：1、15：2、15：3、15：4、60、62、或66)。Examples of the cyan coloring material include copper phthalocyanine compounds, anthraquinone compounds, and alkali dye lake compounds. Cyan coloring materials include, for example, C.I. Pigment Blue (1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, or 66).
作為黃之著色材，可列舉例如縮合偶氮化合物、異吲哚啉酮化合物、蒽醌化合物、偶氮金屬錯合物、次甲基(methine)化合物、或芳基醯胺化合物。黃色之著色材，可列舉例如C.I.顏料黃(1、3、12、13、14、15、17、62、74、83、93、94、95、97、109、110、111、120、127、128、129、138、147、151、154、155、168、174、175、176、180、181、185、191、194、及214)。Examples of yellow coloring materials include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex compounds, methine compounds, or arylamine compounds. Yellow coloring materials, for example, CI pigment yellow (1, 3, 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 138, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191, 194, and 214).
作為洋紅色之著色材，可列舉例如縮合偶氮化合物、二酮吡咯並吡咯化合物、蒽醌化合物、喹吖啶酮化合物、鹼染料色澱化合物、萘酚化合物、苯并咪唑酮化合物、硫靛化合物、或苝化合物。洋紅色之著色材，可列舉例如C.I.顏料紅(2、3、5、6、7、19、23、48：2、48：3、48：4、57：1、81：1、122、144、146、150、166、168、177、184、185、202、206、220、221、或254)。Examples of magenta coloring materials include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, alkali dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo Compound, or perylene compound. Magenta coloring materials, for example, CI Pigment Red (2, 3, 5, 6, 7, 19, 23, 48: 2, 48: 3, 48: 4, 57:1, 81:1, 122, 144 , 146, 150, 166, 168, 177, 184, 185, 202, 206, 220, 221, or 254).
作為白色之著色材，可列舉例如白色之有機顏料(更具體而言，pigment white6，18，21等)、白色之無機顏料(更具體而言，鹼性碳酸鉛、氧化鋅、氧化鈦及鈦酸鍶等)。As white coloring materials, for example, white organic pigments (more specifically, pigment white 6, 18, 21, etc.), white inorganic pigments (more specifically, alkaline lead carbonate, zinc oxide, titanium oxide and titanium Strontium acid, etc.).
顏料之分散平均粒徑，就提高墨水組成物中之顏料之分散性的觀點，較佳為20～250nm，更佳為50～230nm。From the viewpoint of improving the dispersibility of the pigment in the ink composition, the dispersed average particle diameter of the pigment is preferably 20 to 250 nm, more preferably 50 to 230 nm.
著色材之含量係相對於墨水組成物100質量份，較佳為0.5質量份以上25質量份以下，更佳為1.0質量份以上20質量份以下，又更佳為2.0質量份以上15質量份以下。The content of the coloring material is relative to 100 parts by mass of the ink composition, preferably 0.5 parts by mass or more and 25 parts by mass or less, more preferably 1.0 parts by mass or more and 20 parts by mass or less, and still more preferably 2.0 parts by mass or more and 15 parts by mass or less .
(4-4.分散劑) 為了在墨水組成物中使著色材分散之目的，墨水組成物也可含有分散劑(更具體而言，顏料分散體等)。作為分散劑，可列舉例如聚乙烯醇、丙烯酸系樹脂、苯乙烯-丙烯酸系樹脂及乙酸乙烯酯系樹脂。丙烯酸系樹脂，可列舉例如聚丙烯酸、丙烯酸-丙烯腈共聚物、及丙烯酸-丙烯酸烷基酯共聚物。苯乙烯-丙烯酸系樹脂，可列舉例如苯乙烯-丙烯酸共聚物、苯乙烯-甲基丙烯酸共聚物及苯乙烯-丙烯酸-丙烯酸烷酯共聚物。乙酸乙烯酯系樹脂，可列舉例如乙酸乙烯酯-乙烯共聚物及乙酸乙烯酯-馬來酸酯共聚物。(4-4. Dispersant) For the purpose of dispersing the coloring material in the ink composition, the ink composition may contain a dispersant (more specifically, a pigment dispersion, etc.). Examples of dispersants include polyvinyl alcohol, acrylic resins, styrene-acrylic resins, and vinyl acetate resins. Acrylic resins include, for example, polyacrylic acid, acrylic acid-acrylonitrile copolymer, and acrylic acid-alkyl acrylate copolymer. Examples of the styrene-acrylic resin include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-acrylic acid-alkyl acrylate copolymers. Examples of the vinyl acetate-based resins include vinyl acetate-ethylene copolymers and vinyl acetate-maleate copolymers.
分散劑之含量，就墨水組成物之分散安定性良好，長期經時後也選自由與初期同等之品質的觀點，相對於墨水組成物100質量份，較佳為0.1質量份以上3質量份以下，更佳為0.5質量份以上1.5質量份以下。The content of the dispersant is selected from the viewpoint of good dispersion stability of the ink composition and the same quality as the initial stage after a long period of time. Relative to 100 parts by mass of the ink composition, preferably 0.1 parts by mass to 3 parts by mass , More preferably 0.5 parts by mass or more and 1.5 parts by mass or less.
(4-5.有機溶劑) 墨水組成物，為了調整墨水組成物之黏度之目的，也可含有有機溶劑。就提高墨水組成物之乾燥性及形成圖像之轉印性的觀點，墨水組成物實質上不含有機溶劑為佳。如此，墨水組成物為了稀釋目的，不需要含有有機溶劑，故吐出墨水組成物時，以調整黏度之目的，不需要將墨水組成物過度加熱。又，墨水組成物以稀釋之目的，不需要含有有機溶劑，故墨水組成物之保存中或使用中，不易產生因墨水組成物中之有機溶劑之揮發所造成之墨水組成物之黏度上昇等。此外，墨水組成物包含顏料時，也可抑制伴隨黏度上昇所造成之顏料沉降，具有良好分散安定性的傾向。如此，墨水組成物就更提高吐出安定性的觀點，實質上不含有機溶劑為佳。有機溶劑之含量係相對於墨水組成物100質量份，較佳為3質量份以下，更佳為1質量份以下，又更佳為0質量份。有機溶劑，可列舉例如芳香族烴、脂肪族烴、醚、及酮。(4-5. Organic solvent) The ink composition may also contain organic solvents for the purpose of adjusting the viscosity of the ink composition. From the viewpoint of improving the dryness of the ink composition and the transferability of the formed image, the ink composition is preferably substantially free of organic solvents. In this way, the ink composition does not need to contain an organic solvent for the purpose of dilution. Therefore, when the ink composition is discharged, the ink composition does not need to be overheated for the purpose of adjusting the viscosity. In addition, the ink composition does not need to contain an organic solvent for the purpose of dilution. Therefore, during storage or use of the ink composition, the viscosity of the ink composition caused by the volatilization of the organic solvent in the ink composition is not likely to increase. In addition, when the ink composition contains pigments, it is also possible to suppress pigment sedimentation caused by the increase in viscosity, which tends to have good dispersion stability. In this way, from the viewpoint of improving the discharge stability of the ink composition, it is preferable that the ink composition does not substantially contain an organic solvent. The content of the organic solvent relative to 100 parts by mass of the ink composition is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0 parts by mass. Examples of organic solvents include aromatic hydrocarbons, aliphatic hydrocarbons, ethers, and ketones.
[5.皮膚第一次刺激指數(PII值)] 墨水組成物之PII值，就提高墨水組成物之安全性的觀點，較佳為未達2，更佳為未達2.00，又更佳為未達1.70。墨水組成物之PII值之算出方法記載於實施例中。[5. The first skin irritation index (PII value)] From the viewpoint of improving the safety of the ink composition, the PII value of the ink composition is preferably less than 2, more preferably less than 2.00, and still more preferably less than 1.70. The calculation method of the PII value of the ink composition is described in the Examples.
皮膚第一次刺激指數為未達2之聚合化合物之含量，就提高墨水組成物之安全性的觀點，相對於聚合性化合物100質量份(聚合性化合物之總質量100質量份)，較佳為3質量份以上35質量份以下，更佳為5質量份以上32質量份以下。The first skin irritation index is the content of the polymer compound less than 2, from the viewpoint of improving the safety of the ink composition, relative to 100 parts by mass of the polymer compound (100 parts by mass of the total mass of the polymer compound), preferably 3 parts by mass or more and 35 parts by mass or less, more preferably 5 parts by mass or more and 32 parts by mass or less.
[6.用途] 墨水組成物，特別是皮膚第一次刺激指數PII值為未達2時，適合於接觸人手之圖像形成物之用途。墨水組成物，也可作為標籤記錄於食品包裝表面用之食品包裝記錄用的墨水組成物使用。標籤可列舉例如商品名、商品之成分、製造者名、製造年月日、批次編號及注意事項記載。[6. Purpose] The ink composition, especially when the PII value of the first skin irritation index is less than 2, is suitable for the use of image forming objects in contact with human hands. The ink composition can also be used as an ink composition for food packaging recording for label recording on the surface of food packaging. The label may include, for example, the name of the product, the ingredients of the product, the name of the manufacturer, the date of manufacture, the batch number, and the notes.
[7.光硬化型噴墨記錄用墨水組成物之調製方法] 墨水組成物之調製方法，可使用以往公知的調製方法。以下，說明墨水組成物包含作為著色材之顏料時之較佳的調製方法。使用分散機，將著色劑、聚合性化合物之一部分及必要時，任意的成分(更具體而言，顏料分散劑等)進行預備混合(premix)，藉由使各成分溶解或分散，調製一次分散體。作為分散機，可列舉例如分散器、容器驅動媒體磨(mill)(更具體而言，球磨機、離心磨及遊星球磨機等)、高速旋轉磨(更具體而言，砂磨機等)及媒體攪拌磨(更具體而言，攪拌槽型磨等)。[7. Preparation method of photocurable ink composition for inkjet recording] For the preparation method of the ink composition, a conventionally known preparation method can be used. Hereinafter, a preferable preparation method when the ink composition contains a pigment as a coloring material will be described. Use a disperser to premix a part of the colorant, polymerizable compound and, if necessary, optional components (more specifically, pigment dispersant, etc.), and prepare a primary dispersion by dissolving or dispersing each component body. Examples of dispersers include dispersers, container-driven media mills (more specifically, ball mills, centrifugal mills, and planetary mills, etc.), high-speed rotary mills (more specifically, sand mills, etc.), and media stirring. Mill (more specifically, stirred tank mill, etc.).
接著，在所得之一次分散液中，添加其餘之聚合性化合物、光聚合起始劑、界面活性劑(表面張力調整劑)及必要時之添加劑(更具體而言，凝膠化防止劑等)，使用攪拌機均勻地混合。作為攪拌機，可列舉例如分散器、攪拌器(Three-One Motor)、均質器及磁力攪拌器。如此可得到墨水組成物。又，使用線混合機等之混合機，也可混合墨水組成物。此外，為了使墨水組成物中之粒子更微細化之目的，也可使用如珠磨機及高壓噴射磨之分散機，也可混合墨水組成物。Next, to the obtained primary dispersion, add the remaining polymerizable compound, photopolymerization initiator, surfactant (surface tension adjuster), and if necessary additives (more specifically, gelation inhibitor, etc.) , Use a blender to mix evenly. As a stirrer, a disperser, a stirrer (Three-One Motor), a homogenizer, and a magnetic stirrer are mentioned, for example. In this way, an ink composition can be obtained. In addition, it is also possible to mix the ink composition using a mixer such as a line mixer. In addition, for the purpose of making the particles in the ink composition finer, dispersing machines such as bead mills and high-pressure jet mills can also be used, and the ink composition can also be mixed.
＜墨水套組＞ 墨水套組包含光硬化型噴墨記錄用墨水組成物。墨水套組包含複數色(例如青色、洋紅色、黃色、黑色、及白色)之光硬化型噴墨記錄用彩色墨水組成物。光硬化型噴墨記錄用彩色墨水組成物，例如包含著色材之光硬化型噴墨記錄用墨水組成物。＜Ink set＞ The ink set contains a photocurable ink composition for inkjet recording. The ink set includes a light-curable inkjet recording color ink composition of plural colors (for example, cyan, magenta, yellow, black, and white). The color ink composition for photocurable inkjet recording, for example, a photocurable ink composition for inkjet recording containing a coloring material.
[實施例][Example]
以下使用實施例，更說明本發明。又，本發明不限定於實施例之範圍者。無特別聲明時，「%」表示「質量%」，「份」表示「質量份」。The following examples are used to further illustrate the present invention. In addition, the present invention is not limited to the scope of the embodiments. When there is no special statement, "%" means "mass%", and "parts" means "mass parts".
[1.墨水組成物之調製] (1-1.顏料分散體之調製) (黑顏料分散體) 顏料 碳黑顏料(Degussa公司製「Special Black250」15.0份 顏料分散劑 Solsperse32000(Lubrizol公司製) 6.0份 二官能丙烯酸單體 二丙二醇二丙烯酸酯(DPGDA) 79.0份 將上述材料(顏料、顏料分散劑、及二官能丙烯酸單體)投入於塑膠製瓶中。使用快速混合機，將塑膠製瓶之內容物攪拌至均勻為止，得到研磨份(mill base)。接著，使用塗料調整劑(東洋精機公司製)將研磨份分散2小時，得到黑顏料分散體。[1. Preparation of ink composition] (1-1. Preparation of pigment dispersion) (Black pigment dispersion) Pigment Carbon black pigment (15.0 parts of "Special Black 250" manufactured by Degussa) Pigment dispersant Solsperse 32000 (manufactured by Lubrizol) 6.0 parts Difunctional acrylic monomer Dipropylene glycol diacrylate (DPGDA) 79.0 parts Put the above-mentioned materials (pigment, pigment dispersant, and difunctional acrylic monomer) into a plastic bottle. Using a quick mixer, stir the contents of the plastic bottle until it is uniform to obtain a mill base. Next, the ground material was dispersed for 2 hours using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to obtain a black pigment dispersion.
(青色顏料分散體、洋紅色顏料分散體、黃色顏料分散體) 除了將作為黑色顏料之碳黑顏料(Degussa公司製「Special Black250」)變更為作為青色顏料之銅酞菁顏料(Clariant公司製「P-BFS」)、作為洋紅色之顏料之喹吖啶酮顏料(BASF公司製「RT-355D」)、及作為黃色顏料之雙偶氮顏料(Clariant公司製「4GC」)外，與黑顏料分散體之調製方法同樣，分別調製青色顏料分散體、洋紅色顏料分散體、及黃色顏料分散體。(Cyan pigment dispersion, magenta pigment dispersion, yellow pigment dispersion) In addition to changing the carbon black pigment (“Special Black250” manufactured by Degussa) as a black pigment to a copper phthalocyanine pigment (“P-BFS” manufactured by Clariant Company) as a cyan pigment, and a quinacridone pigment as a magenta pigment ("RT-355D" made by BASF), and bisazo pigment as a yellow pigment ("4GC" made by Clariant), the same as the preparation method of the black pigment dispersion, separately prepare a cyan pigment dispersion and a magenta pigment Dispersion, and yellow pigment dispersion.
(白色顏料分散體) 將作為黑色顏料之碳黑顏料(Degussa公司製「Special Black250」)15.0份變更為作為白色顏料之氧化鈦顏料(石原產業公司製「CR-60」)50.0份，且將二丙二醇二丙烯酸酯之添加量由79.0份變更為45.0份外，與黑顏料分散體之調製方法同樣調製白色顏料分散體。(White pigment dispersion) Changed 15.0 parts of carbon black pigment (“Special Black250” manufactured by Degussa Co., Ltd.) as a black pigment to 50.0 parts of titanium oxide pigment (“CR-60” manufactured by Ishihara Sangyo Co., Ltd.) as a white pigment, and used dipropylene glycol diacrylate as the The addition amount was changed from 79.0 parts to 45.0 parts, and the white pigment dispersion was prepared in the same manner as the preparation method of the black pigment dispersion.
(1-2.墨水組成物(A-1)之調製) 在包含黑顏料分散體之塑膠製瓶中，再投入作為(甲基)丙烯酸酯類(I)之丙烯酸2-(2-乙烯氧基乙氧基)乙酯(VEEA)、作為單官能單體之丙烯酸異冰片酯(IBOA)、作為多官能(甲基)丙烯酸單體之二丙二醇二丙烯酸酯(DPGDA)、新戊二醇羥基新戊酸酯二丙烯酸酯(HPNDA)、及三丙二醇二丙烯酸酯(TPGDA)與作為光聚合起始劑之2,4,6-三甲基苯甲醯基-二苯基-膦氧化物(BASF公司製「IRGACURE(註冊商標)TPO」)與作為界面活性劑之聚醚改質聚二甲基矽氧烷(BYK-Chemie公司製「BYK(註冊商標)-UV3510」)及作為聚合抑制劑之丁基羥基甲苯(BHT)。使用磁力攪拌器，將黑顏料分散體及追加投入之成分進行30分鐘攪拌得到混合物。攪拌後，使用玻璃過濾器(桐山製作所製)，將混合物進行吸引過濾，調製墨水組成物(A-1)。表1表示墨水組成物(A-1)之組成及各成分之調配量。(1-2. Preparation of ink composition (A-1)) In a plastic bottle containing black pigment dispersion, add 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA) as a (meth)acrylate (I) as a monofunctional monomer Isobornyl acrylate (IBOA), dipropylene glycol diacrylate (DPGDA) as a multifunctional (meth)acrylic monomer, neopentyl glycol hydroxypivalate diacrylate (HPNDA), and tripropylene glycol diacrylate Ester (TPGDA) and 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide ("IRGACURE (registered trademark) TPO" manufactured by BASF Corporation) as a photopolymerization initiator and as an interfacial activity Polyether modified polydimethylsiloxane ("BYK (registered trademark)-UV3510" manufactured by BYK-Chemie) and butylated hydroxytoluene (BHT) as a polymerization inhibitor. Using a magnetic stirrer, stir the black pigment dispersion and the added ingredients for 30 minutes to obtain a mixture. After stirring, the mixture was suction-filtered using a glass filter (manufactured by Kiriyama Manufacturing Co., Ltd.) to prepare an ink composition (A-1). Table 1 shows the composition of the ink composition (A-1) and the blending amount of each component.
(1-3.墨水組成物(A-2)～(A-7)及墨水組成物(B-1)～(B-9)之調製) 依據表1及表2所記載之成分及含量，與墨水組成物(A-1)之調製方法同樣調製墨水組成物(A-2)～(A-7)及墨水組成物(B-1)～(B-9)。例如墨水組成物(A-2)係除了將單官能單體由丙烯酸異冰片酯(IBOA)9份變更為丙烯酸異冰片酯(IBOA)5份及丙烯醯基嗎啉(ACMO)4份外，與墨水組成物(A-1)之調製方法同樣調製。又，墨水組成物(A-4)係除了將黑顏料分散體變更為青色顏料分散體，將單官能單體由丙烯酸異冰片酯(IBOA)9份變更為3,3,5-三甲基環己基丙烯酸酯(TMCHA)5份，將多官能(甲基)丙烯酸單體由新戊二醇羥基新戊酸酯二丙烯酸酯(HPNDA)12份及三丙二醇二丙烯酸酯(TPGDA)9.5份變更為新戊二醇環氧丙烷二丙烯酸酯(NPGPODA)25.5份外，與墨水組成物(A-1)之調製方法同樣調製。(1-3. Preparation of ink composition (A-2)～(A-7) and ink composition (B-1)～(B-9)) According to the components and contents described in Table 1 and Table 2, the ink composition (A-2) to (A-7) and the ink composition (B-1) were prepared in the same way as the preparation method of the ink composition (A-1) ~(B-9). For example, the ink composition (A-2) is based on changing the monofunctional monomer from 9 parts of isobornyl acrylate (IBOA) to 5 parts of isobornyl acrylate (IBOA) and 4 parts of acrylomorpholine (ACMO). It is prepared in the same way as the preparation method of the ink composition (A-1). In addition to the ink composition (A-4), the black pigment dispersion was changed to the cyan pigment dispersion, and the monofunctional monomer was changed from 9 parts of isobornyl acrylate (IBOA) to 3,3,5-trimethyl Cyclohexyl acrylate (TMCHA) 5 parts, the multifunctional (meth) acrylic monomer is changed from 12 parts of neopentyl glycol hydroxypivalate diacrylate (HPNDA) and 9.5 parts of tripropylene glycol diacrylate (TPGDA) It was prepared in the same manner as the preparation method of the ink composition (A-1) except that it was 25.5 parts of neopentyl glycol propylene oxide diacrylate (NPGPODA).
(聚合物之玻璃轉移溫度之測量方法) 將聚合性化合物之1種(單官能(甲基)丙烯酸單體及多官能(甲基)丙烯酸單體之中之1種)與作為光聚合起始劑之1-羥基-環己基-苯基酮(Ciba公司製「IRGACURE184」)以質量比(聚合性化合物/光聚合起始劑)95/5進行混合調製溶液。使用棒塗佈器(#20)，將此溶液塗佈於玻璃基板上，形成均勻的塗佈膜。其次，使用金屬鹵素燈，以積分光量200mJ/cm2 的條件，將紫外線照射於塗佈膜，使硬化得到硬化物。將所得之硬化物自玻璃基板剝離，作為測量試料。使用熱重量測量裝置(Mac Science公司製「TG-GDA」)，測定測量試料之玻璃轉移溫度(單位：溫度)。將測量後之測量試料之玻璃轉移溫度作為單官能(甲基)丙烯酸單體或多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度。所得之玻璃轉移溫度彙整於表1及表2。又，測量條件係在氮氣氛下，昇溫速度10℃/分鐘、測量溫度範圍-100～180℃下進行。(Method for measuring the glass transition temperature of polymers) One type of polymerizable compound (one of monofunctional (meth)acrylic monomer and multifunctional (meth)acrylic monomer) is combined with the photopolymerization starter 1-hydroxy-cyclohexyl-phenyl ketone ("IRGACURE184" manufactured by Ciba) as the agent was mixed at a mass ratio (polymerizable compound/photopolymerization initiator) 95/5 to prepare a solution. Using a bar coater (#20), apply this solution on the glass substrate to form a uniform coating film. Next, using a metal halide lamp, the coating film was irradiated with ultraviolet rays under the condition of an integrated light amount of 200 mJ/cm 2 to harden the cured product. The obtained cured product was peeled from the glass substrate and used as a measurement sample. Using a thermogravimetric measuring device ("TG-GDA" manufactured by Mac Science Corporation), the glass transition temperature (unit: temperature) of the measurement sample was measured. The glass transition temperature of the measured sample after the measurement is taken as the glass transition temperature of the polymer of the monofunctional (meth)acrylic monomer or the polyfunctional (meth)acrylic monomer. The resulting glass transition temperatures are summarized in Table 1 and Table 2. In addition, the measurement conditions were performed under a nitrogen atmosphere, a temperature increase rate of 10°C/min, and a measurement temperature range of -100 to 180°C.
表1及表2中，欄「Tg」表示各成分之聚合物之玻璃轉移溫度。欄「成分」之字母(alphabet)表示表3所示之成分的簡稱或型號。欄「黏度」表示25℃下之各成分的黏度。欄「實施例1」～「實施例7」及欄「比較例1」～「比較例9」，各自表示墨水組成物(A-1)～(A-7)及墨水組成物(B-1)～(B-9)之各成分之含量(單位：份)。In Table 1 and Table 2, the column "Tg" represents the glass transition temperature of the polymer of each component. The alphabet in the column "Component" represents the abbreviation or model number of the component shown in Table 3. The column "Viscosity" indicates the viscosity of each component at 25°C. The columns "Example 1" to "Example 7" and the columns "Comparative Example 1" to "Comparative Example 9" each represent ink composition (A-1) to (A-7) and ink composition (B-1) )～(B-9) The content of each component (unit: part).
表3表示墨水組成物之成分之詳細內容。Table 3 shows the details of the components of the ink composition.
[2.評價方法] (2-1.墨水組成物之吐出安定性之評價：墨水組成物之黏度測量) 依據JIS Z8803的方法，使用R100型黏度計(東機產業公司製)，在溫度25℃及圓錐轉數5rpm的條件下，測量墨水組成物的黏度。所得之黏度(單位：mPa･s)如表4所示。 又，在25℃下墨水組成物的黏度為10.5mPa･s以下時，墨水組成物之吐出安定性，評價為實用上沒有問題的水準。在25℃下墨水組成物之黏度為10.5mPa･s以下時，噴墨記錄裝置之標準的使用條件(通常40℃)下，墨水組成物由噴墨頭之噴嘴，安定被吐出的緣故。[2. Evaluation method] (2-1. Evaluation of spitting stability of ink composition: measurement of viscosity of ink composition) According to the method of JIS Z8803, the viscosity of the ink composition was measured using a R100 type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25°C and a cone rotation of 5 rpm. The obtained viscosity (unit: mPa･s) is shown in Table 4. In addition, when the viscosity of the ink composition at 25°C was 10.5 mPa·s or less, the ejection stability of the ink composition was evaluated as a practically no problem level. When the viscosity of the ink composition is below 10.5mPa･s at 25°C, the ink composition is stably discharged from the nozzle of the inkjet head under the standard operating conditions of the inkjet recording device (usually 40°C).
(2-2.墨水組成物之安全性之評價：PII值之算出) 依據表1及表2所記載之墨水組成物之成分之PII值及墨水組成物之組成，算出墨水組成物之PII值。所得之PII值如表4所示。(2-2. Evaluation of the safety of the ink composition: calculation of the PII value) Calculate the PII value of the ink composition based on the PII value of the ink composition and the composition of the ink composition described in Table 1 and Table 2. The PII values obtained are shown in Table 4.
(2-3.密著性之評價：方格試驗) 在液滴大小7pL及解析度600×600dpi的條件下，使墨水組成物由噴墨頭吐出，塗佈於基材(白PET)上形成塗佈膜。此噴墨頭係搭載於單一路徑方式之噴墨記錄裝置的噴墨頭。使用紫外線LED(日亞化學工業公司製「NCCU001E」)，以總照射光量成為300mJ/cm2 ，對塗佈膜照射紫外線，使塗佈膜硬化，在基材上形成塗膜(膜厚3μm)。結果得到密著性測量用試料。其次，將密著性測量用試料之塗膜表面進行十字切割，然後黏貼黏著薄片(nichiban公司製「透明膠帶(Cellotape) (註冊商標)」)之黏著層側之面，再將黏著薄片拉剝離。以目視觀察塗膜的狀態。由觀察結果，依據下述評價基準評價密著性。將評價S(特別良好)、A(良好)、及B(良)判斷為密著性在實用上無問題的水準。密著性之評價結果如表4所示。又，密著性之評價係在溫度25℃下實施。 (密著性之評價基準) S(特別良好)：塗膜完全無剝離。 A(良好) ：塗膜稍微剝離。 B(良) ：塗膜局部剝離。 C(不良) ：黏貼黏著薄片之部分之塗膜全面剝離。(2-3. Evaluation of adhesion: checkered test) Under the conditions of a droplet size of 7pL and a resolution of 600×600dpi, the ink composition is discharged from the inkjet head and coated on the substrate (white PET) The coating film is formed. This inkjet head is an inkjet head mounted on a single-path type inkjet recording device. Using an ultraviolet LED ("NCCU001E" manufactured by Nichia Chemical Industry Co., Ltd.), the total irradiated light amount is 300mJ/cm 2 , and the coating film is irradiated with ultraviolet rays to harden the coating film and form a coating film on the substrate (film thickness 3μm) . As a result, a sample for adhesion measurement was obtained. Next, cross-cut the surface of the coating film of the sample for adhesion measurement, then stick the adhesive sheet ("Cellotape (registered trademark)" made by nichiban) on the side of the adhesive layer, and then pull off the adhesive sheet . The state of the coating film was visually observed. From the observation results, the adhesion was evaluated based on the following evaluation criteria. The evaluations S (particularly good), A (good), and B (good) were judged to be a level at which adhesion is not practically problematic. The evaluation results of adhesion are shown in Table 4. In addition, the evaluation of adhesion was carried out at a temperature of 25°C. (Evaluation Criteria for Adhesion) S (particularly good): No peeling of the coating film at all. A (good): The coating film is slightly peeled off. B (good): The coating film is partially peeled off. C (bad): The coating film on the part where the adhesive sheet is stuck is completely peeled off.
(2-4.塗膜強度之評價：鉛筆硬度試驗) 在液滴大小7pL及解析度600×600dpi的條件下，使墨水組成物由噴墨頭吐出，塗佈於基材(白PET)上形成塗佈膜。此噴墨頭係搭載於單一路徑方式之噴墨記錄裝置的噴墨頭。使用紫外線LED(日亞化學工業公司製「NCCU001E」)，以總照射光量成為300mJ/cm2 ，對塗佈膜照射紫外線，使塗佈膜硬化，在基材上形成塗膜(膜厚3μm)。結果得到塗膜強度測量用試料。測量如此硬化之塗膜強度測量用試料的鉛筆硬度，以下述基準評價。又，依據日本工業規格(JIS)K5400所規定之鉛筆硬度的測量方法，使用表面性試驗機(新東科學公司製「HEIDON-14DR」)測量。評價S(特別良好)、A(良好)及B(良)判斷為塗膜強度在實用上無問題的水準。評價結果如表4所示。 (塗膜強度之評價基準)(2-4. Evaluation of coating film strength: pencil hardness test) Under the conditions of a droplet size of 7pL and a resolution of 600×600dpi, the ink composition is discharged from the inkjet head and coated on the substrate (white PET) The coating film is formed. This inkjet head is an inkjet head mounted on a single-path type inkjet recording device. Using an ultraviolet LED ("NCCU001E" manufactured by Nichia Chemical Industry Co., Ltd.), the total irradiated light amount is 300mJ/cm 2 , and the coating film is irradiated with ultraviolet rays to harden the coating film and form a coating film on the substrate (film thickness 3μm) . As a result, a sample for coating film strength measurement was obtained. The pencil hardness of the sample for measuring the strength of the coating film hardened in this way was measured, and evaluated based on the following criteria. In addition, it was measured using a surface tester (“HEIDON-14DR” manufactured by Shinto Scientific Co., Ltd.) in accordance with the pencil hardness measurement method prescribed by Japanese Industrial Standards (JIS) K5400. S (particularly good), A (good), and B (good) were evaluated as a level at which the coating film strength was judged to be practically no problem. The evaluation results are shown in Table 4. (Evaluation criteria of coating film strength)
S(特別良好)：鉛筆硬度為4H以上。 S (particularly good): The pencil hardness is 4H or more.
A(良好)：鉛筆硬度為3H以上未達4H。 A (good): The pencil hardness is 3H or more but not 4H.
B(良)：鉛筆硬度為HB以上未達3H。 B (good): The pencil hardness is higher than HB and less than 3H.
C(不良)：鉛筆硬度未達HB。 C (bad): The pencil hardness does not reach HB.
如表1所示，墨水組成物(A-1)~(A-7)含有聚合性化合物與光聚合起始劑。聚合性化合物包含(甲基)丙烯酸酯類(I)與、單官能單體與、多官能(甲基)丙烯酸單體。單官能單體為單官能(甲基)丙烯酸單體及丙烯醯胺系單體之中之至少1種。單官能單體之含有率係包含於1%以上9%以下之範圍內的數值。多官能(甲基)丙烯酸單體之含有率係包含於10%以上40%以下之範圍內的數值。單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃以上。多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度為30℃ 以上。 As shown in Table 1, the ink compositions (A-1) to (A-7) contain a polymerizable compound and a photopolymerization initiator. The polymerizable compound includes (meth)acrylates (I), monofunctional monomers, and polyfunctional (meth)acrylic monomers. The monofunctional monomer is at least one of a monofunctional (meth)acrylic monomer and an acrylamide-based monomer. The content of the monofunctional monomer is a value included in the range of 1% to 9%. The content rate of the polyfunctional (meth)acrylic monomer is a value included in the range of 10% to 40%. The glass transition temperature of the monofunctional (meth)acrylic monomer polymer is 30°C or higher. The glass transition temperature of the polymer of polyfunctional (meth)acrylic monomer is 30℃ the above.
如表4所示，墨水組成物(A-1)~(A-7)中，黏度為10.5mPa．s以下，PII值為1.83以下，密著性之評價均為A(良好)，塗膜強度之評價為S(特別良好)或A(良好)。 As shown in Table 4, the ink composition (A-1)~(A-7) has a viscosity of 10.5mPa. s or less, the PII value is 1.83 or less, the adhesion evaluation is A (good), and the coating film strength evaluation is S (particularly good) or A (good).
如表2所示，墨水組成物(B-1)~(B-2)不含(甲基)丙烯酸酯類(I)。墨水組成物(B-3)中，單官能單體之含有率大於9%。墨水組成物(B-1)~(B-2)及(B-4)~(B-7)中，多官能(甲基)丙烯酸單體之含有率未達10%或大於40%。墨水組成物(B-4)~(B-5)中，單官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg為未達30℃。墨水組成物(B-8)~(B-9)中，多官能(甲基)丙烯酸單體之聚合物之玻璃轉移溫度Tg為未達30℃。 As shown in Table 2, the ink compositions (B-1) to (B-2) do not contain (meth)acrylates (I). In the ink composition (B-3), the monofunctional monomer content is greater than 9%. In the ink compositions (B-1)~(B-2) and (B-4)~(B-7), the content of the polyfunctional (meth)acrylic monomer is less than 10% or more than 40%. In the ink compositions (B-4) to (B-5), the glass transition temperature Tg of the polymer of the monofunctional (meth)acrylic monomer is less than 30°C. In the ink compositions (B-8) to (B-9), the glass transition temperature Tg of the polymer of the polyfunctional (meth)acrylic monomer is less than 30°C.
如表4所示，墨水組成物(B-1)~(B-2)、(B-4)~(B-5)及(B-7)~(B-9)中，黏度為13.1mPa．s以上。墨水組成物(B-1)~(B-3)及(B-8)中，PII值為2.00以上。墨水組成物(B-4)~(B-6)及(B-8)~(B-9)中，密著性為C(不良)。墨水組成物(B-1)~(B-9)，均未完全滿足黏度為10.5mPa．s以下，PII值為未達2.00，密著性之評價S(特別良好)或A(良好)及塗膜強度之評價S(特別良好)或A(良好)。 As shown in Table 4, the ink composition (B-1)~(B-2), (B-4)~(B-5) and (B-7)~(B-9) have a viscosity of 13.1mPa . s above. In the ink compositions (B-1) to (B-3) and (B-8), the PII value is 2.00 or more. In the ink compositions (B-4) to (B-6) and (B-8) to (B-9), the adhesion is C (poor). Ink composition (B-1)~(B-9), none of them fully satisfy the viscosity of 10.5mPa. Below s, the PII value is less than 2.00, the adhesion evaluation S (particularly good) or A (good) and the coating film strength evaluation S (particularly good) or A (good).
由以上可知，墨水組成物(A-1)~(A-7)相對於墨水組成物(B-1)~(B-9)，其墨水之吐出安定性及安全性較優異，且所得之塗膜之密著性及強度優異。 From the above, it can be seen that the ink composition (A-1)~(A-7) has better ink discharge stability and safety than the ink composition (B-1)~(B-9), and the resulting The coating film has excellent adhesion and strength.
本發明之光硬化型噴墨記錄用墨水組成物，適用於與其他之光硬化型噴墨記錄用墨水組成物一同作為噴墨記錄用墨水套組。The photo-curable ink composition for inkjet recording of the present invention is suitable for use as an ink set for inkjet recording together with other photo-curable ink composition for inkjet recording.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201345738A (en) * | 2012-04-27 | 2013-11-16 | Seiko Epson Corp | Printing apparatus and printing method |
| JP2014058622A (en) * | 2012-09-18 | 2014-04-03 | Ricoh Co Ltd | Active energy ray-curable ink, active energy ray-curable process liquid, and inkjet recording method |
| CN106189502A (en) * | 2012-06-06 | 2016-12-07 | 爱克发印艺公司 | Radiation curable inkjet ink and industrial inkjet printing process |
| JP2017095531A (en) * | 2015-11-18 | 2017-06-01 | サカタインクス株式会社 | Ink composition for photosetting inkjet printing |
| CN107541113A (en) * | 2016-06-29 | 2018-01-05 | 精工爱普生株式会社 | Radiation curable inkjet compositions and ink jet recording method |
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| ES2361861T3 (en) * | 2007-10-24 | 2011-06-22 | Agfa Graphics N.V. | CURABLE LIQUIDS AND INKS FOR APPLICATIONS TO FOOD TOYS AND PACKAGING. |
| JP5803258B2 (en) * | 2010-09-30 | 2015-11-04 | セイコーエプソン株式会社 | UV-curable ink composition for ink jet and ink jet recording method |
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| JP6134090B2 (en) * | 2011-03-16 | 2017-05-24 | セイコーエプソン株式会社 | UV curable ink composition for inkjet |
| JP5927818B2 (en) | 2011-09-14 | 2016-06-01 | セイコーエプソン株式会社 | Photocurable ink composition for ink jet recording and ink jet recording method |
| JP6236768B2 (en) * | 2012-04-27 | 2017-11-29 | セイコーエプソン株式会社 | Ink jet recording method and ink jet recording apparatus |
| JP5939114B2 (en) | 2012-09-28 | 2016-06-22 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable inkjet ink composition |
| JP6126378B2 (en) | 2012-12-26 | 2017-05-10 | サカタインクス株式会社 | UV-LED photocurable ink composition for inkjet printing |
| JP6065733B2 (en) * | 2013-04-25 | 2017-01-25 | 東洋インキＳｃホールディングス株式会社 | Ink for inkjet |
| JP5748014B1 (en) * | 2014-03-26 | 2015-07-15 | 東洋インキＳｃホールディングス株式会社 | Active energy ray curable inkjet ink |
| JP6671838B2 (en) * | 2014-08-29 | 2020-03-25 | 東洋アルミニウム株式会社 | Packaging material and manufacturing method thereof |
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| JP6265286B2 (en) * | 2017-01-18 | 2018-01-24 | セイコーエプソン株式会社 | UV curable ink composition for inkjet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106189502A (en) * | 2012-06-06 | 2016-12-07 | 爱克发印艺公司 | Radiation curable inkjet ink and industrial inkjet printing process |
| JP2014058622A (en) * | 2012-09-18 | 2014-04-03 | Ricoh Co Ltd | Active energy ray-curable ink, active energy ray-curable process liquid, and inkjet recording method |
| JP2017095531A (en) * | 2015-11-18 | 2017-06-01 | サカタインクス株式会社 | Ink composition for photosetting inkjet printing |
| CN107541113A (en) * | 2016-06-29 | 2018-01-05 | 精工爱普生株式会社 | Radiation curable inkjet compositions and ink jet recording method |
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