CN100569877C - Branched structure compound containing UV crosslinking reactive group and application thereof - Google Patents

Branched structure compound containing UV crosslinking reactive group and application thereof Download PDF

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CN100569877C
CN100569877C CN 200510137412 CN200510137412A CN100569877C CN 100569877 C CN100569877 C CN 100569877C CN 200510137412 CN200510137412 CN 200510137412 CN 200510137412 A CN200510137412 A CN 200510137412A CN 100569877 C CN100569877 C CN 100569877C
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CN1990620A (en
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吴凤美
张信贞
张立中
林家群
林弘晔
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财团法人工业技术研究院;新力美科技股份有限公司
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Abstract

本发明涉及一种含多UV交联反应基的球形分枝状结构化合物,其核心为异三聚氰酸酯基团,其骨架含有多个极性官能团且末端为UV交联基。 The present invention relates to a compound of spherical structure containing the branched multi UV crosslinking reaction group, the core of heterotrimeric isocyanate groups, whose backbone comprising a plurality of polar functional group and a UV crosslinkable terminal group. 本发明也提供这种化合物的前体,以及多种化合物的应用如粘合促进剂、感光树脂组合物、喷墨墨水,特别是喷墨墨水于喷印后的硬度及水稳定性可大幅提升。 The present invention also provides a precursor of such compounds, and the application of a variety of compounds, such as adhesion promoter, a photosensitive resin composition, inkjet inks, especially the water hardness and stability after printing in the inkjet ink may be dramatically .

Description

含多UV交联反应基的分枝状结构化合物及其应用 Containing multiple UV crosslinking reactive group of the branched structure of the compound and its Applications

技术领域 FIELD

本发明涉及一种含多UV交联反应基的球形分枝状结构化合物,进一步特别涉及此化合物于喷墨墨水组合物中的应用。 The present invention relates to a compound of spherical structure containing the branched multi UV crosslinking reaction group, in particular, further relates to the use of this compound in the inkjet ink composition.

背景技术 Background technique

多种喷墨技术已应用于快速印刷上,较常见的几个方法包括连续喷墨法(continuous ink jet printing)与即需即印法(drop-on-demand)。 Inkjet technology has been applied to a variety of fast printing, several of the more common methods include the continuous inkjet method (continuous ink jet printing) and printed on-demand method (drop-on-demand). 前者可利用电压产生偏斜的原理如双向偏斜与多向偏斜,依据带电时喷墨和不带电时不喷墨的方式供墨。 The former may utilize the principle of deflection voltage generating multi bidirectional deflection and deflection, based on the charged ink non-discharge of ink jet and uncharged manner. 后者的原理通常为下述两种方式:移动压电变压器产生压力波以形成墨滴,通称压电法,另一种以热脉冲形成墨滴,通称为热泡式。 The latter principle is generally the following two ways: moving the piezoelectric transformer generates a pressure wave to form a droplet, known piezoelectric method, a thermal pulse to form another droplet, known as thermal bubble.

墨水的组成可粗分为水溶型、油溶型、溶剂型、热熔型与光固化型。 Composition of ink is roughly divided into water-soluble type, type of oil-soluble, solvent-based, hot melt and photocurable. 由于前两型的机制相当依赖墨水的渗透吸收与干燥,后三者较适合运用于金属、陶瓷、塑胶等不吸墨的材质上。 Since the first two types of ink penetration mechanism heavily dependent absorption and drying, after three more suitable for the material used in the ink does not absorb metals, ceramics, plastics and the like. 本发明特别有关于光固化型的喷墨墨水,其最重要也最基本的专利为美国专利第4,303,924号已揭示运用多种含碳碳双键的低分子量分子为光固化成分。 In particular the present invention relates to a photocurable inkjet ink, which is also the most important basic patent U.S. Pat. No. 4,303,924 has disclosed the use of a variety of carbon-carbon double bonds in the molecule is a low molecular weight photo-curable component. 其他如中国台湾省专利第207302号所揭示的可光固化墨水,或中国台湾省专利第207308号所揭示,是运用含有碳碳双键的单体、寡聚物、或树脂作为颜料的可光固化成分,并将该颜料运用于LCD彩色滤光片的制作。 Others such as China Taiwan Province Patent No. 207,302 disclosed a photocurable ink or China Taiwan Province Patent No. 207,308 disclosed, is the use of carbon-containing monomer, oligomer, or resin as a pigment may be light curing component, and the pigment used in making LCD color filter. 美国专利第4,680,368号已揭示一种光固化墨水成分包括一多胺甲酸乙酯。 U.S. Patent No. 4,680,368 has disclosed an optical component comprising a polyamine curing ink-carboxylate. 欧洲专利第A0465039与第A0540203也揭示含多种含可聚合单体的光固化墨水。 European Patent A0465039 A0540203 also discloses and the second containing more photocurable ink containing a polymerizable monomer. 这些专利都难以避免交联度不足所造成的附着力不足,耐化学性、耐热性不足,脆化等问题。 These patents are difficult to avoid the lack of cross-linking degree caused by insufficient adhesion, chemical resistance, insufficient heat resistance, embrittlement problems. 除此之外,过高的流动性将造成颜料分散时稳定度的问题。 In addition, excessive liquidity will cause a problem when the pigment dispersion stability. 但若将链状可光固化成分拉长增加其稳定度,又会使墨水在喷墨匣的粘度提高,为解决此问题,又必需导入多种可光固化的单体做微调。 However, if the photocurable composition may be elongated linear increase stability, and will increase in viscosity of the inkjet ink cassette to solve this problem, but also necessary to import more photocurable monomer may be adjusted finely. 这在后续的改良以及品质的控制上都会造成麻烦,进而提高成本。 This will cause trouble on the follow-up and improvement of quality control, thereby increasing costs.

因此如何进一步设计一个解决上述问题的可光固化分子,进而应用于喷墨墨水,便是亟需解决的一个问题。 Therefore, how to design further molecules of a photocurable solve the above problems, and further applied to an inkjet ink, is a problem to be resolved. 枝状体(dendrimer)由于具有大量可修饰的支链,近几年已被广泛运用于制药、合成、超分子化学等领域中。 Dendrite (a dendrimer) can be modified because of a large number of branched, it has been widely used in recent years the field of pharmaceuticals, synthetic, supramolecular chemistry and the like. 枝状体在可光固化墨水的应用上,包括US2005/0147834 A1所揭示的多酯类胺化物,但如同本领域大部分的技术人员一样,该专利的支链末端也为胺化物,且无法进行光固化反应。 Dendrimer in the application photocurable ink comprising US2005 / 0147834 A1 disclosed multi-ester amine compounds, but as most of the skilled artisan as branched end of this patent is also an amine compound, and can not be photocuring reaction. US 6,221,933 B1揭示的枝状物具有末端胺基,改善墨水喷印于玻璃表面的耐湿性,且可用碱水洗净喷印的墨水以回收玻璃。 US 6,221,933 B1 disclosed dendrites having terminal amine, to improve the printing ink to the glass surface of the moisture resistance, and can be used in ink jet printing alkaline cleaning recycled glass. 即使如US 6,300,388 B1所揭示的枝状物虽具有可进行光固化反应的碳碳双键,其支链末端仍为胺化物,但置于分子内部而非末端的双键,将造成光固化反应的立体障碍并降低墨水固化的速率与程度。 Even if, as disclosed in US 6,300,388 B1 dendrites although having a carbon double bond may be carried out photocuring reaction, a branched chain ends which still amine compounds, but not the double bond is placed inside the end of the molecule, the resulting photocuring reaction steric hindrance and reduce the rate and degree of cure of the ink. 此外也有许多人将枝状体的末端悬吊染料发色基,其中之一是US 2003/0096885 A1,虽可改善喷墨性,增强耐光、耐水、耐污等性质,仍如同US 6,300,388 B1缺乏可光固化的末端官能团。 There are also many dendrite tip suspending the dye chromophores, one of which is US 2003/0096885 A1, although the ink jet properties can be improved, enhancing the light fastness properties, water resistance, stain, etc. still lacking as US 6,300,388 B1 photocurable terminal functional group.

枝状体的核心种类是一个基本但重要的选择。 The core of the dendrimer is a kind of basic but important choice. 一般是以平面分子如三嗪(triazine)或苯做为中心分子,但因上述两者的芳香性与平面性不易造成三维立体四面八方的交联,而降低物性如硬度、耐光性。 As it is generally planar molecules triazine (triazine) or benzene as the core molecule, but with the plane of the above-described aromatic both difficult to cause three-dimensional cross-linking in all directions, while reducing the physical properties such as hardness, light resistance. 因此出现许多这方面的改良,其中之一为美国专利公告号US 2004/0163570 A1,以对称的硅氧笼(cage)外接多个支链成为一多链的球状物(非枝状体),其末端为碳碳双键以进行光固化。 Thus many modifications occur in this area, one of which is U.S. Patent Publication No. US 2004/0163570 A1, silicone symmetrical cages (Cage) External branched into a plurality of multi-chain of balls (non dendrites), carbon-terminus thereof for photocuring. 该专利的大核心虽然可避免立体障碍的问题,但其过大的硅氧笼以及不寻常的化学特性,在进一步的延伸及改良上将比以有机分子为核心的枝状物更为困难。 While the core of this patent a large steric hindrance problems can be avoided, but it is too large cage and silicone unusual chemical properties, on further extension and improvement to organic molecules than the core of the dendrites more difficult.

发明内容 SUMMARY

有鉴于此,本发明特别提供一含多UV交联反应基的球形分枝状结构化合物,包含:一核心,其结构为异三聚氰酸酯基团;以及多个分枝状取代基,其骨架含有多个极性官能团,且末端为UV交联反应基。 Accordingly, the present invention particularly provides a compound spherical branched structure containing multiple UV crosslinkable group, comprising: a core, which is a heterotrimeric structure of isocyanate groups; and a plurality of branched substituents, whose backbone comprising a plurality of polar functional groups, and the terminal group is a UV crosslinking reaction.

本发明的含多UV交联反应基的球形分枝状结构化合物中,该多个分枝状取代基,其骨架还包含多个芳香基。 Multi UV crosslinking reactive group-containing spherical branched structures of the compounds of the present invention, the plurality of branched substituents, which backbone further comprises a plurality of aromatic groups.

本发明的含多UV交联反应基的球形分枝状结构化合物中,该UV交联反应基包括碳碳双键。 Multi UV crosslinking reactive group-containing spherical branched structures of the compounds of the present invention, the UV crosslinking reactive group comprises a carbon-carbon double bond.

本发明的含多UV交联反应基的球形分枝状结构化合物,其结构可如下: Containing multiple UV crosslinking reactive group spherical branched structures of the compounds of the present invention, the structure may be as follows:

式(I) Formula (I)

式(I)中,R 1为环氧烷烃开环后的链段;Ar为具有多个极性官能团的芳香基;以及R 2为UV交联反应基,n为1~5的整数。 In the formula (I), R 1 is the ring-opened alkylene oxide segment; Ar is an aromatic group having a plurality of polar functional groups; and R 2 is a UV crosslinking reaction group, n is an integer of 1 to 5.

上述式(I)中,该Ar具有的这些极性官能团可为酯基与羟基。 In the above formula (I), in which Ar has the polar functional group may be a hydroxyl group and an ester group.

上述式(I)的化合物,其具体结构可为: Compound of formula (I), which may be a specific configuration:

式(II) Of formula (II)

本发明还提供一种球形分枝状结构化合物,其为上述含多UV交联反应基的球形分枝状结构化合物的前体,其结构如下: The present invention also provides a compound spherical branched structure, the branched structure of the spherical precursor compound which is UV cross-linked multi-containing reactive group has the following structure:

式(III) Of formula (III)

式(III)中,R 1为环氧烷烃开环后的链段,Ar为具有多个极性官能团的芳香基。 In formula (III), R 1 is the ring-opened alkylene oxide segment, Ar is an aromatic group having a plurality of polar functional groups.

上述式(III)中,该Ar还可包括下列至少一种取代基:羧酸基、羟基、或胺基。 In the above formula (III), the Ar substituents may further comprise at least one of the following groups: a carboxylic acid group, a hydroxyl group, or amine groups.

上述式(III)的化合物,其具体结构可为: Compound of the formula (III), which may be a specific configuration:

式(IV) Formula (IV)

本发明还包括一种感光树脂组合物,包括:a)0.02~25wt%感光引发剂;b)1~99.8wt%上述的具多UV交联反应基的球形分枝状结构化合物;c)0~98.98wt%其他感光反应物。 The present invention also includes a photosensitive resin composition, comprising: a) 0.02 ~ 25wt% photosensitive initiator; spherical branched structure of the compound b) 1 ~ 99.8wt% with the aforementioned plurality of UV crosslinking reactive group; c) 0 ~ 98.98wt% photosensitive other reactants.

本发明还包括一种喷墨墨水组合物,包括a)0.5~50wt%的溶媒;b)0.5~20wt%的色料;c)1~90wt%的光固化单体;d)1~40wt%上述的具多UV交联反应基的球形分枝状结构化合物。 The present invention further comprises an ink jet ink composition comprising a) 0.5 ~ 50wt% of solvent; b) 0.5 ~ 20wt% of pigment; c) 1 ~ 90wt% of the photocurable monomer; d) 1 ~ 40wt% spherical branched structure of the compound having the above-described multi UV crosslinking reactive group.

本发明的喷墨墨水组合物,还可包括e)0.1~25wt%的光引发剂。 The inkjet ink composition of the present invention may further comprise e) 0.1 ~ 25wt% of a photoinitiator.

本发明的喷墨墨水组合物中,该溶媒包括水、溶剂、或单体。 The inkjet ink composition according to the present invention, the vehicle including water, solvent, or monomers.

本发明的喷墨墨水组合物,其粘度介于1~35cps,表面张力介于20~50毫牛顿/米,硬度介于4H~4B。 The inkjet ink composition of the present invention, a viscosity of between 1 ~ 35cps, a surface tension between 20 to 50 milliNewtons / meter, hardness range 4H ~ 4B.

本发明的含多UV交联反应基的球形分枝状结构化合物,可用于粘合促进剂、感光树脂组合物、喷墨墨水,特别是包含本发明的含多UV交联反应基的球形分枝状结构化合物的喷墨墨水,其于喷印后的硬度及水稳定性可大幅提升,且具有良好的耐擦性以及附着力。 The present invention containing a multi-branched structure compound spherical UV crosslinking groups, adhesion promoters may be used, a photosensitive resin composition, an inkjet ink, containing in particular the present invention comprising a plurality of UV-crosslinking reaction of the spherical sub-group inkjet ink branched structure compound, water hardness and stability after printing can be significantly improved, and good abrasion resistance and adhesion.

附图说明 BRIEF DESCRIPTION

图1A是实施红墨3的实际喷墨图示。 FIG 1A is a practical embodiment of red ink in the ink jet 3 illustrated.

图1B是实施绿墨3的实际喷墨图示。 FIG 1B is a green ink practical embodiment of an inkjet 3 illustrated.

图1C是实施蓝墨3的实际喷墨图示。 1C is a practical embodiment of an inkjet ink Blue 3 illustrated.

图2A是比较红墨3的实际喷墨图示。 2A is actual inkjet ink Redder 3 is illustrated.

图2B是比较绿墨3的实际喷墨图示。 FIG 2B is a more practical ink jet ink green 3 illustrated.

图2C是比较蓝墨3的实际喷墨图示。 FIG. 2C is a more practical ink jet ink Blue 3 illustrated.

具体实施方式 Detailed ways

本发明特别提供一含多UV交联反应基的球形分枝状结构化合物,包含一核心,其结构为异三聚氰酸酯基团;多个分枝状取代基,其骨架含有多个芳香基、多个极性官能团,且末端为UV交联反应基。 The present invention particularly provides a compound spherical branched structure containing multiple UV crosslinking group comprising a core having the structure heterotrimeric isocyanate groups; a plurality of branched substituents, which contain a plurality of aromatic backbone group, more polar functional groups, and the terminal group is a UV crosslinking reaction. 含多UV交联反应基的球形分枝状结构化合物所具有的极性官能团包含酰胺基、胺基、酯基、羟基、或酮基,本发明的较佳实施例为酯基、羟基与胺基,这些极性官能团可增加墨水喷墨成型后的附着性、硬度及耐擦性。 Spherical branched structure compound having a polar functional group containing a plurality of UV crosslinkable group comprises an amide group, an amine group, an ester group, a hydroxyl group, or keto group, the preferred embodiment of the present invention is an ester group, a hydroxyl group with an amine group, the adhesion of these polar functional group forming an ink jet ink can be increased, hardness and abrasion resistance. 芳香基包括苯基、吡啶基、萘基、蒽基,较佳为苯基。 Aromatic groups include phenyl, pyridyl, naphthyl, anthryl, preferably phenyl. 末端的UV交联反应基,不似插置于骨架中的UV交联反应基具有不同的化学环境与立体障碍,因此可使该分子快速并均匀的进行光固化反应。 UV-terminated cross-linking reaction, unlike interposed backbone UV crosslinking reactive groups having different chemical environments and steric hindrance, so that the molecule can be quickly and uniformly photocuring reaction. 上述的UV交联反应基可包括碳碳三键、碳碳双键、及其他合适的官能团,本实验的较佳实施例为碳碳双键。 UV crosslinking reaction of the above groups may include a carbon-carbon triple bond, carbon-carbon double bond, and other appropriate functional groups, preferred embodiment of the present experiment is a carbon-carbon double bond. 较佳的含多UV交联反应基的球形分枝状结构化合物具有18个酯基、3个胺基、与15个羟基,且末端具有12个碳碳双键。 Preferred multi-containing UV-crosslinking reactive group spherical branched structure of the compound having an ester group 18, group 3, and 15 hydroxyl groups and having a terminal carbon-carbon double bonds 12. 酯基、胺基、与羟基的排列方式并不受限于一定顺序或规则,本领域技术人员自可随其需要调整极性官能团的种类与数目,只要末端具有UV交联反应基以进行光固化反应,比如下列结构的化合物: An ester group, amine group arrangement, and a hydroxyl group is not limited to a certain sequence or rule, one skilled in the art from the type and number can be adjusted as a function of its polar functional groups, as long as the terminal group having a crosslinking reaction to UV light curing reaction, such as compounds of the following structure:

式(I) Formula (I)

R 1为环氧烷烃开环后的链段;Ar为具有多个极性官能团的芳香基;R 2是UV交联反应基,n是1~5的整数。 R 1 is the ring-opened alkylene oxide segment; Ar is an aromatic group having a plurality of polar functional groups; R 2 is UV crosslinking reaction group, n is an integer of 1 to 5.

较佳实施例包括一结构如下: The preferred embodiment includes a structure as follows:

式(II) Of formula (II)

本发明提供了一种核心为异三聚氰酸酯基团的枝状物,可做为具多UV交联反应基的球形分枝状结构化合物的前体,其结构如下: The present invention provides a core for the dendrimers heterologous trimerization of isocyanate groups, may be branched as a spherical precursor compound having the structure of multi UV crosslinking reactive group of the following structure:

式(III) Of formula (III)

核心结构为异三聚氰酸酯基团;R 1为环氧烷烃开环后的链段;Ar为具有多个极性官能团的芳香基,这些极性官能团包括羧酸基、羟基、或胺基,芳香基包括苯基、吡啶基、萘基、蒽基,较佳为苯基。 The core structure is a heterotrimeric isocyanate groups; R 1 is the ring-opened alkylene oxide segment; Ar is an aromatic group having a plurality of polar functional groups, such polar functional groups include a carboxylic acid group, a hydroxyl group, or an amine group, an aromatic group include phenyl, pyridyl, naphthyl, anthryl, preferably phenyl. 此前体并非完成本发明目的的唯一途径,分子间的排列仍具有其他可能。 Previously the only way to accomplish the objectives of the present invention is not a member, the arrangement between the molecules may have other yet. 值得注意的是,上述前体也可进行其他枝状化(dendrimerize)反应后,再进行后续步骤使其末端具有UV交联反应基,较佳的前体具有以下的结构式: Notably, of the precursor may be performed after treeing (dendrimerize) other reaction, and then the subsequent step of its distal end with a UV crosslinkable group, preferably a precursor having the structural formula:

式(IV) Formula (IV)

枝状物可选择的合成方式主要分两种:由内向外的发散式(divergent)和由外向内的收敛式(convergent)。 Alternatively dendrites are two main methods of synthesis: convergent (Convergent) diverging (divergent) from outside to inside and from the inside outward. 若核心与末端官能团间的“代”(generation)较多,则采用收敛式较佳;若代较少,则以较单纯的发散式为主;也可以发散式建立较少代的核心后,与收敛式合成的末端官能团键结形成目标分子。 If "generation" between the core and the terminal functional group (Generation) are more preferred the use of convergent; if substituting less, more simply places mainly divergent; the less substituted core also be divergent established, and convergent synthetic terminal functional group bonded to form the target molecule. 本发明由于代较少,因此以发散式为主要的合成策略,但也可以收敛式或两者均有的方式合成。 The present invention, due to less generation diverging therefore mainly synthetic strategies, but there may be converging or both synthesized. 举例来说,含有核心为异三聚氰酸酯基团的起始物包括三氯异三聚氰酸(trichloroisocyanuric acid)、三(2,3-环氧丙基)-异三聚氰酸酯(tris(2,3-epoxypropyl)isocyanurate)、三烯丙基异三聚氰酸酯(triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione),较佳的起始物为三(2,3-环氧丙基)-异三聚氰酸酯。 For example, starting from a core containing iso cyanurate groups include iso-trichloro cyanuric acid (trichloroisocyanuric acid), tris (2,3-epoxypropyl) - iso cyanurate (tris (2,3-epoxypropyl) isocyanurate), triallyl cyanurate (triallyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), more excellent starting from tris (2,3-epoxypropyl) - iso cyanurate. 将三(2,3-环氧丙基)-异三聚氰酸酯于溶剂下与一亲核性(Nucleophile)试剂进行开环反应,该亲核性试剂包括下列化合物: Tris (2,3-epoxypropyl) - iso cyanurate ring-opening reaction with a nucleophilic (nucleophile) reagent in a solvent, the nucleophilic reagent include the following compounds:

式(V) Of formula (V)

其中C n为一C 1 -C 10的烷基,Nu为反应性较仲胺反应性差的亲核性官能团,包括羟基、以保护基保护的伯胺(若不保护其反应性将高于仲胺),较佳的Nu为羟基。 Wherein C n alkyl group a C 1 -C 10 is, Nu is a reactive than secondary amine poorly nucleophilic functional groups including hydroxyl, protecting the primary amine group protected (if not protect its reactivity higher than secondary amines) , Nu is preferably a hydroxyl group. 该亲核性试剂也包括其他可能,比如1,3,5-三胺基苯、1,3,5-三羟基苯、或其他具有对称性三亲核性官能团的化合物。 The nucleophile may also include other, such as 1,3,5-triamino benzene, 1,3,5-trihydroxybenzene, or other compounds having symmetric three nucleophilic functional group.

进行上述反应后,得到一末端为亲核性反应基的枝状物中间体。 After the above reaction, to give a nucleophilic end group is the reaction intermediate dendrimer. 将该中间体与一具有多个极性官能团的芳香基进行反应,若中间体的末端官能团为羟基,芳香基的极性官能团为羧酸或酸酐时,则进行一酯化反应。 The intermediate with a plurality of aromatic groups having a polar functional group is reacted, if the intermediate terminal functional group is a polar functional hydroxyl group, an aromatic group or a carboxylic acid anhydride, an esterification reaction is performed. 若中间体的末端官能团为伯胺(先进行去保护反应),芳香基的极性官能团为羧酸或酸酐时,则进行一酰胺化反应。 If the intermediate terminal primary amine functional groups (first deprotection reaction), an aromatic group, a polar functional group is a carboxylic acid or anhydride when, an amidation reaction is performed. 具有多个极性官能团的芳香基包括1,2,3-苯三甲酸酐、1,2,4-苯三甲酸酐、1,3,5-三甲酸苯。 An aromatic group having a plurality of polar functional groups include 1,2,3-benzene tricarboxylic acid anhydride, trimellitic anhydride, benzene 1,3,5-tricarboxylic acid. 具有极性官能团的芳香基还包括下列结构: An aromatic group having a polar functional group further comprises the following structure:

式(VI) Of formula (VI)

C m为一具有极性官能团如酯基或酰胺基的C 1 -C 10的烷基。 C m is a functional group having a polar group such as an ester or amide group is C 1 -C 10 alkyl group. n为1-6的整数,X为一卤基,好与上述的亲核性官能团进行取代反应。 n is an integer from 1-6, X is a halo, a good substitution reaction with the above-described nucleophilic functional group.

最后,芳香基上其他未反应的极性官能团如羧酸基与一末端具有UV交联反应基的化合物进行反应,则得到一具多UV交联反应基的球形分枝状结构化合物。 Finally, the compounds of UV crosslinking reactive group other polar functional group such as a carboxylic acid group unreacted aromatic group and having one end of the reaction, to give a compound of the structure of a multi-branched spherical UV crosslinking reactive group. 这些极性官能团并非与UV交连反应基进行反应,而是与该化合物的其他官能团进行反应,比如环氧基(进行开环反应)、卤基(进行取代反应)。 These are not the polar functional group with UV cross-linking reactive groups, but reacted with other functional groups on the compound, such as an epoxy group (ring opening reaction), halo (substitution reaction). 若具有极性官能团的芳香基其结构为下述式(VI),则末端具有UV交联反应基的化合物必需具有亲核性官能团如羟基或胺基以进行取代反应,而非环氧基或卤基。 If an aromatic group having a polar functional group having the structure by the following formula (Vl), UV cross-linking reaction a compound of the terminal group has the required nucleophilic functional groups such as hydroxyl or amine groups in a substitution reaction rather than an epoxy group, or halo.

式(VI) Of formula (VI)

简言之,只要是能以异三聚氰酸酯基团为核心,可UV交联官能团为末端,且以多种极性官能团为骨架的枝状物,在合理的反应条件下,均在本发明的设计中,而不受限于上述的合成策略与下列实施例。 In short, as long as capable of heterotrimeric isocyanate groups as the core, UV cross-linkable functional group terminated, and a more polar functional groups in dendrimers skeleton, under reasonable reaction conditions were design of the present invention, without being limited to the synthetic strategy with the following examples.

本发明也包括将多UV交联反应基的球形分枝状结构化合物应用于粘合促进剂,可用于纸张、金属、陶瓷、木材、玻璃、塑胶等材料粘合时的粘合剂。 The present invention also includes a plurality of spherical branched structure compound UV-crosslinking reactive group is applied to adhesion promoter, may be used when the adhesive paper, metal, ceramics, wood, glass, plastic and other materials adhesion.

本发明提供一种感光树脂组合物,包括了0.02~25wt%的感光引发剂与1~99.8wt%的上述具多UV交联反应基的球形分枝状结构化合物及0~98.98wt%其他感光反应物。 The present invention provides a photosensitive resin composition comprising a photosensitive 0.02 ~ 25wt% and the initiator 1 ~ 99.8wt% with the UV-crosslinking reactive group plurality of spherical branched structure compound and the other photosensitive 0 ~ 98.98wt% Reactant. 常见的感光引发剂包括下列分子:安息香基烷基醚(benzoin alkyl ether)、2,2-二甲氧基-2-苯基乙酰苯(2,2-dimethoxy-2-phenylacetophenone)、二苯酮(benzophenone)、五溴一氯环己烷(pentabromomonochlorocyclohexane)、五氯苯(pentachlorobenzene)、多氯联苯(polychlorinated biphenyl)、2-乙基蒽醌(2-ethylanthraquinone)、1-氯乙基萘(1-chloroethylnaphthalene)、2-溴乙基醚(2-bromoethyl ether)、或其他合适的光引发剂。 Common photosensitive initiator molecules include the following: alkyl ether, benzoin (benzoin alkyl ether), 2,2- dimethoxy-2-phenylacetophenone (2,2-dimethoxy-2-phenylacetophenone), benzophenone (benzophenone), a five-bromo-HCH (pentabromomonochlorocyclohexane), PeCB (pentachlorobenzene), PCB (polychlorinated biphenyl), 2- ethylanthraquinone (2-ethylanthraquinone), 1- chloroethyl naphthalene ( 1-chloroethylnaphthalene), 2- bromoethyl ether (2-bromoethyl ether), or other suitable photoinitiators. 其他感光反应物如四甘醇二丙烯酸酯(tetraethylene glycoldiacrylate,TGD),异冰片丙烯酸酯(isobornyl acrylate,IBOA),抑制剂如:1,6-已二醇二丙稀酸酯(1,6-hexanediol diacrylate,HPDA)。 Other photosensitive reactants such as tetraethylene glycol diacrylate (tetraethylene glycoldiacrylate, TGD), isobornyl acrylate (isobornyl acrylate, IBOA), inhibitors, such as: acrylic esters of 1,6-hexanediol di (1,6- hexanediol diacrylate, HPDA). 该感光树脂的应用包括制造光电产品的负光阻。 Application of the photosensitive resin include a negative photoresist for producing optoelectronic products.

本发明提供一种喷墨墨水组合物,包括0.5~50wt%的溶媒,可为;0.5~20wt%的色料;1~90wt%的光固化单体;1~40wt%上述的具多UV交联反应基的球形分枝状结构化合物。 The present invention provides an inkjet ink composition, comprising 0.5 ~ 50wt% of solvent, it may be; 0.5 ~ 20wt% of a colorant; 1 ~ 90wt% of the photocurable monomer; 1 ~ 40wt% with the aforementioned plurality of cross-UV spherical-linking reaction of the branched structure of the compound groups. 将上述组合物搅拌10~20分钟,即可得一喷墨墨水。 The above composition was stirred for 10 to 20 minutes, to give an inkjet ink. 溶剂为可溶其他组合物的有机溶剂,上述的色料包括了染料或颜料,例如Ciba公司所售的Pigment Red 149、Pigment Green 36、或Pigment Blue 15:3,颜料的平均粒径介于70~220nm,较佳为90~200nm。 The solvent soluble organic solvent other compositions, the above-described colorant include a dye or pigment, for example sold by the company Ciba Pigment Red 149, Pigment Green 36, or Pigment Blue 15: 3, the average pigment particle size is between 70 ~ 220nm, preferably 90 ~ 200nm. 光固化单体例如是四甘醇二丙烯酸酯(tetraethylene glycol diacrylate,TGD),异冰片丙烯酸酯(isobornyl acrylate,IBOA),抑制剂如:1,6-已二醇二丙烯酸酯(1,6-hexanediol diacrylate,HPDA),2,6-二叔丁基-4-甲基苯酚(2,6-di-tert-butyl-4-methyphenol,BHT)。 Photocurable monomers, for example, tetraethylene glycol diacrylate (tetraethylene glycol diacrylate, TGD), isobornyl acrylate (isobornyl acrylate, IBOA), inhibitors such as: 1,6-hexanediol diacrylate (1,6- hexanediol diacrylate, HPDA), 2,6- di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methyphenol, BHT). 较佳的实施例中,还包括0.1~15wt%的光引发剂。 Preferred embodiment further includes 0.1 ~ 15wt% of a photoinitiator. 常见的感光引发剂包括下列分子:2-羟基-1-苯基-1-丙酮(2-hydroxy-1-phenyl-propyl-1-one),安息香基烷基醚(benzoin alkyl ether)、2,2-二甲氧基-2-苯基乙酰苯(2,2-dimethoxy-2-phenylacetophenone)、二苯酮(benzophenone)、五溴一氯环己烷(pentabromomonochlorocyclohexane)、五氯苯(pentacjlorobenzene)、多氯联苯(polychlorinated biphenyl)、2-乙基蒽醌(2-ethylanthraquinone)、1-氯乙基萘(1-chloroethylnaphthalene)、2-溴乙基醚(2-bromoethyl ether)、或其他合适的光引发剂。 Common photosensitive initiator molecules include the following: 1-phenyl-2-hydroxy (2-hydroxy-1-phenyl-propyl-1-one), benzoin alkyl ethers (benzoin alkyl ether), 2, 2-dimethylamino-2-phenyl acetophenone (2,2-dimethoxy-2-phenylacetophenone), benzophenone (benzophenone), a five-bromo-HCH (pentabromomonochlorocyclohexane), PeCB (pentacjlorobenzene), PCBs (polychlorinated biphenyl), 2- ethylanthraquinone (2-ethylanthraquinone), 1- chloroethyl naphthyl (1-chloroethylnaphthalene), 2- bromoethyl ether (2-bromoethyl ether), or other suitable photoinitiator.

上述的喷墨墨水组合物粘度介于1~35cps,表面张力介于20~50毫牛顿/米,此粘度范围的墨水在喷出前不会太粘以至于堵塞喷嘴,也不会太稀造成喷出后无法成型。 An inkjet ink composition has a viscosity of between 1 ~ 35cps, a surface tension between 20 to 50 milliNewtons / meter, this viscosity range of the ink before ejection nozzle is not clogged too viscous, it will not cause too thin after molding can not be ejected. 墨水在喷出成型后的硬度介于4H~4B,且具有良好的水稳定性、耐擦性以及附着力(百格测试,Cross-Cut Tester),可喷印于无吸墨的基材如金属、陶瓷、玻璃、塑胶上,其具有良好的硬度与耐刮性。 Ink discharge forming between the hardness 4H ~ 4B, and good water stability, abrasion resistance and adhesion (tested per cell, Cross-Cut Tester), the ink jet printing on non-absorbing substrates such as metal, ceramic, glass, plastic, which has a good hardness and scratch resistance. 再者,喷印后照射UV光时,由于可照光固化的UV交联反应基可增加与其他单体或寡聚物的聚合反应,可进一步增进列印物的保存性和物性。 Moreover, when irradiated with UV light after the printing, since the photocurable UV crosslinking reactive group can be increased as the polymerization with other monomers or oligomers, may further enhance the physical properties and print preservability thereof.

制备例一: Preparation Example:

第一阶段: The first stage:

将2.55g(10mmol)三(2,3环氧丙基)-异三聚氰酸酯(TGIC,tris(2,3-epoxypropyl)isocyanurate)与3.75g(36mmol,1.2当量)二乙醇胺(diethanolamine)于室温下搅拌三小时后产生剧烈放热,将温度控制于120℃以下,待放热结束后将反应温度控制于100℃并持续反应10小时,以FT-IR(傅立叶变换红外光谱)追踪反应,待3050~3000cm -1 (NH的信号)与950~810cm -1 (环氧基的信号)的信号消失即表示反应完成,其反应式如下图: The 2.55g (10mmol) tris (2,3-epoxypropyl) - iso cyanurate (TGIC, tris (2,3-epoxypropyl) isocyanurate) and 3.75g (36mmol, 1.2 eq.) Diethanolamine (Diethanolamine) after stirring at room temperature for three hours with vigorous heat generation, the temperature was controlled at 120 deg.] C or less, after the completion of the exothermic reaction temperature was controlled at 100 deg.] C and the reaction was continued for 10 hours to FT-IR (Fourier transform infrared spectroscopy) Tracking reaction , -1 (NH signals) to be 3050 ~ 3000cm with 950 ~ 810cm -1 (signal epoxy group) means that the reaction was complete signal disappears, the reaction is as follows:

(反应式1) (Scheme 1)

第二阶段: second stage:

将17.28g(90mmol,1.5当量)1,2,4-苯三甲酸酐(trimelliticanhydride,TMA)与100mL的N-甲基-α-吡咯烷酮(NMP,N-methyl-α-pyrrolidone),加入上述反应并于90℃反应4小时,以FT-IR追踪反应,待1780cm -1 (酸酐的信号)消失即表示反应完成,其反应式如下图: The 17.28g (90mmol, 1.5 equiv) trimellitic anhydride (trimelliticanhydride, TMA) -α- with 100mL of methyl N- methylpyrrolidone (NMP, N-methyl-α-pyrrolidone), and added to the above reaction the reaction at 90 ℃ 4 hours, the reaction is followed FT-IR, 1 (signal anhydride) until disappearance of 1780 cm means that the reaction was complete, the reaction is as follows:

(反应式2) (Scheme 2)

第三阶段: The third phase:

将17.04g(120mmol,2当量)甲基丙稀酸缩水甘油脂(GMA,glycidyl methacrylate)加入上述反应并于90℃反应6小时后即得产物,其结构如下: The 17.04g (120mmol, 2 eq) of glycidyl methyl acrylic acid glycerides (GMA, glycidyl methacrylate) was added to the reaction and the reaction product was obtained after 6 hours at 90 ℃, the following structure:

式(II) Of formula (II)

此外本发明提供较佳的喷墨墨水实施例与比较实施例如下: Furthermore, the present invention provides inkjet inks preferred embodiment and Comparative Example are as follows:

实施例1 Example 1

以光引发剂(2-羟基-1-苯基-1-丙酮)、可光固化单体(BHT、TGD)、以及本发明的枝状化合物(制备例一)依不同比例形成光固化型墨水的基本配方,以光引发剂为重量基准(1份),BHT固定为0.04份,并调整TGD与本发明枝状物的比例以形成实施配方1~3。 In photoinitiator (2-hydroxy-1-phenyl-1-propanone), the photocurable monomer (BHT, TGD), and the present invention is a dendrimer (prepared in Example a) forming a light curable ink in different proportions. the basic formulation to light on weight initiator ratio (1 part), BHT 0.04 parts fixed, TGD and adjust the dendrites of the present invention 1 to 3 to form formulation embodiment.

表1 Table 1

配方编号 Recipe number 光引发剂 Photoinitiator BHT BHT TGD TGD 本发明化合物 Compounds of the invention
实施配方1 Implementation of Formula 1 1份 1 part 0.04份 0.04 parts 109.5份 109.5 parts 52份 52 parts
实施配方2 Implementation of Formula 2 1份 1 part 0.04份 0.04 parts 142.8份 142.8 parts 26份 26 parts
实施配方3 Implementation of Formula 3 1份 1 part 0.04份 0.04 parts 165份 165 parts 9份 9 parts

之后根据下表将实施配方1~3、共溶剂、表面活性剂混合并搅拌十分钟。 After the formulation according to the following table 1 to 3 embodiment, co-solvent, surfactant mixture and stirred for ten minutes. 共溶剂为2-吡咯烷酮(2-pyrrolidone,2PO),表面活性剂较佳为BYK公司贩售的BYK 333。 Co-solvent is 2-pyrrolidinone (2-pyrrolidone, 2PO), is preferably a surfactant sold by BYK of BYK 333. 将上述混合物加入水,并用高速搅拌均质机以每分钟5000转搅拌5分钟后静待泡沫消失。 The mixture was added water, and stirred with a high speed homogenizer stirring revolutions per minute wait after 50,005 minutes, the foam has disappeared. 以刮刀将三种配方涂布于玻璃上形成25微米厚的薄膜并以110℃烘烤60分钟,再以170℃烘烤45分钟后进行紫外灯照射以固化薄膜,进行硬度测试如表2。 In three formulations doctor blade forming a thin film coated on a glass thickness of 25 microns and baked at 110 ℃ 60 minutes and then baked for 45 min irradiation of UV light at 170 ℃ to cure the film hardness test are shown in Table 2.

表2 Table 2

批号 lot number H<sub>2</sub>O H <sub> 2 </ sub> O 2PO 2PO 基本配方(12.5份) The basic formula (12.5 parts) 水稳定性 Water stability 硬度 hardness 百格% One hundred cells%
实施薄膜1 Embodiment 1 film 20份 20 parts 50份 50 parts 实施配方1 Implementation of Formula 1 稳定 stable 5H 5H 100 100
实施薄膜2 Embodiment 2 film 20份 20 parts 50份 50 parts 实施配方2 Implementation of Formula 2 稳定 stable 4H 4H 100 100
实施薄膜3 Embodiment 3 film 20份 20 parts 50份 50 parts 实施配方3 Implementation of Formula 3 稳定 stable 3H 3H 100 100

由表2可发现,当本发明的枝状物比例提高时,确实能提高光固化后的薄膜硬度。 Can be found from Table 2, when the branch ratio of the present invention was improved, really improve film hardness after photocuring.

比较实施例1 Comparative Example 1

以环氧丙烯寡聚物(epoxy acrylic oligomer,Sartomer N120)做为光固化型墨水的配方。 To propylene oxide oligomer (epoxy acrylic oligomer, Sartomer N120) as photocurable ink formulation. 其比例如下,除了将本发明化合物置换成N120外,其他成分的比例均相同。 Ratios below, except that the compound of the present invention is replaced with N120, the proportion of the other components are the same.

表3 table 3

配方编号 Recipe number 光引发剂 Photoinitiator BHT BHT TGD TGD N120 N120
比较配方1 Comparison of Formula 1 1份 1 part 0.04份 0.04 parts 109.5份 109.5 parts 52份 52 parts
比较配方2 Compare Formula 2 1份 1 part 0.04份 0.04 parts 142.8份 142.8 parts 26份 26 parts
比较配方3 Compare Formula 3 1份 1 part 0.04份 0.04 parts 165份 165 parts 9份 9 parts

粘合如同实施例1的作法,以一样的步骤将比较配方1~3形成比较薄膜1~3并进行硬度测试如表4。 Bonding practice as Example 1 embodiment, to the same steps 1 to 3 of Comparative Formulation 1 to 3 to form a relatively thin film and hardness test are shown in Table 4.

表4 Table 4

批号 lot number H<sub>2</sub>O H <sub> 2 </ sub> O 2PO 2PO 比较配方(12.5份) Compare formula (12.5 parts) 水稳定性 Water stability 硬度 hardness 百格% One hundred cells%
比较薄膜1 Comparison Film 1 20份 20 parts 50份 50 parts 比较配方1 Comparison of Formula 1 稳定 stable 2H 2H 100 100
比较薄膜2 Comparison Film 2 20份 20 parts 50份 50 parts 比较配方2 Compare Formula 2 稳定 stable 2H 2H 100 100
比较薄膜3 Comparison Film 3 20份 20 parts 50份 50 parts 比较配方3 Compare Formula 3 稳定 stable F F 100 100

虽然由表4可发现N120一样具有光固化的效果,但在一样的比例下,本发明的球形枝状物在光固化的效果较链状寡聚物N120的效果佳。 Although N120 can be found in Table 4 as a light curing effect, but in the same proportion, the spherical dendrimers of the present invention was better than the effect of the photocurable oligomer chain of N120 good.

实施例2 Example 2

将实施配方1~3与L1R1、L1G03、L1B14的颜料浓缩液混合搅拌以测其性质。 The embodiments 1 to 3 and Formulation L1R1, L1G03, the pigment concentrate L1B14 kneading to measure its properties. 将红色颜料如Pigment Red(颜料红)21、Pigment Green(颜料绿)03、与Pigment Blue(颜料蓝)15:3分别研磨可得自制颜料L1R21、L1G03、L1B14,其物性如下表: Red pigments such as Pigment Red (Pigment Red) 21, Pigment Green (Pigment Green) 03, and Pigment Blue (pigment blue) 15: 3, respectively, available self-polishing paint L1R21, L1G03, L1B14, physical properties as follows:

表5 table 5

颜料颜色 Color pigments L1R21(红色) L1R21 (red) L1G03(绿色) L1G03 (green) L1B14(蓝色) L1B14 (blue)
颜料 pigment PR149 PR149 PG36 PG36 PB15:3 PB15: 3
颜料比例(%) Pigment ratio (%) 15.1 15.1 14.9 14.9 14.9 14.9
pH值 pH value 7.9 7.9 5.5 5.5 7.7 7.7
粘度(cps) Viscosity (cps) 7.5 7.5 90 90 62 62
表面张力(毫牛顿/米) The surface tension (milliNewtons / meter) 47 47 48.9 48.9 49.8 49.8
平均粒径(nm) The average particle diameter (nm) 198.8 198.8 91 91 155.8 155.8

将实施配方1~3(实施例1)与比较配方1~3(比较实施例1)各自加入一样比例的水(7.57%)、2PO(20.83%)、表面活性剂BYK333(均占0.8%)、自制颜料(均占58.3%)后,搅拌15分钟以形成喷墨墨水组合物,以刮刀将其涂布于玻璃上形成25微米厚的墨水薄膜并以110℃烘烤60分钟,再以170℃烘烤45分钟后进行紫外灯照射以固化墨水薄膜,进行硬度测试如表6。 Formulation 1 to 3, the embodiment (Example 1) and Comparative Formulation 1-3 (Comparative Example 1) were each added to the same proportions of water (7.57%), 2PO (20.83%), a surfactant BYK333 (account for 0.8%) after self pigment (account for 58.3%), stirred for 15 minutes to form an ink jet ink composition, the coated blade to form an ink film thickness of 25 microns on glass and baked at 110 ℃ 60 minutes, then 170 ℃ ultraviolet light irradiation after baking for 45 minutes to cure the ink film hardness test are shown in table 6.

表6 Table 6

墨水编号 Ink numbers 配方 formula 颜料 pigment 水稳定性 Water stability 粘度(cps) Viscosity (cps) 表面张力(毫牛顿/米) The surface tension (milliNewtons / meter) 硬度 hardness 百格(%) One hundred cells (%)
实施红墨1 Embodiment red ink 1 实施配方1 Implementation of Formula 1 L1R21 L1R21 稳定 stable 11.8 11.8 34.5 34.5 4H 4H 100 100
实施红墨2 Embodiment 2 Red Ink 实施配方2 Implementation of Formula 2 L1R21 L1R21 稳定 stable 10.1 10.1 34.5 34.5 3H 3H 100 100
实施红墨3 Embodiment 3 Red Ink 实施配方3 Implementation of Formula 3 L1R21 L1R21 稳定 stable 7.98 7.98 34 34 H H 100 100
实施绿墨1 Embodiment 1 green ink 实施配方1 Implementation of Formula 1 L1G03 L1G03 稳定 stable 8.47 8.47 33.5 33.5 4B 4B 100 100
实施绿墨2 Embodiment 2 green ink 实施配方2 Implementation of Formula 2 L1G03 L1G03 稳定 stable 7.94 7.94 33 33 4B 4B 100 100
实施绿墨3 Green ink Embodiment 3 实施配方3 Implementation of Formula 3 L1G03 L1G03 稳定 stable 7.87 7.87 33 33 4B 4B 100 100
实施蓝墨1 Embodiment 1 Blue Ink 实施配方1 Implementation of Formula 1 L1B14 L1B14 稳定 stable 18.6 18.6 34.5 34.5 <4B <4B 100 100
实施蓝墨2 Embodiment 2 Blue Ink 实施配方2 Implementation of Formula 2 L1B14 L1B14 稳定 stable 17.9 17.9 34 34 F F 100 100
实施蓝墨3 Embodiment 3 Blue Ink 实施配方3 Implementation of Formula 3 L1B14 L1B14 稳定 stable 16.7 16.7 34.5 34.5 HB HB 100 100
比较红墨1 Ink 1 Redder 比较配方1 Comparison of Formula 1 L1R21 L1R21 胶状物 Jelly 胶状物 Jelly 胶状物 Jelly - - - -
比较红墨2 Ink 2 Redder 比较配方2 Compare Formula 2 L1R21 L1R21 变稠 Thickens 11.8 11.8 34.5 34.5 HB HB 100 100
比较红墨3 Ink 3 Redder 比较配方3 Compare Formula 3 L1R21 L1R21 稳定 stable 9.53 9.53 34 34 HB HB 100 100
比较绿墨1 Green Ink 1 Comparative 比较配方1 Comparison of Formula 1 L1G03 L1G03 稳定 stable 8.84 8.84 32.5 32.5 <4B <4B 100 100
比较绿墨2 Comparison green ink 2 比较配方2 Compare Formula 2 L1G03 L1G03 稳定 stable 7.92 7.92 32.5 32.5 <4B <4B 100 100
比较绿墨3 Comparative Ink 3 Green 比较配方3 Compare Formula 3 L1G03 L1G03 稳定 stable 7.62 7.62 33 33 <4B <4B 100 100
比较蓝墨1 Compare blue ink 1 比较配方1 Comparison of Formula 1 L1B14 L1B14 稳定 stable 23.7 23.7 34 34 3B 3B 100 100
比较蓝墨2 Blue Ink Compare 2 比较配方2 Compare Formula 2 L1B14 L1B14 稳定 stable 20.3 20.3 33.5 33.5 <4B <4B 100 100
比较蓝墨3 Comparison of blue ink 3 比较配方3 Compare Formula 3 L1B14 L1B14 稳定 stable 19.1 19.1 34 34 2B 2B 100 100

上表清楚的揭示应用本发明化合物的实施红墨1~3、实施绿墨1~3、实施蓝墨1~3与应用Sartomer N120的比较红墨1~3、比较绿墨1~3、比较蓝墨1~3相较下,均具有较佳的硬度,特别是在红色颜料的水稳定性上有较佳的表现。 Table clearly disclosed embodiments red ink compound of the present invention is 1 to 3, Embodiment green ink 1 to 3, Embodiment blue inks 1 to 3 and Comparative red ink application Sartomer N120 1 to 3 and Comparative green ink 1 to 3, Comparative blue ink compared with the 1-3, they have better hardness, a better performance especially in the water stability of the red pigment.

实施例3 Example 3

为进一步比较本发明实施例2中,本发明实施例与比较实施例的墨水于实际应用的表现,将9种实施例的墨水与9种比较实施例的墨水各自装入HP51626喷墨匣,以墨滴成型观测仪量测喷墨墨滴以比较喷墨表现,如表7与图1A~图1C,图2A~图2C所示: Comparative Example of the present invention further 2 Example Comparative Example embodiment of the ink performance in the practical application of the embodiment of the present invention, the nine kinds of ink with Example Comparative Example 9 kinds of ink each ink jet cartridge HP51626 charged to an ink droplet forming observer to compare measured droplet inkjet ink jet performance, as shown in table 7 and FIGS. 1A ~ 1C, the Figure FIG. 2A ~ 2C:

表7 Table 7

墨水编号 Ink numbers 喷墨速度 Speed ​​inkjet 喷墨表现 Inkjet performance
实施红墨1 Embodiment red ink 1 2m/sec 2m / sec 喷墨太短 Inkjet is too short
比较红墨1 Ink 1 Redder 胶状物 Jelly 胶状物 Jelly
实施红墨2 Embodiment 2 Red Ink 3m/sec 3m / sec 喷墨很稳 Inkjet very stable
比较红墨2 Ink 2 Redder 5m/sec 5m / sec 喷墨会偏 Inkjet will be biased
实施红墨3(图1A) Red Ink Embodiment 3 (FIG. 1A) 5m/sec 5m / sec 喷墨很稳 Inkjet very stable
比较红墨3(图2A) Comparative Ink Red 3 (FIG. 2A) 6m/sec 6m / sec 喷墨会偏 Inkjet will be biased
实施绿墨1 Embodiment 1 green ink 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较绿墨1 Green Ink 1 Comparative 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will
实施绿墨2 Embodiment 2 green ink 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较绿墨2 Comparison green ink 2 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will
实施绿墨3(图1B) Green ink Embodiment 3 (FIG. 1B) 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较绿墨3(图2B) Comparative Green Ink 3 (FIG. 2B) 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will
实施蓝墨1 Embodiment 1 Blue Ink 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较蓝墨1 Compare blue ink 1 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will
实施蓝墨2 Embodiment 2 Blue Ink 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较蓝墨2 Blue Ink Compare 2 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will
实施蓝墨3(图1C) Embodiment 3 Blue ink (FIG. 1C) 8m/sec 8m / sec 喷墨很稳 Inkjet very stable
比较蓝墨3(图2C) Comparative Ink Blue 3 (FIG. 2C) 8m/sec 8m / sec 喷墨会积墨 The inkjet ink deposits will

由表7与图1A~图1C、图2A~图2C可清楚发现本发明的喷墨稳定性较佳。 Table 7 and FIGS. 1A ~ FIG. 1C, FIG. 2A ~ 2C better ejection stability can be clearly found in the present invention. 由此可知本发明的枝状物比链状的可光固化寡聚物更适合做为喷墨墨水组合物。 Dendrites can be seen the present invention can control curing light chain oligomer is more suitable as an inkjet ink composition.

以上所述仅为本发明较佳实施例,然其并非用以限定本发明的范围,任何熟悉本项技术的人员,在不脱离本发明的精神和范围内,可在此基础上做进一步的改进和变化,因此本发明的保护范围当以本申请的权利要求书所界定的范围为准。 The foregoing is only preferred embodiments of the present invention, they are not intended to limit the scope of the present invention, any person skilled in the art items, without departing from the spirit and scope of the present invention may be further on the basis of modifications and variations, and the scope of the present invention when in application of the scope of the claims and their equivalents.

Claims (14)

1.一种含多UV交联反应基的球形分枝状结构化合物,其特征在于,包含: 1. spherical branched structure compound containing multiple UV crosslinking reactive group, wherein, comprising:
一核心,其结构为异三聚氰酸酯;以及 A core having the structure iso-cyanurate; and
多个分枝状取代基,其骨架含有多个极性官能团,且末端为UV交联反应基。 A plurality of branched substituents which backbone comprises a plurality of polar functional groups, and the terminal group is a UV crosslinking reaction.
2.根据权利要求1所述的含多UV交联反应基的球形分枝状结构化合物,其特征在于,该多个分枝状取代基,其骨架还包含多个芳香基。 2. The multiple-containing UV-crosslinking reactive group spherical branched structure compound as claimed in claim, wherein the plurality of branched substituents, which backbone further comprises a plurality of aromatic groups.
3.根据权利要求1所述的含多UV交联反应基的球形分枝状结构化合物,其特征在于,该UV交联反应基包括碳碳双键。 3. The multiple-containing UV-crosslinking reactive group spherical branched structure compound as claimed in claim, characterized in that the UV crosslinking reactive group comprises a carbon-carbon double bond.
4.根据权利要求1所述的含多UV交联反应基的球形分枝状结构化合物,其特征在于,其结构如下: 4. The multiple-containing UV-crosslinking reactive group spherical branched structure compound as claimed in claim, characterized in that its structure is as follows:
上式(I)中,R 1为环氧烷烃开环后的链段; In the above formula (I), R 1 is the ring-opened alkylene oxide segment;
Ar为具有多个极性官能团的芳香基;以及 Ar is an aromatic group having a plurality of polar functional groups; and
R 2为UV交联反应基,n为1~5的整数。 R 2 is a UV crosslinking reaction group, n is an integer of 1 to 5.
5.根据权利要求4所述的多UV交联反应基的球形分枝状结构化合物,其特征在于,该Ar具有的这些极性官能团为酯基与羟基。 Compound multi-branched structure spherical UV crosslinking reactive group according to claim 4, wherein Ar has the polar functional group such as a hydroxyl group and an ester group.
6.根据权利要求4所述的多UV交联反应基额达的球形分枝状结构化合物,其特征在于,其结构如下式(II)所示。 Compound multi-branched structure spherical UV cross-linking reaction amounted to the group according to claim 4, characterized in that, having the structure of formula (II) shown in FIG.
7.一种球形分枝状结构化合物,其特征在于,所述球形分枝状结构化合物是权利要求1所述的含多UV交联反应基的球形分枝状结构化合物的前体,其结构如下: A spherical branched structure compound, wherein said spherical branched structure-containing compound is according to more than one UV-crosslinking reactive group precursor spherical branched structure of the compound of Claim structure as follows:
上式(III)中,R 1为环氧烷烃开环后的链段;以及 In formula (III), R 1 is the ring-opened alkylene oxide segment; and
Ar为具有多个极性官能团的芳香基。 Ar is an aromatic group having a plurality of polar functional groups.
8.根据权利要求7所述的球形分枝状结构化合物,其特征在于,该Ar还包括下列至少一种取代基:羧酸基、羟基、或胺基。 8. The spherical structure of the branched compound according to claim 7, wherein the Ar substituents further comprising at least one group: carboxylic acid group, a hydroxyl group, or amine groups.
9.根据权利要求7所述的球形分枝状结构化合物,其特征在于,其结构如下式(IV)所示。 9. The spherical structure of the branched compound according to claim 7, characterized in that the structure of the following formula (IV) shown in FIG.
10.一种感光树脂组合物,其特征在于,包括: A photosensitive resin composition, characterized by comprising:
a)0.02~25wt%感光引发剂; a) 0.02 ~ 25wt% photosensitive initiator;
b)1~99.8wt%根据权利要求1所述的含多UV交联反应基的球形分枝状结构化合物;以及 b) 1 ~ 99.8wt% branched structure compound plurality spherical UV crosslinking reactive group-containing according to the claim 1; and
c)0~98.98wt%其他感光反应物。 c) 0 ~ 98.98wt% photosensitive other reactants.
11.一种喷墨墨水组合物,其特征在于,包括: 11. An inkjet ink composition comprising:
a)0.5~50wt%的溶媒; a) 0.5 ~ 50wt% of the vehicle;
b)0.5~20wt%的色料; b) 0.5 ~ 20wt% of pigment;
c)1~90wt%的光固化单体;以及 c) 1 ~ 90wt% of the photocurable monomer; and
d)1~40wt%根据权利要求1所述的含多UV交联反应基的球形分枝状结构化合物。 d) containing multiple UV crosslinkable group spherical branched structure of the compound of claim 1 1 ~ 40wt% claims.
12.根据权利要求11所述的喷墨墨水组合物,其特征在于,还包括e)0.1~25wt%的光引发剂。 12. The inkjet ink composition according to claim 11, characterized by further comprising e) 0.1 ~ 25wt% of a photoinitiator.
13.根据权利要求11所述的喷墨墨水组合物,其特征在于,该溶媒包括水、溶剂、或单体。 13. The inkjet ink composition according to claim 11, wherein the solvent comprises water, solvent or monomer.
14.根据权利要求11所述的喷墨墨水组合物,其特征在于,其粘度介于1~35cps,表面张力介于20~50毫牛顿/米,硬度介于4H~4B。 14. The inkjet ink composition according to claim 11, wherein the viscosity is between 1 ~ 35cps, a surface tension between 20 to 50 milliNewtons / meter, hardness range 4H ~ 4B.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1264716A (en) 1999-02-04 2000-08-30 巴斯福股份公司 Branch-like and high branching polyurethane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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