TW201249880A

TW201249880A - Stable curable thiol-ene composition

Info

Publication number: TW201249880A
Application number: TW101109628A
Authority: TW
Inventors: Zoubair Cherkaoui; Parichehr Esfandiari; Richard Frantz; Jean Jacques Lagref; Robert Liska
Original assignee: Huntsman Adv Mat Switzerland
Priority date: 2011-03-23
Filing date: 2012-03-21
Publication date: 2012-12-16

Abstract

Curable composition comprising: (A) at least one ethylenically or acetylenically unsaturated monomer or a mixture thereof; (B) at least one thiol; (D) at least one phosphonic acid; (E) a component of the benzene or naphthalene series exhibiting at least one benzene ring or naphthalene ring containing at least two hydroxyl substituents.

Description

201249880 六、發明說明：【發明所屬之技術領域】、本發明係關'"於可固化或光可固化之硫醇-烯基或硫醇_ 炔基組成物。硫醇-烯基組成物包含硫醇組分及烯基組分，其為烤系或炔系不飽和單體且適用於塗佈應用、黏著劑、添加劑製造技術（AMT )及快速成型（rapid prototyping， Rp)中’尤其適於使用立體微影（SLA)技術及數位光處理（DLP )生產三維（3D )物件。根據該定義，術語硫醇· 稀基組成物亦包括硫醇·炔基組成物。【先前技術】一種熟知的快速成型方法（亦即立體微影（SLA乃廣泛流行且現今常常用於寬廣的技術應用領域中，主要用於航空、自動及機械工程行業。立體微影技術使用液體光聚口物，其藉由uv相干或非相干光源（如雷射或uv燈）局部固化（參見專利申請案WO 2010/043559及W0 /043 275 )。現今之標準立體微影樹脂係基於（甲基）丙稀酉文或％氧基光聚合物。（甲基）丙烯酸酯光聚合物展現相對較向的收縮率及氧抑制’而在環氧基光聚合物中可避免此等缺Pa ’然而’聚合物之不良反應性、高脆性、水分敏感性及高吸水性為不利效應。 (T基）丙婦酸醋及陽離子單體光聚合之替代方案涉及最近已再現的硫醇-烯基聚合。與簡單的(甲基)丙烯酸醋相 1匕，硫醇·稀基聚合在空氣中藉由自由基逐步生長方法迅速達到南轉化率。硫醇·烯基逐步生長自由基聚合係基於將硫 3 201249880 醇添加至乙烯基官能基中。硫醇-稀基聚合物近來已作為適用於心之光聚再度出現於行業舞台上（參見專利申請案二 /043463 )。與丙烯酸酷聚合相比之多種優勢，諸如〇聚合速率、最小氧抑制、近乎完、' 疋王的钬合及較低收使硫醇-烯基成為SLA技術之合適候選物。儘管硫醇烯基材料展現許多優勢，但難以使尤其難以獲得長期存放穩定性。，再有長期存放穩定性配物可例如被定義為A官，，° 我為在至/皿下’在6個月内黏度未加倍的調配物。黏度增加表明在聚婦與聚硫醇之間發生自發聚反應。在極個別情況下，不穩定調配物將產生難處理的不可溶凝膠。習知自由基穩定劑（諸如氣酿、啡嗟啡及复類似物）常用作硫醇烯基調配物之穩定劑，但早已切識到該等穩定劑常常不能有效提供具有商業上可接受之存二期的硫醇-烯基調配物。即使仔細封裝以隔絕任何光，但硫醇- 烯基調配物仍常常在製造的幾曰内於其封裝中聚合。儘管具有明顯優勢，諸如無光引發劑反應、降低的氧敏感性、快速聚合速率及形成具有良好物理機械性的交聯網，但硫醇-烯基系統展示有限的存放期穩定性◎所有硫醇_ 烯基反應均展現自發的暗反應，在不存在引發劑的情況下產生聚合物（寡聚物> 暗反應於密閉容器中在輻射可固化調配物中進行’-般引起提前聚合。硫醇·縣系統之儲存穩定性以不.同程度受暗反應的影響，取決於不飽和烯基及硫醇之活性。 201249880 坪多優^Γ_烯基逐步生長反應’所以4醇_縣聚合展現 :夕=知UV固化樹脂的優勢’包括固有的快速反應速率、減小的氧抑制及降低的收縮率。 ^ ^ 手然·^，不良存放期穩疋丨生限制硫醇-烯基應用。硫醇-烯基調配物之自發暗反應伴以# 4 β 5 Λ 拟屮 * - 丁黏度增加及寡聚物 ^成’為實際應用之顯著缺陷。因& 物夕勉种* *要硫醇-烯基調配物之經改良之穩定系統。本發明之一目標為至少 _ 兄服先刖技術之缺陷。之，本發明之一目標為接徂為知供穩定的可固化或光可口化之&醇-烯基組成物，並 ^ 八展現長存放期及適用期，使得黏度在儲存期内有限增加。詳言之’本發明之一目標為提供在室溫（25〇下及定：r:c)下均具有長期存放穩定性之光可固化的穩又硫醇-烯基組成物。本發明之一目標亦為捉彳/、種，、有呵反應性及光敏性 I先可固化的穩定硫醇.嫌其 ^^咚婶基組成物，其在固化後產生由低 * ^ 衡擎強度（細ch impact strength) 表徵之3D物件。本發明之目標根據以下獨申姓解央 Γ询立項甲3月專利範圍之特徵來發明内容】根據本發明之第一態樣，提供一種可固化（較佳光可固化）組成物，其包含： Α)至少-種婦系或炔系不飽和單體，較佳—種丙稀酸201249880 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a curable or photocurable thiol-alkenyl or thiol-alkynyl composition. The thiol-alkenyl composition comprises a thiol component and an alkenyl component which are roasting or acetylenically unsaturated monomers and are suitable for coating applications, adhesives, additive manufacturing techniques (AMT) and rapid prototyping (rapid) Prototyping, Rp) is especially suitable for producing three-dimensional (3D) objects using stereo lithography (SLA) technology and digital light processing (DLP). According to this definition, the term thiol dilute composition also includes thiol-alkynyl compositions. [Prior Art] A well-known rapid prototyping method (ie, stereo lithography (SLA) is widely used and is often used in a wide range of technical applications, mainly in the aerospace, automatic and mechanical engineering industries. Stereo lithography uses liquids. a light concentrating material which is partially cured by a uv coherent or incoherent light source such as a laser or a uv lamp (see patent applications WO 2010/043559 and W0 /043 275). Today's standard stereo lithography resins are based on ( Methyl) propyl or % oxyphotopolymer. (Meth) acrylate photopolymer exhibits relatively relatively shallow shrinkage and oxygen inhibition ' while avoiding such abs in the epoxy photopolymer 'However' the adverse reactivity, high brittleness, moisture sensitivity and high water absorption of the polymer are unfavorable effects. Alternatives to photopolymerization of (T-based) acetoacetate and cationic monomers involve recently recreated thiol-enes. Base polymerization. With simple (meth)acrylic acid vinegar phase, thiol·thin base polymerization rapidly reaches south conversion rate by free radical growth method in air. Thiol-alkenyl group gradually grows free radical polymerization system The sulfur 3 201249880 alcohol is added to the vinyl functional group. The mercaptan-dilute polymer has recently appeared on the industrial stage as a suitable light for the heart (see Patent Application No. 2/043463). Advantages over many advantages, such as ruthenium polymerization rate, minimum oxygen inhibition, near-end, 'King's combination, and lower yield thiol-alkenyl are suitable candidates for SLA technology. Although thiol-alkenyl materials exhibit many advantages However, it is difficult to make it particularly difficult to obtain long-term storage stability. Further long-term storage stability of the ligand can be defined as, for example, A official, ° ° I am under the / / dish 'without doubling the viscosity within 6 months of the formulation An increase in viscosity indicates an autopolymerization reaction between the compound and the polythiol. In rare cases, unstable formulations will produce intractable insoluble gels. Conventional free radical stabilizers (such as gas, corn) Quinone and analogs are commonly used as stabilizers for thiol alkenyl formulations, but it has long been recognized that such stabilizers are often not effective in providing commercially available thiol-alkenyl formulations. Even if carefully packaged to isolate any light, thiol-alkenyl formulations often polymerize in their packages within a few gallons of manufacture. Despite significant advantages such as no photoinitiator reaction, reduced oxygen sensitivity, fast polymerization Rate and formation of a network with good physical and mechanical properties, but the thiol-alkenyl system exhibits limited shelf life stability. All thiol-alkenyl reactions exhibit spontaneous dark reactions and are produced in the absence of initiator. Polymer (oligomers> dark reaction in a viscous container in a radiation-curable formulation to cause premature polymerization. The storage stability of the thiol system is not affected by the dark reaction, depending on the degree of dark reaction Activity of unsaturated alkenyl groups and thiols 201249880 Ping Duoyou ^Γ_alkenyl step-growth reaction 'so 4 alcohol_counter polymerization shows: Xi = know the advantages of UV-curing resin' including inherent rapid reaction rate, reduction Oxygen inhibition and reduced shrinkage. ^ ^ Handle · ^, poor shelf life stable thiol-alkenyl applications. The spontaneous dark reaction of the thiol-alkenyl formulation is accompanied by a significant defect in the practical application of #4β5ΛΛ*-butyl viscosity increase and oligomerization. Because & 物勉 * * * A modified stabilization system for thiol-alkenyl formulations. One of the objects of the present invention is to at least _ swear the deficiencies of the prior art. One of the objectives of the present invention is to provide a stable curable or lightly pourable & alcohol-alkenyl composition, and to exhibit a long shelf life and pot life, so that the viscosity is limited during storage. . DETAILED DESCRIPTION OF THE INVENTION One object of the present invention is to provide a photocurable stable thiol-alkenyl composition having long-term storage stability at room temperature (25 Torr and R:c). One of the objectives of the present invention is also to stabilize the thiol which is capable of curing 彳/, species, responsiveness and photosensitivity I. It is a composition of the thiol group which is produced by a low concentration after curing. 3D object characterized by fine impact strength. SUMMARY OF THE INVENTION The object of the present invention is to provide a curable (preferably photocurable) composition comprising a composition according to the first aspect of the present invention. : Α) at least - a gynomatic or acetylenically unsaturated monomer, preferably a kind of acrylic acid

S 5 201249880 酯或甲基丙烯酸酯或烯丙基醚或炔烴或烯丙基畊 (allylazine)或其混合物； B )至少一種硫醇； D )至少一種膦酸； Ε )展現至少一個含有至少兩個羥基取代基之苯環或萘環的笨或奈系列組分，較佳視情況經取代之聚羥基苯。藉由添加與酸性化合物D組合於組成物令之自由基穩定劑Ε發現令人驚訝的協同效應。組成物可藉由加熱固化，但較佳光可固化，亦即藉由光化輻射或紫外光（υν )可固化。在一較佳具體實例中，可固化或光可固化之組成物包含： A )至少一種烯系或炔系不飽和單體或其混合物； B )至少一種硫醇； C)至少一種自由基光引發劑； D )至少一種膦酸； E)展現至少一個笨環或萘環之笨或萘系列之組分，其含有至少兩個羥基取代基連接於該苯環或萘環。在一較佳具體實例中，組分E展現以下結構（i :S 5 201249880 Ester or methacrylate or allyl ether or alkyne or allylazine or mixtures thereof; B) at least one thiol; D) at least one phosphonic acid; Ε) exhibiting at least one containing at least one A stupid or naphthalene series component of a benzene ring or a naphthalene ring of two hydroxy substituents, preferably a polyhydroxy benzene which is optionally substituted. A surprising synergistic effect was found by adding a free radical stabilizer to the composition in combination with the acidic compound D. The composition can be cured by heating, but is preferably photocurable, i.e., curable by actinic radiation or ultraviolet light (?ν). In a preferred embodiment, the curable or photocurable composition comprises: A) at least one olefinic or acetylenically unsaturated monomer or mixture thereof; B) at least one thiol; C) at least one free radical light An initiator; D) at least one phosphonic acid; E) a component of the stupid or naphthalene series exhibiting at least one stupid or naphthalene ring having at least two hydroxy substituents attached to the phenyl or naphthalene ring. In a preferred embodiment, component E exhibits the following structure (i:

其中η為2至6之整數，m為〇至（6_n)之整數，且 Rm彼此獨立地為有機基團，較佳C1-C6燒基。 201249880 在組分E之結構（1 )中，最佳地，η為2 ' 3或4且m 為0或1。根據本發明之—姓a _ 将弋具體實例，可固化或光可固化組成物包含： A) 25-98 wt%、較佳 5〇 95 wt%之組分 a ; B ) 1-70 Wt%、較佳 3-40 wt%之組分 B ; C) 0-10 wt%、較佳 1-7wt%之組分 c; D) 0.01_l〇 wt%、較佳〇 5 5 wt%之組分 d ; E) 0.01-10 wt%、較佳〇 01_3 wt%之組分 E ; 各以該組成物之總重量計。根據本發明之另一具體實例，可固化組成物包含： A ) 6 0-9 0 wt% 之組分 a ; B) 5-40 wt%之組分 B ; C ) 1-5 wt%之組分 C ; D) 1-4 wt%之組分 D ; E ) 0.0 5 - 2 wt % 之組分 E ; 各以該組成物之總重量計。在本發明之一個具體實例中’以光可固化組成物之總重量計’該組成物包含25-98 wt°/〇、較佳50-95 wt%、最佳 60-90 wt%之組分 A。在本發明之另一具體實例中，以光可固化組成物之總重量計’該組成物包含1-70 wt%、較佳3-40 wt%、最佳5-40 wt%之組分B。在本發明之另一具體實例中’以光可固化組成物之總 7 201249880 重量計，該組成物包含0_l0wt%、較佳Μ wt%、最佳Μ wt%之組分C。在本發明之另一具體實例中，以光可固化組成物之總重量計’該組成物包含0.01_10wt%、較佳〇 5_5 wt%、最佳 1-4 wt%之組分〇。在本發明之另一具體實例中，以光可固化組成物之總重量計，該組成物包含0.01-10 wt%、較佳〇〇13 wt%、最佳0.05-2 wt%之組分E。根據本發明之一較佳具體實例’組分E展現至少一個本裱或萘環，其中兩個、三個或四個羥基取代基直接鍵結於§亥笨環或萘環。根據本發明之另一較佳具體實例，組分E包含視情況經取代之苯二酚、苯三酚或五倍子酚。根據本發明之另一較佳具體實例，組分d包含苯膦酸、乙烯膦酸、辛二膦酸或2_丙烯酸、2_[(2_膦醯乙氧基）甲基]_卜乙酯（亦稱為2-[4-(二羥基磷醯基）-2_氧_丁基]丙烯酸乙酯）。根據本發明之一較佳具體實例，組分B為展現2至4 個SH基團之聚硫醇。根據本發明之一較佳具體實例，組分B包含季戊四醇四（3-锍基丙酸酯）、乙二醇二_3_巯基丙酸酯、三羥曱基丙烷二-3-巯基丙酸酯或季戊四醇四（3_巯基丁酸能）。根據本發明之一較佳具體實例’組分A包含二丙烯酸酯或二甲基丙烯酸酯，尤其1.6-己二醇二丙烯酸酯或雙酚a 乙氧基化二（曱基）丙烯酸酯。 201249880 根據本發明之一較佳具體實例，光可固化組成物在65 C下76天或110天後’在25 〇c下之黏度仍小於該組成物在 25 °C下之最初黏度的3.5倍、較佳2.5倍、最佳2倍。根據本發明之第二態樣，提供根據物品模型以連續截面製造三維物品之方法，其包含以下步驟： •开> 成第一層本發明之光可固化組成物； •使該第一層暴露於對應該模型各別截面之圖案中足以硬化該影像區中之第一層的光化輻射； •在該硬化第一層上形成第二層本發明之光可固化組成物；使5玄第二層暴露於對應該模型各別截面之圖案中足以硬化該影像區中之第二層的光化輻射； .及視需要重複先前兩個步驟以形成連續層以形成該專三維物品。光化輻射較佳不相干且由紫外線（uv )燈發出。 (A )組分a 根據本發明，可固化組成物包含一種組分A，其可例如為一種丙烯酸酯或甲基丙烯酸酯或烯丙基醚或炔烴或烯丙基啡或其混合物。在以下段落中，列舉適用於本發明之樹脂組成物的丙烯酸酯組分。丙烯酸醅έ日八可^ 』岬馱S曰組/刀可指早一丙烯酸酯化合物或不同丙稀酸醋化合物之，、早人札人、* τ β t混&物。合適丙烯酸酯組分可為單官能、雙官能或更高官能性的。單官能丙烯酸酯可用於修改樹脂性質。 9 201249880 單官能丙烯酸酯之實例包括諸如丙烯酸異冰片自t 烯酸四氫糠酯、乙氧基化丙烯酸苯酯、丙烯酸十二尸妒丙烯酸硬脂酼酯、丙烯酸辛酯、丙烯酸異癸酯、丙烯^十三烷酯、丙烯酸己内酯、壬苯酚丙烯酸酯、環狀三羥甲美丙烷縮甲醛丙烯酸酯、甲氧基聚乙二醇丙烯酸酯、甲氧^ 聚丙二醇丙烯酸酯、丙烯酸羥乙酯、丙烯酸羥丙酯、丙烯馱縮水甘油酯。此清單並不詳盡且在各情況下，彼等丙烯酸酯之乙氧基化作用及/或丙氧基化作用可用於進一步修改性質。乂根據本發明之一較佳具體實例’丙烯酸酯為雙官能的月曰知或壤脂族雙官能丙婦酸醋之實例包括三環癸烧二甲醇二丙烯酸酯（Sartomer ® 833s )、二〇号烷甘油二丙烯酸酉曰（Sartomer ® CD 5 3 6 )、1,6-己二醇二丙烯酸醋（Sartomer ® 23 8)、3 -甲基 ι，5-戊二醇二丙烯酸酯（Sart〇mer ⑧ 341 )、一丙一醇二丙稀酸酯（Sartomer® 3 06 )、新戊二醇二丙烯酸醋（Sartomer® 247 )、二羥甲基三環癸烷二丙烯酸酯 (Kayarad R-684 )、1，4-二羥基曱基環己烷二丙烯酸酯、2,2-雙（4-羥基_環己基）丙烷二丙烯酸酯、雙（4_羥基環己基）曱烷二丙稀酸酯。非環狀脂族雙官能丙烯酸酯之實例包括美國專利第6,413,697號之式（F-I)至（F-IV )之化合物’該專利以引用的方式併入本文中。可能的雙官能丙烯酸酯之其他實例為美國專利第6,413,697號之式（F-V)至（F-VIII) 之化合物。其製備亦描述於ΕΡ-Α-0 646 580中，該案以引用的方式併入本文中。式（F-I)至（F-VIII )之一些化合物Wherein η is an integer of 2 to 6, m is an integer of 〇 to (6_n), and Rm is independently of each other an organic group, preferably a C1-C6 alkyl group. 201249880 In the structure (1) of component E, optimally, η is 2' 3 or 4 and m is 0 or 1. According to the invention, the surname a _ will be a specific example, the curable or photocurable composition comprises: A) 25-98 wt%, preferably 5 〇 95 wt% of component a; B) 1-70 Wt% Preferably, 3-40 wt% of component B; C) 0-10 wt%, preferably 1-7 wt% of component c; D) 0.01_l〇wt%, preferably 〇5 5 wt% component d; E) 0.01-10 wt%, preferably _01_3 wt% of component E; each based on the total weight of the composition. According to another embodiment of the present invention, the curable composition comprises: A) 6 0-9 0 wt% of component a; B) 5-40 wt% of component B; C) 1-5 wt% of the group Part C; D) 1-4 wt% of component D; E) 0.0 5 - 2 wt% of component E; each based on the total weight of the composition. In one embodiment of the invention 'in terms of the total weight of the photocurable composition', the composition comprises 25 to 98 wt.%, preferably 50 to 95% by weight, most preferably 60 to 90% by weight of the component. A. In another embodiment of the present invention, the composition comprises 1-70 wt%, preferably 3-40 wt%, and most preferably 5-40 wt% of component B based on the total weight of the photocurable composition. . In another embodiment of the present invention, the composition comprises 0 to 10 wt%, preferably Μ wt%, and most preferably Μ wt% of component C, based on the total of 7 201249880 of the photocurable composition. In another embodiment of the present invention, the composition comprises 0.01 to 10% by weight, preferably 5% to 5% by weight, and most preferably 1-4% by weight of the component 〇 based on the total weight of the photocurable composition. In another embodiment of the present invention, the composition comprises 0.01 to 10 wt%, preferably 13 wt%, and most preferably 0.05 to 2 wt% of component E based on the total weight of the photocurable composition. . According to a preferred embodiment of the present invention, component E exhibits at least one indole or naphthalene ring in which two, three or four hydroxy substituents are directly bonded to a helix or naphthalene ring. According to another preferred embodiment of the invention, component E comprises optionally substituted benzenediol, benzenetriol or gallic phenol. According to another preferred embodiment of the present invention, component d comprises phenylphosphonic acid, vinylphosphonic acid, octodiphosphonic acid or 2-acrylic acid, 2-[(2-phosphinylethoxy)methyl]-ethyl bromide (Also known as 2-[4-(dihydroxyphosphonyl)-2_oxy-butyl]ethyl acrylate). According to a preferred embodiment of the invention, component B is a polythiol exhibiting from 2 to 4 SH groups. According to a preferred embodiment of the present invention, component B comprises pentaerythritol tetrakis(3-mercaptopropionate), ethylene glycol di- 3 -mercaptopropionate, trishydroxypropylpropane di-3-mercaptopropionic acid Ester or pentaerythritol tetrakis(3_mercaptobutyric acid). According to a preferred embodiment of the invention, component A comprises a diacrylate or dimethacrylate, especially 1.6-hexanediol diacrylate or bisphenol a ethoxylated bis(indenyl)acrylate. 201249880 According to a preferred embodiment of the present invention, the photocurable composition has a viscosity at 25 〇c after 76 days or 110 days at 65 C which is still less than 3.5 times the initial viscosity of the composition at 25 ° C. , preferably 2.5 times, best 2 times. According to a second aspect of the present invention, there is provided a method of manufacturing a three-dimensional article in a continuous section according to an article model, comprising the steps of: • opening a first layer of the photocurable composition of the present invention; • making the first layer Exposure to actinic radiation sufficient to harden the first layer of the image area in a pattern corresponding to the respective cross-section of the model; • forming a second layer of the photocurable composition of the present invention on the first layer of the hardening; The second layer is exposed to actinic radiation sufficient to harden the second layer of the image area in a pattern corresponding to the respective cross-section of the model; and the previous two steps are repeated as needed to form a continuous layer to form the specialized three-dimensional article. The actinic radiation is preferably incoherent and is emitted by an ultraviolet (uv) lamp. (A) Component a According to the present invention, the curable composition comprises a component A which may, for example, be an acrylate or methacrylate or allyl ether or an alkyne or allyl or a mixture thereof. In the following paragraphs, the acrylate component suitable for the resin composition of the present invention is listed. Acrylic 醅έ 八可』岬驮曰曰曰 group / knife can refer to the early acrylate compound or different acrylic acid vinegar compound, early Zha Ren, * τ β t mixed & Suitable acrylate components can be monofunctional, difunctional or higher functional. Monofunctional acrylates can be used to modify the properties of the resin. 9 201249880 Examples of monofunctional acrylates include, for example, isobornyl acrylate from tetrahydrofurfuryl t-carboxylate, ethoxylated phenyl acrylate, benzoic acid octyl acrylate, octyl acrylate, isodecyl acrylate, Propylene tridecyl ester, caprolactone acrylate, phenol phenol acrylate, cyclic trimethylolpropane acetal acrylate, methoxy polyethylene glycol acrylate, methoxy propylene glycol acrylate, hydroxy acrylate Ester, hydroxypropyl acrylate, propylene diglycidyl ester. This list is not exhaustive and in each case, the ethoxylation and/or propoxylation of the acrylates can be used to further modify the properties.较佳In accordance with a preferred embodiment of the present invention, an example of an acrylate-based bifunctional or gluten-based bifunctional acetoacetate includes tricyclic tert-doped dimethanol diacrylate (Sartomer ® 833s ), diterpene Sodium glycerol diacrylate (Sartomer ® CD 5 3 6 ), 1,6-hexanediol diacrylate vinegar (Sartomer ® 23 8), 3-methyl ι, 5-pentanediol diacrylate (Sart〇 Mer 8 341 ), monopropanol diacrylate (Sartomer® 3 06 ), neopentyl glycol diacrylate (Sartomer® 247 ), dimethylol tricyclodecane diacrylate (Kayarad R-684) ), 1,4-dihydroxydecylcyclohexane diacrylate, 2,2-bis(4-hydroxy-cyclohexyl)propane diacrylate, bis(4-hydroxycyclohexyl)decane diacrylate . Examples of acyclic aliphatic difunctional acrylates include the compounds of the formulae (F-I) to (F-IV) of U.S. Patent No. 6,413,697, the disclosure of which is incorporated herein by reference. Other examples of possible difunctional acrylates are the compounds of formula (F-V) to (F-VIII) of U.S. Patent No. 6,413,697. Its preparation is also described in ΕΡ-Α-0 646 580, which is incorporated herein by reference. Some compounds of formula (F-I) to (F-VIII)

S 201249880 為市售的。此清單並不詳盡且在各情況下，彼等二丙烯酸酯之乙氧基化作用及/或丙氧基化作用可用於進一步修改性質。芳族雙官能丙烯酸酯之實例包括雙酚A聚乙二醇二醚二丙烯酸酯（KayaradR_551)、2,2i_亞曱基雙[對伸苯基聚（氧乙烯）氧基]二乙基二丙烯酸酯（KayaradR_712)、氫醌二丙烯酸酯、4,4，·二羥基聯苯二丙烯酸酯、雙酚A二丙烯酸酯、雙酚F二丙烯酸酯、雙酚s二丙烯酸酯、乙氧基化或丙氧基化雙酚A二丙烯酸酯、乙氧基化或丙氧基化雙酚^^二丙S 201249880 is commercially available. This list is not exhaustive and in each case, the ethoxylation and/or propoxylation of their diacrylates can be used to further modify the properties. Examples of the aromatic difunctional acrylate include bisphenol A polyethylene glycol diether diacrylate (Kayarad R_551), 2,2i_arylene di [p-phenylene poly(oxyethylene)oxy]diethyl Acrylate (Kayarad R_712), hydroquinone diacrylate, 4,4, dihydroxybiphenyl diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, bisphenol s diacrylate, ethoxylation Or propoxylated bisphenol A diacrylate, ethoxylated or propoxylated bisphenol ^^ dipropyl

烯酸酯、乙氧基化或丙氧基化雙酚s二丙烯酸酯、雙酚_A 環氧基一丙烯酸酯（Ebecryl⑧37〇〇 ucb Surface Specialties ) ° 本發明之樹脂中所用之較佳聚乙二醇雙官能丙烯酸酯之實例為四乙二醇二丙烯酸酯（Sart〇mer⑧268 )、聚乙二醇（200)二丙烯酸酯（Sartomer® 259 )、聚乙二醇（4〇〇)二丙烯酸酯（Sart〇mer® 344 )。此清單並不詳盡且在各情況下，彼等二丙職sm氧基化作用及/或丙氧基化作用可用於進一步修改性質。三官能丙婦酸醋4具有甚至t高官能性之丙婦酸醋的為己烷-2,4,6-三醇三丙烯酸酯、三丙烯酸甘油酯、乙氧基化或丙氧基化三丙烯酸實例二趣甲基丙炫三丙烯酸酯甘油酯、乙氧基化或丙氧基化醋' 季戊四醇四丙烯酸酯、雙季戊四醇單羥基三丙烯酸酯、 1，1，1-三羥甲基丙烷三丙烯酸二經T基丙烷四丙烯酸酯、二季戊四醇單羥基五丙烯酸 3」 11 201249880 酶、二季戊四醇五丙烯酸酯（Sart〇mer® 399 ) '季戊四醇三丙烯酸醋（Sart〇mer⑧444 )、季戊四醇四丙烯酸酯 (Sartomer® 295 )、三羥甲基丙烷三丙烯酸酯（Sart〇mer⑧ 351 )、參（2-丙稀醯氧基乙基）異氰尿酸酯三丙烯酸酯 (Sart〇mer® 368 )、乙氧基化（3)三羥甲基丙烷三丙烯酸酯 (Sartomer® 454 )、二季戊四醇五丙稀酸醋（sart〇mer⑧ 9041)。合適芳族三丙烯酸酯之實例為三元酚及含有三個羥基之笨齡或甲齡酴路之三縮水甘油醚與丙烯酸之反應產物。此清單並不詳盡且在各情況下，彼等三丙烯酸酯之乙氧基化作用及/或丙氧基化作用可用於進一步修改性質。聚丙烯酸g旨亦可為多官能丙烯酸胺基甲酸酯。丙烯酸胺基甲酸醋可藉由例如使羥基封端之聚胺基曱酸酯與丙烯酸反應或藉由使異氰酸酯封端之預聚物與丙烯酸羥基烷基醋反應來製備得到丙烯酸胺基甲酸酯。較佳為由聚酯二醇、脂族異氰酸酯及丙烯酸羥基烷基酯製成之丙烯酸胺基甲k自曰。較佳亦為具有丙烯酸酯多官能性或混合的丙烯酸及甲基丙歸酸官能性的聚丙稀酸醋。此外’更高官能性的丙烯酸酯，包括超分支聚酯型，亦可用於樹脂改質。市售實例包括來自Sartomer之 CN2301、CN2302、CN2303、CN2304。可用於調配物中之丙烯酸酯之其他實例包括諸如來自Ethyl ester, ethoxylated or propoxylated bisphenol s diacrylate, bisphenol _A epoxy acrylate (Ebecryl 837 〇〇ucb Surface Specialties) ° preferred polyethylene used in the resin of the invention Examples of diol difunctional acrylates are tetraethylene glycol diacrylate (Sart 〇mer 8268), polyethylene glycol (200) diacrylate (Sartomer® 259), polyethylene glycol (4 oxime) diacrylate. (Sart〇mer® 344). This list is not exhaustive and in each case, their propylene sm oxylation and/or propoxylation may be used to further modify the properties. Trifunctional propylene vinegar 4 has even t-high functionality of acetoacetate which is hexane-2,4,6-triol triacrylate, glyceryl triacrylate, ethoxylated or propoxylated Examples of acrylic acid are dimethyl glyceryl triacrylate glyceride, ethoxylated or propoxylated vinegar 'pentaerythritol tetraacrylate, dipentaerythritol monohydroxy triacrylate, 1,1,1-trimethylolpropane three Acrylic acid by T-based propane tetraacrylate, dipentaerythritol monohydroxypentaacrylic acid 3" 11 201249880 Enzyme, dipentaerythritol pentaacrylate (Sart〇mer® 399) 'Pentaerythritol triacrylate vinegar (Sart〇mer8444), pentaerythritol tetraacrylate ( Sartomer® 295), Trimethylolpropane triacrylate (Sart〇mer 8 351 ), ginseng (2-propanyloxyethyl)isocyanurate triacrylate (Sart〇mer® 368 ), ethoxylated (3) Trimethylolpropane triacrylate (Sartomer® 454), dipentaerythritol pentaacetic acid vinegar (sart〇mer 8 9041). Examples of suitable aromatic triacrylates are the reaction products of trihydric phenols and triglycidyl ethers containing three hydroxyl groups or age-old triterpene glycol and acrylic acid. This list is not exhaustive and in each case, the ethoxylation and/or propoxylation of their triacrylates can be used to further modify the properties. The polyacrylic acid g may also be a polyfunctional urethane urethane. Acryl acrylate can be prepared by, for example, reacting a hydroxy-terminated polyamino phthalate with acrylic acid or by reacting an isocyanate-terminated prepolymer with hydroxyalkyl acrylate. . Preferred is an amino acid amide which is made of a polyester diol, an aliphatic isocyanate and a hydroxyalkyl acrylate. Preferred are also acrylic acid and methacrylic acid functional polyacrylate acrylates having acrylate polyfunctional or mixed acrylate. In addition, 'higher functionality acrylates, including superbranched polyesters, can also be used for resin modification. Commercially available examples include CN 2301, CN 2302, CN 2303, CN 2304 from Sartomer. Other examples of acrylates that can be used in the formulation include, for example, from

Kayarad 之 D-310、D-33 0、DPHA-2H、DPHA-2C、DPHA-21、 DPCA-20、DPCA_3〇 ' DPCA-60、DPCA-120、DN-0075、 DN-2475、Τ-2020、T-2040、TPA.320、TPA-330、T-1420、Kayarad's D-310, D-33 0, DPHA-2H, DPHA-2C, DPHA-21, DPCA-20, DPCA_3〇' DPCA-60, DPCA-120, DN-0075, DN-2475, Τ-2020, T-2040, TPA.320, TPA-330, T-1420,

12 201249880 PET-30、THE-330 及 RP-1040 ;來自 Nippon Kayaku 有限公司之 R-526、R-604、R-011、R-300 及 R-205 ;來自 Toagosei Chemical Industry 有限公司之 Aronix M-210、M-220、 M-233、M-240、M-215、M-305、M-309、M-310、M-315、 M-325、M-400、M-6200 及 M-6400;來自 Kyoeisha Chemical Industry 有限公司之 Light acrylate BP-4EA、BP-4PA、 BP-2EA、BP-2PA 及 DCP-A ;來自 Daichi Kogyo Seiyaku 有限公司之 New Frontier BPE-4、TEICA、BR-42M 及 GX-8345 ;來自 Nippon Steel Chemical 有限公司之 ASF-400 ;來自 Showa Highpolymer 有限公司之 Ripoxy SP-1506、SP-1507、SP-1509、VR-77、SP-4010 及 SP-4060 ; 來自 Shin-Nakamura Chemical Industry 有限公司之 NK Ester A-BPE-4 ;來自 Mitsubishi Chemical 有限公司之 SA-1002 ; 來自 Osaka Organic Chemical Industry 有限公司之12 201249880 PET-30, THE-330 and RP-1040; R-526, R-604, R-011, R-300 and R-205 from Nippon Kayaku Co., Ltd.; Aronix M- from Toagosei Chemical Industry Co., Ltd. 210, M-220, M-233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200 and M-6400; Light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA and DCP-A from Kyoeisha Chemical Industry Co., Ltd.; New Frontier BPE-4, TEICA, BR-42M and GX- from Daichi Kogyo Seiyaku Co., Ltd. 8345; ASF-400 from Nippon Steel Chemical Co., Ltd.; Ripoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010 and SP-4060 from Showa Highpolymer Co., Ltd.; from Shin-Nakamura Chemical Industry NK Ester A-BPE-4 from Ltd.; SA-1002 from Mitsubishi Chemical Co., Ltd.; from Osaka Organic Chemical Industry Co., Ltd.

Viscoat-195、Viscoat-230、Viscoat-260、Viscoat-310、 Viscoat-214HP、Viscoat-295、Viscoat-300、Viscoat-360、 Viscoat-GPT、Viscoat-400、Viscoat-700、Viscoat-540、 Viscoat-3000 及 Viscoat-3700。在下文中，列舉適用於本發明之樹脂組成物的甲基丙烯酸酯組分。曱基丙烯酸酯組分可指單一甲基丙烯酸醋化合物或不同甲基丙烯酸酯化合物之混合物。合適曱基丙烯酸醋組分可為單官能、雙官能或更高官能性的。單官能曱基丙烯酸酯可用於修改樹脂性質。單官能甲基丙稀酸醋之實例包括諸如甲基丙烯酸異冰 13 201249880 片醋、曱基丙烯酸四氫糠醋、乙氧基化甲基丙稀酸苯酿、曱基丙烯酸十二烷酯、甲基丙烯酸硬脂醯酉旨 '曱基丙稀奶辛酯 '曱基丙烯酸異癸酯、甲基丙烯酸十三烧醋、甲夷丙稀酸己内酯、壬苯酚曱基丙烯酸酯、環狀三羥甲基丙燒縮甲醛曱基丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸酯、^氣基聚丙二醇曱基丙烯酸酯、甲基丙烯酸羥乙酯、曱基丙稀酸羥丙酯、甲基丙烯酸縮水甘油酯。此清單並不詳盡且在各情況下，彼等甲基丙烯酸酯之乙氧基化作用及/或丙氧基化作用可用於進一步修改性質。脂族或環脂族雙官能甲基丙烯酸酯之實例包括丨，4_二羥基甲基環己烷二甲基丙烯酸酯、2,2_雙（4_羥基-環己基）丙烷二曱基丙烯酸酯、雙（4-羥基環己基）甲烷二甲基丙烯酸酉旨。非環狀脂族雙官能_曱基丙烯酸酯之實例包括美國專利第M13,697號之式（^)至（F_IV)-之化合^，該專利以引用的方式併入本文中。可能的二甲基丙烯酸酯之其他實例為美國專利第6,413,697號之式（F_v)至（F_VIn)之化合物。其製備亦描述於EP_A_〇 646 58〇中，該案以引用的方式併入本文中。式（Fd)至（F_VIn)之一些化合物為市 :的。此清單並不詳盡且在各情況下，彼等二甲基丙烯酸曰之乙氧基化作用及/或丙氧基化作用可用於進一步修改性質。本發明之樹脂中所用的較佳芳族雙官能甲基丙烯酸酯之實例包括6氧基化（2)雙_ A二甲基丙稀酸醋（San〇mer⑧ 14 201249880 101K)、乙氧基化（2)雙酚A二曱基丙烯酸酯（Sartomer ® 348L)、己氧基化（3)雙酚A二甲基丙烯酸酯（Sartomer ® 348C)、乙氧基化（4)雙紛A二甲基丙稀酸醋（Sartomer ® 150 )、乙氧基化（4)雙盼A二甲基丙稀酸g旨（Sartomer⑧ 540)、乙氧基化（1〇)雙盼A二甲基丙烯酸@旨（Sartomer ® 480 )、氫醌二曱基丙烯酸酯、4,4’-二羥基聯苯二曱基丙烯酸酯、雙酚A二曱基丙晞酸酯、雙酚ρ二甲基丙烯酸酯、雙盼S —曱基丙烯酸醋、乙氧基化或丙氧基化雙紛a二甲基丙稀酸酯、乙氧基化或丙氧基化雙酚F二甲基丙稀酸酯及乙氧基化或丙氧基化雙酚S二甲基丙烯酸酯。三官能甲基丙烯酸酯或具有甚至更高官能性之曱基丙烯酸醋的實例包括諸如三環癸烷二甲醇二甲基丙稀酸酯 (Sartomer® 834 )、三羥甲基丙烷三曱基丙烯酸酯 (_Sart〇mer(| 350 )、四羥甲基曱烷四甲基丙烯酸酯 (Sartomer® 367 )、己烷-2,4,6-三醇三甲基丙烯酸酯、三曱基丙烯酸甘油酯、1，1，1-三經甲基丙炫三曱基丙婦酸酯、乙氧基化或丙氧基化三甲基丙烯酸甘油酯、乙氧基化或丙氧基化1，1，1-三經甲基丙烧三曱基丙烯酸酯、季戊四醇四曱基丙烯酸酯、雙三羥甲基丙烷四甲基丙烯酸酯、季戊四醇單羥基三甲基丙烯酸酯、二季戊四醇單羥基五甲基丙烯酸酯。合適芳族三官能甲基丙烯酸酯之實例為三元酚及含有三個經基之苯紛或甲盼盼路之三縮水甘油醚與甲基丙烯酸之反應產物。此清早並不洋盡且在各情況下，彼等甲其丙烯酸S旨之乙氧基化作用及/或丙氧基化作用可用於進一步修 3 15 201249880 改性質。合適芳族三甲基丙烯酸酯之實例為三元酚及含有三個經基之笨盼或曱酴紛酸之三縮水甘油謎與甲基丙稀酸之反應產物。可使用聚甲基丙烯酸酯。聚甲基丙烯酸酯可為多官能甲基丙烯酸胺基甲酸醋。曱基丙炜酸胺基曱酸醋可藉由例如使羥基封端之聚胺基曱酸酯與甲基丙烯酸反應或藉由使異氰酸酯封端之預聚物與曱基丙烯酸經基烧基酯反應來製備得到甲基丙烯酸胺基甲酸酯。較佳為由聚酯二醇、脂族異氰酸酯及甲基丙烯酸羥基烷基酯製成之甲基丙烯酸胺基甲酸s旨。較佳亦為具有甲基丙烯酸酯多官能性或混合的丙烯酸及曱基丙烯酸官能性的聚甲基丙稀酸醋。本發明之树月曰中所用之較佳脂族甲基丙姊酸胺基甲酸醋之實例包括 Genomer® 4205、Genomer® 4256 及 Genomer® 4297 ° 此外’更高官能性的曱基丙烯酸酯，包括超分支聚酉旨型，亦可用於樹脂改質。可作為組分A用於本發明之可固化組成物中之烯丙基醚的實例為含有一或多個烯丙基醚基之單體，該等烯丙基醚基通常鍵結於可以多種多元醇為主之核心結構基團上。合適多元醇之非限制性實例包括新戊二醇、三羥曱基丙烷、乙二醇、丙二醇、丁二醇、二乙二醇、丨，3_丙二醇、亞甲基二醇（Methylene glyc〇l )、三羥甲基乙烷、季戊四醇' 甘油、雙甘油、1，4-丁二醇、M-已二醇、〗，4•環己烷二甲醇。其他例示性烯丙基醚單體包括羥乙基烯丙基醚、羥丙 16 201249880 基稀丙基峻、三敍甲I工^ ^ 一甲基丙烷皁烯丙基醚、三羥甲基丙烷二烯丙基醚、三羥曱某r„ 乙坑早烯丙基鰱、三羥甲基乙烷二烯丙基鍵、甘油單嫌而其— 佈丙基醚、甘油二烯丙基醚、季戊四醇單烯丙基越、季戍四醇；-，膝工好一 ^ 醉—烯丙基醚、季戊四醇三烯丙基醚、 A6-己三醇單締丙基n，2,6_己三醇二稀丙基…類似物。較㈣丙基峻為季戊四醇稀丙基驗。可作為組分A用於本發明之可固化組成物令之块煙的實例包括苯乙炔、；!_己炔炔1-辛炔、卜癸炔、15_己二炔、 I7-辛二炔、3,3-二甲其 1 丁认土 _丁炔、炔丙基氯、炔丙基溴、炔丙醇、3-丁炔醇、丨_奈执辛炔-3·醇、甲基炔丙基醚、炔丙基趟、3 - ψ乳基-3 _甲基_ 1 _ 丁伊、7。 „ J炔、2_甲基-3-丁炔-2-醇' 1_乙炔環己胺、單炔丙基胺、卜二甲基了悉版基-2-丙炔、三炔丙基胺、 3-丁炔-2-酮、丙炔酸、卜乙访识:暴_ 1 -¼己醇、丙炔酸甲酯及二甲基矽烷基乙炔、2_戊炔、4_辛千狀 2-丁块-1，4_二醇、3- 己块-2,5-二醇及苯基· y 块較佳炔烴為1，7·辛二炔。待用作本發明之可固化組成中之組分Α的適當化合物亦為二聚氰酸三烯丙基酯、二一 —炸丙基二畊三酮及其類似類生之化合物。較佳化合二刃两一烯丙基三哄三酮 (TATATO)。 (B )組分B (硫醇）根據本發明，可固化組成物包含至少一種硫醇組分Β 樹脂組成物包含至少一種單官能或多官能硫醇。多官能硫醇意指具有兩個或兩個以上硫醇基之硫醇多官能硫醇可為不同多官能硫醇之混合物。 5 17 201249880 本發明組成物之多官能硫醇組分可為每個分子具有兩個或兩個以上硫醇基之任何化合物。合適多官能硫醇描述於美國專利第3,661，744號第8行第76列至第9行第46列; 美國專利第4，119,617號第7行第.57^美國專利第號；及第4,289,867號。尤其較佳為藉由^或β_ 疏基㈣（諸如硫代乙醇酸$ ρ_織基丙酸）酯化多元醇而獲得的多官能硫醇。本發明之組成物中所用之較佳硫醇之實例包括季戊四醇四-(3-魏基丙酸醋）（ΡΕΤΜΡ)、季戊四醇肆（3_毓基丁酸 (ΡΕΤΜΒ )、二經曱基丙燒二_(3_疏基丙酸酶）（ΤΜρΜρ )、乙二醇二-(3-巯基丙酸酯）（GDMp)、季戊四醇四毓基乙酸 S旨（PETMA)、三經曱基丙烧三毓基乙酸酯（tmpma)'乙二醇二巯基乙酸酷（GDMA)、乙氧基化三甲基丙烷三（3•毓基-丙酸酯）700 (ETTMP 700 )、乙氧基化三曱基丙烷三（3_ 巯基丙酸酯）1300 (ETTMP 1300 )、丙二醇3_巯基丙酸酯 800 ( PPGMP 800 )、丙二醇 3-疏基丙酸酯 2200 ( PPGMP 2200 ) 〇 (C)組分C (自由基光引發劑）根據本發明’可固化組成物較佳為光可固化的且較佳包含至少一種自由基光引發劑。自由基光引發劑可為光引發系統，其包含不同光引發劑及/或增敏劑之組合。然而，光引發系統亦可為包含不同化合物之組合的系統’該等化合物在單獨使用時不展現任何光引發性，但當組合在一起時展現光引發性。 18 201249880 光引發劑可選自常用以引發自由基光聚合之彼等光引發劑。自由基光引發劑之實例包括安息香類，例如安息香、安息香鍵（諸如安息香曱醚、安息香乙醚、安息香異丙醚、安息香苯基醚）及乙酸安息香酯；苯乙酮類，例如苯乙酮、 2,2_ —曱氧基本乙酮及1，1_二氣苯乙_ ;二苯基乙二_縮網類’例如二笨基乙二酮二曱基縮酮及二苯基乙二酮二乙基縮酮；蒽醌類’例如2-甲基蒽醌、2-乙基蒽醌、2_第三丁基蒽醌、1-氯蒽醌及2-戊基蒽醌；三苯基膦；氧化苯曱醯基膦類’例如氧化2,4,6-三曱基苯甲醯基-二苯基膦（Lucirin⑧ TPO );氧化雙醯基膦；二苯曱酮類’例如二苯甲酮及4,4,_ 雙（N，N -二-曱基胺基）二苯甲酮；9_硫氧蔥酮及氧蔥酮；。丫咬衍生物；啡畊衍生物；喹喏啉衍生物；丨_苯基-丨，2_丙二嗣 2-0-笨甲醯基肟；4_(2_羥乙氧基）苯基_(2_丙基）酮（卜以⑶“ 2959; Ciba Specialty Chemicals); 1-胺基苯基酮或經基苯基網’例如1-經基環己基苯基酮（Irgacure ® 184 )、2-經基異丙基苯基酮、苯基丨_羥基異丙基酮及4_異丙基苯基卜經基異丙基酮。在諸如二苯曱酮或9_硫氧蔥_之所謂Η型光引發劑中，通常需要輔助引發劑，其一般以三級胺為主。對於本申請案，較佳選擇自由基光引發劑且較佳調節其濃度以實現吸收能力，使得固化厚度為約0.05 mm至約 2.5mm。 (D)組分D (膦酸）根據本發明，可固化組成物包含至少一種膦酸D。膦酸 201249880 實例為；^基麟酸、甲其膝允、 -文本^基膦酸、芳基膦酸或攜帶可聚合取代基之膦g文。較佳膦酸之實例為乙稀膦酸（νρ )、苯麟酸 (PPA)、2_丙稀酸2_[(2_麟酿乙氧基）甲基]小乙醋，亦稱為 2_[4-(二羥基磷醯基）·2_氧—丁基]丙烯酸乙酯 ΜΑ154) 〇 (Ε )組分ε 根據本發明，可固化組成物包含至少一種組分ε，其為見至ν個3有至少兩個羥基取代基之苯環或萘環的苯或萘系列組分。 «玄至ν兩個羥基取代基較佳直接連接於苯環或萘環上。組分Ε較佳展現以下結構（1 ): R„ (〇H)n 其中η為2至6之整數，m為〇至（6_n)之整數，且彼此獨立地為有機基團，較佳cuC6院基。在組分E之結構（υ中，最佳地，η為2、3或4且m 為0或1。組分E較佳展現至少一個苯環或萘環其具有兩個、三個或四個羥基取代基直接鍵結於該笨環或萘環上。 .、且刀E較佳包含視情況經取代之笨二盼、苯三酚或五倍子盼。具體可能用作組分E之化合物之實例為：五倍子酚 20 201249880 (PRA )、4-第三丁基-1,2-二羥基苯（BDB )。該組成物可含有其他成分。其他成分之實例包括（但不限於）光穩定劑；增敏劑；抗氧化劑；填充劑，諸如強化填充劑、增量填充劑及導電填充劑；助黏劑；及螢光染料。【實施方式】已製造本發明之可固化組成物的若干實施例及比較實施例。表I展示用於製造本發明可固化組成物之實施例及比較實施例的各組分之商標名、供應商及化學名稱（參見表 II A 至表 II F )。商標名供應商 _ 化學名稱組分A : Sartomer SR348L Cray Valley / Sartomer 乙氧基化(2)雙酚A二甲基丙烯酸酯 HDDA Aldrich 1，6-己二醇-丙烯酸酯 Sartomer SR 349 Cray Valley / Sartomer 乙氧基化(3)雙酚A二丙烯酸酯 Sartomer SR 9035 Cray Valley / Sartomer 乙氧基化(15)三羥曱基丙烷三丙烯酸酯 Ebecryl 8402 Cytec --_脂族二丙烯酸胺基甲酸醋_ 季戍四醇稀丙基 Aldrich -^季戊四薛嬙丙基醚 1，7-辛一炔 Aldrich _____1，7-辛二快_ TAICROS Evonik --丙基三明：三酮組分B ： Thiocure PETMP Bruno Bock 李·/¾.四ffit 4舍/^ ίΓί*试：工亦匕、 Thiocure TMPMP Bruno Bock 1 w吁砰签円蚁Θ曰J 二輕中基-兩：r /Γί* 甘：x; sisfc aiti、 Thiocure GDMP Bruno Bock ---1 1 一乂 yhU 丞内 S文 Θ 曰） --酼基-丙酸酯)_ Karenz MT-PE1 Showa Denko ----肆(3-疏基丁酸酯）組分C : Irgacure 184 Ciba Specialty Chemicals 羥基環己基-苯基酮 21 201249880 商標名供應商化學名稱 Irgacure 651 Ciba Specialty Chemicals 2,2-二曱氧基-1,2-二苯基乙-1-酮 Lucirin ΤΡΟ BASF 氧化2,4,6-三甲基苯甲醯基二苯基膦 • 組分D : PPA Aldrich 苯膦酸 VP Aldrich 乙烯膦酸 MAI 54 Ivoclar Vivadent 2-丙烯酸2-[(2-膦醯乙氧基)曱基]-1 -乙酯或2-[4-(二羥基磷醯基)-2-氧-丁基]丙烯酸乙酯其他有機酸： BA Aldrich 苯甲酸 BSA Aldrich 苯續酸組分E : PRA Aldrich 五倍子酚或1，2,3-三羥基苯 BDB Aldrich 4-第三丁基-1,2-二羥基苯其他苯酚： MP Aldrich 4-曱氧基苯酚表I :表II A至表II F中組成物之組分組成物製備：所研究之調配物之可固化組成物描述於表II A至表II F (實施例1至3 2 )中。以組成物之總重量計，所有組分之重量百分比（wt% )指示於表II A至表II F中。表II A描述實施例1至14，其為包含自由基光引發劑、不同苯酚以及膦酸或不包含膦酸的光可固化之硫醇-烯基組成物。表II B描述實施例15至18，其為包含自由基光引發劑、五倍子酚以及膦酸或不包含膦酸的光可固化之硫醇-烯基組成物。 22 201249880 表Π C描述貫施例19至23’其為包含自由基光引發劑 '五倍子酚、膦酸及不同濃度之季戊四醇肆（3-巯基膦酸醋）的光可固化之硫醇-稀基組成物。表II 〇描述實施例24至26 ’其為包含自由基光引發劑、五倍子酴、膦酸及不同硫醇的光可固化之硫醇-烯基組成物。表II E描述實施例27至28，其為包含不同（曱基）丙烯酸酯、不同自由基光引發劑、五倍子酚及不同膦酸的光可固化之硫醇-烯基組成物。表II F描述實施例29至32，其為包含自由基光引發劑、五倍子酚（除實施例32以外）、膦酸及季戊四醇烯丙基醚或1，7-辛二炔或三烯丙基三啡三酮的光可固化之硫醇· 烯基組成物。藉由將組分D (膦酸）、E (酚系組分）及C (光引發劑）添加至5〇xl5mm玻璃瓶中來製備光可固化組成物。緊接著添加組分A且將該瓶置放於40 °C下之超音波浴中。不時地自超音波浴移出該瓶且震盪幾分鐘直到所有固體完全溶解為止。將混合物冷卻至室溫且隨後添加組分B並混合幾分鐘。接著密封玻璃瓶且在室溫（25 °C )下或在65 °C下陳化。整個過程在隔絕光化輕射的情況下且在標準大氣壓下進行。在製備後即刻及在儲存期内定時在25 °C下進行黏度量測。黏度量測：一種明顯不穩定效應為凝膠化，且因此吾人預計調配 23 201249880 物黏度增加直到其凝膠化為止。因此，根據黏度隨時間之變化研究硫醇-烯基調配物之穩定性。使用緊溱型模組化流變儀Physica MCR 3〇〇量測黏度。對於所有測試而言，使用丨。錐角及25 mm錐形直徑之錐/板幾何形狀。測試始終在251:恆溫下進行。在150。遞減至10 S.1之遞減剪切速率下測試黏度，歷時75秒之時間，每5秒進行一次量測。此舉產生15個量測點。在一之剪切速率下量測黏度。用0.1 ml樣品進行量測，精度為約 ±3.5%。將所製備之調配物保存於環境溫度下具有黃光之房間内。此舉將避免光誘發之聚合。在儲存時間0 (亦即在製備後即刻）在2 5 °C下進行黏度量測，及在室溫（2 5 X：)或6 5 C下，於儲存時間後4至11 〇天内進行黏度量測。表II A至表Π F(貫施例1至32)中所述之光可固化組成物的黏度量測結果記錄於表III A至表III F中。硫醇-烯基光可固化組成物在陳化期内可接受之黏度增量的界定取決於應用。由於在室溫（25 υ )下之陳化測試費時太久’故考慮在6 5 °C下進行加速陳化測試，以便評估光可固化組成物隨陳化時間變化的穩定性。若在65下 76-79天後光可固化組成物在25Ό下之黏度仍小於光可固化組成物在25 Ό下之最初黏度的3.5倍、較佳2_5倍，則該光可固化組成物可被定義為穩定的且可視為適於若干立體微影（SLA)應用，例如充當w〇 2010/043559或WO 2010/043 275中所揭示之用於立體微影快速成型設備之光可Viscoat-195, Viscoat-230, Viscoat-260, Viscoat-310, Viscoat-214HP, Viscoat-295, Viscoat-300, Viscoat-360, Viscoat-GPT, Viscoat-400, Viscoat-700, Viscoat-540, Viscoat- 3000 and Viscoat-3700. Hereinafter, the methacrylate component suitable for the resin composition of the present invention is enumerated. The mercapto acrylate component can refer to a single methacrylate compound or a mixture of different methacrylate compounds. Suitable mercapto acrylate vinegar components can be monofunctional, difunctional or higher functional. Monofunctional methacrylates can be used to modify the properties of the resin. Examples of the monofunctional methyl acetonate include, for example, isobutyl methacrylate 13 201249880 vinegar, tetrahydroanthracene acrylate, ethoxylated methacrylic acid benzene, dodecyl decyl acrylate, Styrene methacrylate 曱曱曱丙丙丙丙辛曱曱曱曱曱曱曱曱曱、、、、、、、、、、、、、、、、、、、、、、、、、、 Trimethylol propyl acetal methacrylate, methoxy polyethylene glycol methacrylate, gas-based polypropylene glycol methacrylate, hydroxyethyl methacrylate, hydroxypropyl propyl acrylate , glycidyl methacrylate. This list is not exhaustive and in each case, the ethoxylation and/or propoxylation of their methacrylates can be used to further modify the properties. Examples of aliphatic or cycloaliphatic difunctional methacrylates include anthracene, 4-dihydroxymethylcyclohexane dimethacrylate, 2,2-bis(4-hydroxy-cyclohexyl)propanedidecylacrylic acid. Ester, bis(4-hydroxycyclohexyl)methane dimethacrylate. Examples of the acyclic aliphatic difunctional methacrylate include the compounds of the formula (i) to (F_IV) of the U.S. Patent No. M13,697, which is incorporated herein by reference. Other examples of possible dimethacrylates are the compounds of the formula (F_v) to (F_VIn) of U.S. Patent No. 6,413,697. Its preparation is also described in EP_A_〇 646 58, which is incorporated herein by reference. Some of the compounds of formula (Fd) to (F_VIn) are commercially available. This list is not exhaustive and in each case, their ethoxylation and/or propoxylation of bismuth methacrylate can be used to further modify the properties. Examples of preferred aromatic difunctional methacrylates for use in the resins of the present invention include 6oxylated (2) bis-A dimethyl acrylate vinegar (San〇mer 8 14 201249880 101K), ethoxylated (2) bisphenol A dimercapto acrylate (Sartomer ® 348L), hexyloxylated (3) bisphenol A dimethacrylate (Sartomer ® 348C), ethoxylated (4) double A Acrylic acid vinegar (Sartomer ® 150 ), ethoxylated (4) bis-A dimethyl acrylate acid (Sartomer 8 540), ethoxylated (1 〇) bis expectant A dimethacrylate @ (Sartomer ® 480 ), hydroquinone dimercapto acrylate, 4,4'-dihydroxybiphenyl dimercapto acrylate, bisphenol A dimercaptopropionate, bisphenol ρ dimethacrylate, Shuangyi S-mercapto acrylate, ethoxylated or propoxylated bis-dimethyl acrylate, ethoxylated or propoxylated bisphenol F dimethyl acrylate and B Oxylated or propoxylated bisphenol S dimethacrylate. Examples of trifunctional methacrylates or mercapto acrylates having even higher functionality include, for example, tricyclodecane dimethanol dimethyl acrylate (Sartomer® 834), trimethylolpropane tridecyl acrylate. Ester (_Sart〇mer (| 350 ), tetramethylol decane tetramethacrylate (Sartomer® 367 ), hexane-2,4,6-triol trimethacrylate, glyceryl trimethacrylate , 1,1,1-trimethyl methacrylic trimethyl propyl acrylate, ethoxylated or propoxylated glyceryl trimethacrylate, ethoxylated or propoxylated 1,1, 1-Trimethyl methacrylate tridecyl acrylate, pentaerythritol tetradecyl acrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol monohydroxy trimethacrylate, dipentaerythritol monohydroxypentamethacrylate Esters. Examples of suitable aromatic trifunctional methacrylates are the reaction products of trihydric phenols and triglycidyl ethers containing three transbasic benzene or pirin and methacrylic acid. And in each case, they have an ethoxylation and/or propoxylation of their acrylic acid It can be used to further modify the modification of 3 15 201249880. Examples of suitable aromatic trimethacrylates are trihydric phenols and triglycidime with three bases or sulphuric acid and methyl acrylate The reaction product can be used. Polymethacrylate can be used. The polymethacrylate can be a polyfunctional methacrylic acid carboxylic acid vinegar. The mercaptopropionyl decanoic acid vinegar can be terminated by, for example, a hydroxyl group-terminated polyamine. The phthalic acid ester is reacted with methacrylic acid or a methacrylic acid urethane is prepared by reacting an isocyanate-terminated prepolymer with a mercapto acrylate via a carboxylic acid ester. An aliphatic isocyanate and a hydroxyalkyl methacrylate made of methacrylic acid methic acid. Preferably, it is also a polymethyl group having a methacrylate polyfunctional or mixed acrylic acid and mercaptoacrylic acid functionality. Acrylic vinegar. Examples of preferred aliphatic methacrylic acid carboxylic acid aceton used in the present invention include Genomer® 4205, Genomer® 4256 and Genomer® 4297 ° in addition to 'higher functionality 曱Acrylate, package The super-branched polyfluorene type can also be used for resin modification. An example of the allyl ether which can be used as the component A in the curable composition of the present invention is a monomer having one or more allyl ether groups. The allyl ether groups are typically bonded to a core structural group which may be based on a plurality of polyols. Non-limiting examples of suitable polyols include neopentyl glycol, trishydroxypropyl propane, ethylene glycol, propylene glycol , butylene glycol, diethylene glycol, hydrazine, 3-propylene glycol, methylene glycol, Methylene glycol, trimethylolethane, pentaerythritol, glycerol, diglycerin, 1,4-butanediol, M-hexanediol, 〖, 4•cyclohexanedimethanol. Other exemplary allyl ether monomers include hydroxyethyl allyl ether, hydroxypropyl 16 201249880 propyl propyl sulphate ^ Monomethylpropane soap allyl ether, trimethylolpropane diallyl ether, trioxindole, r 早早 allyl hydrazine, trimethylolethane diallyl bond, glycerol It is suspected that - propyl ether, glycerol diallyl ether, pentaerythritol monoallyl, quaternary tetraol; -, knee work better ^ drunk - allyl ether Pentaerythritol triallyl ether, A6- hexanetriol single associative propyl n, 2,6_ ... hexanetriol diene-propyl analogs. Compared with (four) propyl sulphate, it is a pentaerythritol dilute propyl test. Examples of the blockable tobacco which can be used as the component A in the curable composition of the present invention include phenylacetylene, ?-hexyne acetylene 1-octyne, dioxyne, 15-hexadiyne, I7-octadiyne , 3,3-dimethyl 1, 1 butyl tert-butyne, propargyl chloride, propargyl bromide, propargyl alcohol, 3-butynol, 丨_奈辛辛acetylene-3·alcohol, methyl alkyne Propyl ether, propargyl hydrazine, 3 - hydrazino-3 _methyl _ 1 _ butyl, 7. „ J alkyne, 2-methyl-3-butyn-2-ol' 1- acetylene cyclohexylamine, monopropargylamine, bis-methyl-formyl-2-propyne, tri-propargylamine , 3-butyne-2-one, propynoic acid, and b. access: _1 -1⁄4 hexanol, methyl propiolate and dimethyl decyl acetylene, 2 pentyne, 4 _ _ _ 2-butlyl-1,4-diol, 3-hexyl-2,5-diol and phenyl·y block. The preferred alkyne is 1,7-octadiyne. Curable to be used in the present invention. Suitable compounds of the component Α in the composition are also triallyl cyanurate, di-propyl propylene diterpene ketone and the like. Preferably, the two-edge uni-allyl Triactone (TATATO) (B) Component B (thiol) According to the invention, the curable composition comprises at least one thiol component Β The resin composition comprises at least one monofunctional or polyfunctional thiol. By alcohol is meant a thiol polyfunctional thiol having two or more thiol groups which may be a mixture of different polyfunctional thiols. 5 17 201249880 The polyfunctional thiol component of the composition of the invention may have one for each molecule Any compound of two or more thiol groups Suitable polyfunctional thiols are described in U.S. Patent No. 3,661,744, line 8, column 76 to line 9, column 46; U.S. Patent No. 4,119,617, line 7, s. 57, U.S. Patent No.; No. 4,289,867. Particularly preferred is a polyfunctional thiol obtained by esterifying a polyol with ^ or β_ thioglycol (tetra) (such as thioglycolic acid $ ρ woven propionic acid). Examples of the preferred mercaptan include pentaerythritol tetrakis-(3-propylpropionic acid vinegar) (yttrium), pentaerythritol bismuth (3_mercaptobutyric acid (ΡΕΤΜΒ), di-mercaptopropylpropanoid bis(3-disylpropionic acid) Enzyme) (ΤΜρΜρ), ethylene glycol di-(3-mercaptopropionate) (GDMp), pentaerythritol tetradecyl acetic acid S (PETMA), tri-propyl mercaptotridecyl acetate (tmpma) Glycol dimercaptoacetic acid (GDMA), ethoxylated trimethylpropane tris(3•mercapto-propionate) 700 (ETTMP 700), ethoxylated trimethylstipropane tris(3_mercaptopropionic acid Ester) 1300 (ETTMP 1300), Propylene Glycol 3_Mercaptopropionate 800 (PPGMP 800), Propylene Glycol 3-Silyl Propionate 2200 (PPGMP 2200) 〇 (C) Component C (Free Radical Photoinitiator) The curable composition is preferably photocurable and preferably comprises at least one free radical photoinitiator according to the invention. The free radical photoinitiator can be a photoinitiator system comprising different photoinitiators and/or sensitizers. Combinations. However, the photoinitiator system can also be a system comprising a combination of different compounds that do not exhibit any photoinitiation when used alone, but exhibit photoinitiation when combined. 18 201249880 The photoinitiator can be selected from the group of light initiators commonly used to initiate free radical photopolymerization. Examples of free radical photoinitiators include benzoin, such as benzoin, benzoin bonds (such as benzoin ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether) and benzoin acetate; acetophenones, such as acetophenone, 2,2_-decyloxybenzolone and 1,1_diqibenzene-6; diphenylethylenedi-condensed network such as di-p-ethylidenedione dimethyl ketal and diphenylethylenedione Ethyl ketal; hydrazines such as 2-methyl hydrazine, 2-ethyl hydrazine, 2 - tert-butyl hydrazine, 1-chloroindole and 2-pentyl hydrazine; triphenylphosphine Benzoylphosphine oxides such as 2,4,6-trimercaptobenzylidene-diphenylphosphine (Lucirin8 TPO); bisphosphonium oxide; benzophenones such as diphenyl Ketone and 4,4,_bis(N,N-di-decylamino)benzophenone; 9-thioxanthone and xanthon; Biting derivative; cultivating derivative; quinoxaline derivative; 丨_phenyl-hydrazine, 2_propane bismuth 2-0- benzoyl hydrazide; 4_(2_hydroxyethoxy)phenyl (2-propyl) ketone (Bu (3) "2959; Ciba Specialty Chemicals); 1-aminophenyl ketone or phenyl-based network such as 1-cyclohexyl phenyl ketone (Irgacure ® 184 ), 2 - isopropylidene phenyl ketone, phenyl hydrazine hydroxy isopropyl ketone and 4 isopropyl phenyl propyl isopropyl ketone. In the so-called quinone type such as benzophenone or 9 thiosulfate In the photoinitiator, a co-initiator is generally required, which is generally dominated by a tertiary amine. For the purposes of this application, a free radical photoinitiator is preferred and its concentration is preferably adjusted to achieve an absorption capacity such that the cured thickness is about 0.05. Mm to about 2.5 mm. (D) Component D (phosphonic acid) According to the present invention, the curable composition comprises at least one phosphonic acid D. The phosphonic acid 201249880 is exemplified by: ^ nucleolinic acid, its knees, - text ^ Phosphonic acid, arylphosphonic acid or a phosphine carrying a polymerizable substituent. Examples of preferred phosphonic acids are ethylphosphonate (νρ), phenyl sulphate (PPA), 2-acrylic acid 2_[(2) _ 麟 ethoxylated) Small ethyl vinegar, also known as 2_[4-(dihydroxyphosphonyl)·2_oxy-butyl]ethyl acrylate ΜΑ 154) 〇 (Ε) component ε According to the invention, the curable composition comprises at least one Component ε, which is a benzene or naphthalene series component of benzene or naphthalene ring having ν 3 groups having at least two hydroxy substituents. «The two hydroxy substituents of 玄至ν are preferably directly bonded to a benzene ring or a naphthalene ring. The component Ε preferably exhibits the following structure (1): R „(〇H)n wherein η is an integer from 2 to 6, m is an integer from 〇 to (6_n), and is independently an organic group, Preferred cuC6 yard base. In the structure of component E (υ, optimally, η is 2, 3 or 4 and m is 0 or 1. Component E preferably exhibits at least one benzene or naphthalene ring which has two, three or four The hydroxy substituent is directly bonded to the acyclic or naphthalene ring, and the knives E preferably comprise, as the case may be, a stupid, phloroglucin or a gallnut. It may be used as a compound of component E. Examples are: gallicol 20 201249880 (PRA), 4-tert-butyl-1,2-dihydroxybenzene (BDB). The composition may contain other ingredients. Examples of other ingredients include, but are not limited to, light stabilizers. Sensitizer; antioxidant; filler such as reinforced filler, extender filler and conductive filler; adhesion promoter; and fluorescent dye. [Embodiment] Several embodiments of the curable composition of the present invention have been produced. EXAMPLES AND COMPARATIVE EXAMPLES Table I shows the trade names, suppliers, and chemical names of the components used in the manufacture of the examples of the curable compositions of the present invention and comparative examples (see Tables II A through II F). Supplier _ Chemical Name Component A : Sartomer SR348L Cray Valley / Sartomer Ethoxylated (2) Bisphenol A Dimethacrylate HDDA Aldrich 1,6-Hexanediol-Acrylate Sartomer SR 349 Cray Valley / Sartomer Ethoxylated (3) Bisphenol A Diacrylate Sartomer SR 9035 Cray Valley / Sartomer Ethoxylated (15) Trihydroxydecylpropane Triacrylate Ebecryl 8402 Cytec --_ Aliphatic Dialkyl Amino Acid Hydrate _ Quarterly Tetrahydrin Dilyl Aldrich -^ Dipentazone Propyl ether 1,7-octyl-alkyne Aldrich _____1,7-xin two fast _ TAICROS Evonik - propyl succinimide: triketone component B : Thiocure PETMP Bruno Bock Lee · / 3⁄4. four ffit 4 house / ^ ίΓί * Test: Gong Yizhen, Thiocure TMPMP Bruno Bock 1 w 砰砰円円二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二二丞内 S文Θ 曰) -- mercapto-propionate) _ Karenz MT-PE1 Showa Denko ---- 肆 (3-cisylbutyrate) Component C : Irgacure 184 Ciba Specialty Chemicals Hydroxycyclohexyl- Phenylketone 21 201249880 Trade Name Supplier Chemical Name Irgacure 651 Ciba Specialty Chemicals 2,2-Dimethoxy-1,2-II Phenylethyl-1-one Lucirin ΤΡΟ BASF Oxidation of 2,4,6-trimethylbenzhydryldiphenylphosphine • Component D: PPA Aldrich phenylphosphonic acid VP Aldrich Methylphosphonate MAI 54 Ivoclar Vivadent 2-Acrylic 2-[(2-Pyridinylethoxy)indolyl]-1 -ethyl ester or 2-[4-(dihydroxyphosphonyl)-2-oxo-butyl]ethyl acrylate Other organic acids: BA Aldrich Benzoic acid BSA Aldrich Benzene acid component E : PRA Aldrich Gallic phenol or 1,2,3-trihydroxybenzene BDB Aldrich 4-Ter Butyl-1,2-dihydroxybenzene Other phenol: MP Aldrich 4-oxo Phenols Table I: Component Compositions of the Compositions in Tables II A to II F: The curable compositions of the formulations studied are described in Tables II A through II F (Examples 1 to 3 2) . The weight percentages (wt%) of all components are indicated in Tables II A to II F based on the total weight of the composition. Table II A describes Examples 1 through 14 which are photocurable thiol-alkenyl compositions comprising a free radical photoinitiator, different phenols and phosphonic acids or no phosphonic acid. Table II B describes Examples 15 to 18 which are photocurable thiol-olefin compositions comprising a free radical photoinitiator, gallic phenol and a phosphonic acid or no phosphonic acid. 22 201249880 Table C describes the examples 19 to 23' which are photocurable thiols containing a free radical photoinitiator, gallic phenol, phosphonic acid and different concentrations of pentaerythritol bismuth (3-mercaptophosphonic acid vinegar). Base composition. Table II 〇 describes Examples 24 to 26' which are photocurable thiol-alkenyl compositions comprising a free radical photoinitiator, gallic quinone, phosphonic acid and various thiols. Table II E describes Examples 27 through 28 which are photocurable thiol-alkenyl compositions comprising different (mercapto) acrylates, different free radical photoinitiators, gallic phenols and different phosphonic acids. Table II F describes Examples 29 to 32 which are comprised of a free radical photoinitiator, gallic phenol (other than Example 32), phosphonic acid and pentaerythritol allyl ether or 1,7-octadiyne or triallyl A photocurable thiol·alkenyl composition of trimorphin. A photocurable composition was prepared by adding components D (phosphonic acid), E (phenolic component), and C (photoinitiator) to a 5 〇 x 15 mm glass vial. Component A was then added and the bottle was placed in an ultrasonic bath at 40 °C. From time to time, remove the bottle from the ultrasonic bath and shake for a few minutes until all solids are completely dissolved. The mixture was cooled to room temperature and then component B was added and mixed for a few minutes. The vial was then sealed and aged at room temperature (25 °C) or at 65 °C. The entire process is carried out under conditions of isolation, light and light exposure and at standard atmospheric pressure. Viscosity measurements were made at 25 °C immediately after preparation and during storage. Viscosity measurement: An obvious unstable effect is gelation, and therefore we expect to adjust the viscosity of the compound until it gels. Therefore, the stability of the thiol-alkenyl formulation was investigated based on the change in viscosity over time. Viscosity was measured using a compact modular rheometer Physica MCR 3®. For all tests, use 丨. Cone angle and cone/plate geometry with a 25 mm cone diameter. The test is always performed at 251: constant temperature. At 150. Decrease to a test viscosity at a decreasing shear rate of 10 S.1 for a period of 75 seconds and measure every 5 seconds. This produces 15 measurement points. The viscosity is measured at a shear rate. The measurement was performed with a 0.1 ml sample with an accuracy of about ±3.5%. The prepared formulation was stored in a room with yellow light at ambient temperature. This will avoid photoinduced polymerization. Viscosity measurement at 25 ° C at storage time 0 (ie immediately after preparation) and viscosity at 4 to 11 days after storage time at room temperature (2 5 X:) or 6 5 C Measure. The results of the adhesion measurements of the photocurable compositions described in Tables A through C (Comparative Examples 1 to 32) are reported in Tables III A through III F. The definition of the viscosity increase acceptable for the thiol-alkenyl photocurable composition during the aging period depends on the application. Since the aging test at room temperature (25 υ) takes too long, an accelerated aging test at 65 ° C is considered to evaluate the stability of the photocurable composition as a function of aging time. If the viscosity of the photocurable composition at 25 76 after 65 to 79 days is still less than 3.5 times, preferably 2 to 5 times the initial viscosity of the photocurable composition at 25 ,, the photocurable composition may be Is defined as stable and can be considered to be suitable for several stereo lithography (SLA) applications, for example as light for stereo lithography rapid prototyping equipment as disclosed in WO 〇 2010/043559 or WO 2010/043 275

24 201249880 固化樹脂。在表ΙΠ A中’比較實施例1 ' 2、4、7、9、11至14 展不光可固化的硫醇_烯基組成物在65 t下76天後不穩定且黏度急劇增加或甚至發生凝膠化。在表III A中，本發明之實施例3展示光可固化的硫醇烤基組成物令人驚訝且出乎意料地受五倍子酚與膦酸之組合的協同作用之影響而穩定，且在下76天後僅出現輕微黏度增加（自〇.99 Pa.s至1.64 Pa.〇。實施例3應與實施例1及2相比，實施例1 & 2為類似組成物，但不展現五倍子酚與膦酸之有利穩定組合。在表III A中，本發明之實施例5展示光可固化的硫醇 -烯基組成物令人驚訝且出乎意料地受五倍子酚與膦酸之組合。的協同作用之影響而穩定（若五倍子酚之量僅為 wt% ’亦如此），且在㈣下％天後僅出現輕微黏度增加〔自〇.99?^至實施例5應與實施例1及4相比，實施例1及4為類似組成物，但不展現五倍子酚與膦酸之有利穩定組合。在表III A中，本發明之實施例8展示光可固化的硫醇 -烯基組成物令人驚訝且出乎意料地受4_第三丁基-丨，2·二羥基苯與膦酸之組合的協同作用之影響而穩定，且在Μ。下 76天後僅出現輕微黏度增加（自〇 93 至pa s)。實施例8應與實施例…相比，實施例1及7為類似組成物’但不展現4_第三丁基·1>2_二羥基笨與膦酸之有利穩定組合。 25 201249880 在表III B中’本發明之實施例1 5及16展示光可固化的硫醇-稀基組成物令人驚费且出乎意料地受五倍子紛與不同類型膦酸之組合的協同作用之影響而穩定，且在6 5下 76天後僅出現輕微黏度增加（分別自〇.92Pa.s至i.7ipa. s及自1.03 Pa. s至1.83 Pa. s )。實施例15及16應與實施例 17及1 8相比，實施例1 7及1 8為類似組成物，但展現五倍子紛與非膦酸之組合。在表III C中，本發明之實施例19至23展示光可固化的硫醇-烯基組成物令人驚訝且出乎意料地受五倍子盼與鱗酸之組合的協同作用之影響而穩定，此時季戊四醇肆（3_疏基丙酸酯）之含量自4 wt%變化至34 wt%，且在65 °C下79 天後僅出現輕微黏度增加。在表III D中，本發明之含有不同類型硫醇之實施例24 至26展示光可固化的硫醇-稀基組成物令人驚言牙且出乎专料地受關於不同類型硫醇之五倍子酚與膦酸之組合的協同作用之影響而穩定，且在65Ό下79天後僅出現輕微黏度增加。在表III E中，本發明之含有不同類型（甲基）丙烯酸酯之實施例27至28展示光可固化的硫醇-烯基組成物令人驚舒且出乎意料地受關於不同類型（曱基）丙烯酸酯之五倍子紛與膦酸之組合的協同作用之影響而穩定，且在65 t下％天後僅出現輕微黏度增加（分別自1.84 Pa.s至4 〇1 pa s 及自 1.89 Pa.s 至 3.64 Pa.s)。在表IIIF中，本發明之含有不同類型烯丙基醚或炔烴 26 201249880 或烯丙基啩之實施命"9m示光可固化的硫醇_稀基組成物令人驚訝且出乎意料地受關於不同類型烯丙基醚或炔烃或烯丙基啡之五倍子酚與膦酸之組合的協同作用之影響而穩疋，且在65 C下79天後僅出現輕微黏度增加。比較實施例32展現與實施例3〇相同的組成物，其不含五倍子酚且在65 °C下1天後凝膠化。光可固化組成物之光固化：本發明之光可固化組成物已藉由使用不相干的光化輻射及紫外線（uv)輻射進行固化來製造三維（3D)物件。穩定系統膦酸/酚系組分添加於硫醇_烯基光可固化組成物中既不改變組成物之反應性、光敏性、固化速度，亦不改變所製造3D物件之機械強度、彈性模數、動性。使用數位光處理（DLP )製造缺口衝擊強度測試之試樣使用立體微影设備EnvisionTec Perfactory® SXGA + W/ERM Mini MultiLens，以 1400x 1050 之解析度製造3D部件。在800 mW/dm2之燈功率下，以u秒之暴露時間構建50 μπι層厚度之試樣。在結構化製程完成後，用乙醇沖洗原型，接著在UV燈（INTELLI-RAY 600 Watt UV flood curing system)下進行後固化2〇分鐘（每一側各1〇分鐘）。缺口衝擊強度之試樣為約14/7/55 mm (寬度/高度/ 長度）之尺寸的矩形。伊佐德氏（Izod )缺口衝擊強度測試：使用DLP形成之缺口試樣評估伊佐德氏缺口衝擊強度。根據ISO 180標準，在配備有錘子之Zwick型號5113上 27 201249880 衝擊測試機類型機器（Zwick公司，Germany )上進行測試。表IV展示固化組成物1 (比較實施例）及本發明之組成物5即刻或在65 °C下30天之儲存時間後固化的缺口衝擊強度量測結果。缺口衝擊強度量測展示添加穩定系統膦酸/ 酚系組分完全不削弱固化組成物之衝擊強度。此外，固化穩定組成物之衝擊強度完全不受固化前在65 °C下30天之陳化時間的影響。實施例編號在65 °C下之儲存時間（天）黏度 (Pa·s ) acN [kJ/m2】標準差 [kJ/m2] 方差[%】 1 0 1.71 7.25 0.087 12.01 5 0 0.90 6.80 0.117 17.25 30 1.34 6.54 0.024 3.73 表IV :固化組成物1及5之缺口衝擊強度量測結果實施例編號 1 (wt%) 2 (wt%) 3 (wt%) 4 (wt%) 5 (wt%) 6 (wt%) 7 (wt%) 8 (wt%) 9 (wt%) 10 (wt%) 11 (wt%) 12 (wt%) 13 (wt%) 14 (wt%) SR348L 61.8 62.37 61.17 62.94 61.74 61.80 62.18 60.99 62.92 61.72 62.37 61.17 62.94 61.74 PETMP 33.35 33.66 33.01 33.97 33.32 33.35 33.56 32.91 33.96 33.31 33.66 33.01 33.97 33.32 IRG184 2.95 2.97 2.92 2.99 2.94 2.94 2.96 2.90 2.99 2.94 2.97 2.92 2.99 2.94 PRA - 1 1 0.1 0.1 0.01 - - BDB 1.3 1.3 0.13 0.13 - - MP - 1 1 0.1 0.1 MA154 1.9 - 1.9 - 1.9 1.9 - 1.9 量 1.9 1.9 - 1.9 總計 100 100 100 100 100 100 100 100 100 100 100 100 100 100 表II A :具有不同酚系組分之組成物 28 201249880 實施例編號 15 (wt%) 16 (wt% ) 17 (wt% ) 18 (wt%) SR348L 62.37 62.12 62.31 62.12 PETMP 33.66 33.52 33.63 33.52 IRG184 2.97 2.96 2.96 2.96 PRA 0.1 0.1 0.1 0.1 VP 0.9 - - - PPA - 1.3 - - BA - - 1 BSA - - - 1.3 總計 100 100 100 100 表II B :具有膦酸及不具有膦酸之組成物實施例編號 19 (wt% ) 20 (wt% ) 21 (wt% ) 22 (wt%) 23 (wt% ) SR348L 61.86 69.14 80.11 87.02 90.93 PETMP 33.44 26.15 15.15 8.23 4.31 IRG184 2.85 2.85 2.85 2.85 2.85 PRA 0.1 0.1 0.1 0.1 0.1 MAI 54 1.75 1.76 1.79 1.80 1.81 總計 100 100 100 100 100 表II C :具有不同PETMP濃度之組成物實施例編號 24 (wt% ) 25 (wt% ) 26 (wt% ) SR348L 62.39 60.00 59.44 GDMP 32.88 - - TMPMP - 35.27 - Karenz PEI - - 35.82 IRG184 2.86 2.86 2.86 PRA 0.1 0.1 0.1 MAI 54 1.77 1.77 1.78 總計 100 100 100 表II D :具有不同硫醇之組成物 29 201249880 實施例編號 27 (wt% ) 28 (wt%) SR348 31.7 31.91 SR349 18.1 18.22 SR9035 9.51 9.58 Ebecryl 8402 26.28 26.46 IRG651 1.31 1.32 Lucirin ΤΡΟ 1.1 1.11 ΡΕΤΜΡ 10 10 PRA 0.1 0.1 ΡΡΑ - 1.3 MAI 54 1.9 - 總計（wt%) 100 100 表II E :具有不同（甲基）丙烯酸酯之組成物實施例編號 29 (wt%) 30 (wt% ) 31 (wt%) 32 (wt% ) 季戊四醇烯丙基醚 39.62 - - - 1,7-辛二炔 28.81 - 29.45 三烯丙基三明^ 三酮 - 38.60 - PETMP 55.63 66.35 56.78 67.65 IRG184 2.86 2.86 2.86 2.90 PRA 0.1 0.1 0.1 - MA154 1.79 1.88 1.66 - 總計（wt%) 100 100 100 100 表II F:具有烯丙基醚或炔烴或烯丙基啡之組成物 30 201249880 實施例編號儲存時間（天）在25。(：下在6 下黏度（Pa-s) 1 在室溫下22天後及在65 °C下19小時内凝膠化 2 0 0.95 0.95 21 1.00 2.48 76 1.10 16.2 110 1.10 35.65 3 0 0.99 0.99 21 0.98 1.21 76 0.97 1.64 110 0.97 1.89 4 0 0.88 0.88 20 0.95 5.85 76 1.24 31.27 110 1.54 固體 5 0 0.90 0.90 20 0.90 1.08 76 0.87 1.46 110 0.88 1.71 6 0 0.89 245 3.15 7 0 0.89 0.89 20 0.95 7.11 76 1.22 64.98 110 1.40 固體實施儲存時在25°C下在65°C下黏度（Pa-s) 8 0 0.93 0.93 21 0.96 1.22 76 0.95 2.12 110 0.95 2.94 9 0 0.86 0.86 21 1.04 9.72 76 1.51 34.23 110 1.831 固體 10 0 0.89 21 0.90 76 0.91 110 0.93 11 0 0.89 0.89 14 3.46 8.26 22 4.51 16.52 76 2.87 固體 12 0 0.85 0.85 14 固體固體 13 0 0.84 0.84 14 23.63 固體 14 0 0.90 0.90 14 1.74 固體 22 固體固體表III A :表II A中具有不同酚系組分之組成物隨著在25 °C及65 °C下之陳化時間變化的在25°C下之黏度 31 201249880 實施例在65eC下之儲編號存時間（天) 黏度（Pa-s) 1 0 0.92 -^=1==4 1.35 / 1.90 實施例編號丨 1 〇' s~〜 / 1.05 / 19 u_xm / 1.35 26 ~~ 1.32 79 I 1.41 0 1 1.15 I 20 , 5 1.60 1 26~~~ 1 1.45 1 79 1.73 I 21 5 1.78 1 26 1.46 79 1 1.76 1 0 -—-- 1.41 22 5 1.95 1.59 79 1.67 0 | 1.50 23 5 1.96 1.40 1 1.76 表III C :表II C中具有不同 10 I 9^2 小時後 3 表III B ··表11 B中具有膦醆及不具有膦酸之組成物隨著在65 X： T之陳化時間變化的在25 Γ Τ之黏度 ΡΕΤΜΡ濃度之組成物隨著在下之陳化時間變化的在 32 201249880 實施例編號在65eC下之儲存時間（天) 黏度（Pa-s) 實施例編號在65°C下之時間（天）黏度 (Pa · s ) 0 0.14 ~ 0 ~~~ 0.065 24 5 0.14 29 5 0.11 26 0.19 26 0.11 79 0.21 79 0.15 0 0.91 0 0.016 25 5 1.19 30 5 0.017 26 1.08 26 0.020 79 1.05 79 0.058 0 1.3 0 0.37 26 5 1.36 31 5 0.79 26 1.48 26 0.73 79 1.71 79 1.17 32 0 0.016 表 III D : 表II D中具有不同 1 凝膠化硫醇之組成物隨著在65 °C下表III F :表π F中具有烯丙之陳化時間變化的在2 5 °C下基醚或炔烴或烯呙基啡之組之黏度成物隨著在6 5 °C下之陳化時實施在 25°C 在 65t：例編儲存時間（天）下」下號黏度（Pa’s) 0 1.84 1.84 20 1.84 2.35 27 76 1.82 4.01 110 1.85 6.30 0 ~T85l 1.89 20 1.84 2.40 28 76 1.83 3.64 110 l.B5_ 4.97 間變化的在2 5。匚"T之黏度表III Ε :表II Ε中異有不同 (曱基）丙烯酸酯之組成物隨著在25 °C及65 Ό下之陳化時間變化的在2 5 Ό下之黏度 33 201249880 【圖式簡單說明】無【主要元件符號說明】無24 201249880 Curing resin. In Table A, 'Comparative Example 1 ' 2, 4, 7, 9, 11 to 14 shows that the curable thiol-alkenyl composition is unstable after 76 days at 65 t and the viscosity increases sharply or even occurs. Gelatinized. In Table III A, Example 3 of the present invention demonstrates that the photocurable thiol bake composition is surprisingly and unexpectedly stabilized by the synergistic effect of the combination of galliclophenol and phosphonic acid, and is under 76 There was only a slight increase in viscosity after day (from .99 Pa.s to 1.64 Pa. 〇. Example 3 should be compared to Examples 1 and 2, Examples 1 & 2 are similar compositions, but do not exhibit gallicol An advantageous and stable combination with phosphonic acid. In Table III A, Example 5 of the present invention demonstrates that the photocurable thiol-alkenyl composition is surprisingly and unexpectedly combined with gallicol and phosphonic acid. It is stable by the influence of synergy (if the amount of gallicol is only wt% '), and only a slight viscosity increase occurs after (D)% of the day [from 99.99?^ to Example 5 and Example 1 and In comparison, Examples 1 and 4 are similar compositions, but do not exhibit an advantageous stable combination of gallicphenol and phosphonic acid. In Table III A, Example 8 of the present invention exhibits a photocurable thiol-alkenyl composition. Surprisingly and unexpectedly subject to 4_t-butyl-indole, 2·dihydroxybenzene and phosphonic acid The effect of the synergistic effect of the combination is stable, and there is only a slight increase in viscosity (from 〇93 to pa s) after the next 76 days. Example 8 should be similar to the examples... The article 'but does not exhibit an advantageous stable combination of 4_t-butyl-1<2_dihydroxy stupate with phosphonic acid. 25 201249880 In Table III B 'Examples 15 and 16 of the present invention show photocurable sulfur The alcohol-dilute composition is surprisingly and unexpectedly stabilized by the synergistic effect of gallnuts and combinations of different types of phosphonic acids, and only a slight increase in viscosity occurs after 76 days at 65 (respectively .92Pa.s to i.7ipa.s and from 1.03 Pa.s to 1.83 Pa.s). Examples 15 and 16 should be compared to Examples 17 and 18, and Examples 17 and 18 are similar compositions. , but exhibiting a combination of gallnut and non-phosphonic acid. In Table III C, Examples 19 to 23 of the present invention show that the photocurable thiol-alkenyl composition is surprisingly and unexpectedly subject to five times The synergistic effect of the combination of squaric acid is stable, at which time the content of pentaerythritol bismuth (3-sulfopropionate) varies from 4 wt% to 34. Wt%, and only a slight viscosity increase occurred after 79 days at 65 ° C. In Table III D, Examples 24 to 26 of the present invention containing different types of mercaptans exhibited photocurable mercaptan-dilute composition It is surprisingly and unexpectedly stable by the synergistic effect of the combination of gallic phenol and phosphonic acid of different types of thiols, and only a slight increase in viscosity occurs after 79 days at 65 。. Examples 27 to 28 of the present invention containing different types of (meth) acrylates exhibit photocurable thiol-alkenyl compositions that are surprisingly and unexpectedly affected by different types of (mercapto) acrylic acid. The synergistic effect of the combination of the gallic acid and the phosphonic acid was stable, and only a slight viscosity increase occurred after % t at 65 t (from 1.84 Pa.s to 4 〇 1 pa s and from 1.89 Pa.s, respectively). 3.64 Pa.s). In Table IIIF, the present invention contains different types of allyl ether or alkyne 26 201249880 or allyl hydrazine, and the 9m light-curable thiol-thin composition is surprisingly and unexpectedly It is stabilized by the synergistic effect of the combination of different types of allyl ether or alkyne or allylic morphine and phosphonic acid, and only a slight viscosity increase occurs after 79 days at 65 C. Comparative Example 32 exhibited the same composition as Example 3, which did not contain gallicol and gelled after 1 day at 65 °C. Photocuring of Photocurable Compositions: The photocurable compositions of the present invention have been fabricated into three dimensional (3D) articles by curing using incoherent actinic radiation and ultraviolet (uv) radiation. The stabilizing system phosphonic acid/phenolic component is added to the thiol-alkenyl photocurable composition without changing the reactivity, photosensitivity, curing speed of the composition, or the mechanical strength and elastic modulus of the manufactured 3D article. Number, mobility. Samples for notched impact strength testing using digital light processing (DLP) 3D parts were fabricated at a resolution of 1400 x 1050 using the stereo vision device EnvisionTec Perfactory® SXGA + W/ERM Mini MultiLens. A sample of 50 μm thickness was constructed with a exposure time of u seconds at a lamp power of 800 mW/dm2. After the structuring process was completed, the prototype was rinsed with ethanol and then post-cured for 2 minutes (1 minute each on each side) under a UV lamp (INTELLI-RAY 600 Watt UV flood curing system). The notched impact strength specimen was a rectangle of about 14/7/55 mm (width/height/length). Izod notched impact strength test: Izod's notched impact strength was evaluated using a notched specimen formed by DLP. Tested on a Zwick model 5113 equipped with a hammer on a 27 201249880 impact tester type machine (Zwick, Germany) according to the ISO 180 standard. Table IV shows the measurement results of the notched impact strength of the cured composition 1 (Comparative Example) and the composition 5 of the present invention immediately after curing at 65 ° C for 30 days. The notched impact strength measurement showed that the addition of the stabilizing system phosphonic acid/phenolic component did not impair the impact strength of the cured composition at all. In addition, the impact strength of the cured stable composition was completely unaffected by the aging time at 65 ° C for 30 days before curing. Example No. Storage time at 65 °C (days) Viscosity (Pa·s) acN [kJ/m2] Standard deviation [kJ/m2] Variance [%] 1 0 1.71 7.25 0.087 12.01 5 0 0.90 6.80 0.117 17.25 30 1.34 6.54 0.024 3.73 Table IV: Notched impact strength measurement results of cured compositions 1 and 5 Example No. 1 (wt%) 2 (wt%) 3 (wt%) 4 (wt%) 5 (wt%) 6 ( Wt%) 7 (wt%) 8 (wt%) 9 (wt%) 10 (wt%) 11 (wt%) 12 (wt%) 13 (wt%) 14 (wt%) SR348L 61.8 62.37 61.17 62.94 61.74 61.80 62.18 60.99 62.92 61.72 62.37 61.17 62.94 61.74 PETMP 33.35 33.66 33.01 33.97 33.32 33.35 33.56 32.91 33.96 33.31 33.66 33.01 33.97 33.32 IRG184 2.95 2.97 2.92 2.99 2.94 2.94 2.96 2.90 2.99 2.94 2.97 2.92 2.99 2.94 PRA - 1 1 0.1 0.1 0.01 - - BDB 1.3 1.3 0.13 0.13 - - MP - 1 1 0.1 0.1 MA154 1.9 - 1.9 - 1.9 1.9 - 1.9 Amount 1.9 1.9 - 1.9 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Table II A: Different phenolic components Composition 28 201249880 Example No. 15 (wt%) 16 (wt%) 17 (wt%) 18 (wt%) SR348L 62.37 62.12 62.31 62.12 PETMP 33.66 33.52 33.63 33.52 IRG184 2.97 2.96 2.96 2.96 PRA 0.1 0.1 0.1 0.1 VP 0.9 - - - PPA - 1.3 - - BA - - 1 BSA - - - 1.3 Total 100 100 100 100 Table II B: with phosphonic acid and without Composition of phosphonic acid Example No. 19 (wt%) 20 (wt%) 21 (wt%) 22 (wt%) 23 (wt%) SR348L 61.86 69.14 80.11 87.02 90.93 PETMP 33.44 26.15 15.15 8.23 4.31 IRG184 2.85 2.85 2.85 2.85 2.85 PRA 0.1 0.1 0.1 0.1 0.1 MAI 54 1.75 1.76 1.79 1.80 1.81 Total 100 100 100 100 100 Table II C: Compositions with different PETMP concentrations Example No. 24 (wt%) 25 (wt%) 26 (wt%) SR348L 62.39 60.00 59.44 GDMP 32.88 - - TMPMP - 35.27 - Karenz PEI - - 35.82 IRG184 2.86 2.86 2.86 PRA 0.1 0.1 0.1 MAI 54 1.77 1.77 1.78 Total 100 100 100 Table II D: Composition with different thiols 29 201249880 Example No. 27 (wt%) 28 (wt%) SR348 31.7 31.91 SR349 18.1 18.22 SR9035 9.51 9.58 Ebecryl 8402 26.28 26.46 IRG651 1.31 1.32 Lucirin ΤΡΟ 1.1 1.11 ΡΕΤΜΡ 10 10 PRA 0.1 0.1 ΡΡΑ - 1.3 MAI 54 1.9 - Total (wt%) 100 100 Table II E: Compositions with different (meth) acrylates Example No. 29 (wt%) 30 (wt%) 31 (wt%) 32 (wt%) Pentaerythritol allyl ether 39.62 - - - 1,7-octadiyne 28.81 - 29.45 triallyl triammonium ketone - 38.60 - PETMP 55.63 66.35 56.78 67.65 IRG184 2.86 2.86 2.86 2.90 PRA 0.1 0.1 0.1 - MA154 1.79 1.88 1.66 - Total (wt%) 100 100 100 100 Table II F: Composition with allyl ether or alkyne or allyl form 30 201249880 Example number Storage time (days) at 25. (: Viscosity at 6 times (Pa-s) 1 Gelation after 22 days at room temperature and 19 hours at 65 °C 2 0 0.95 0.95 21 1.00 2.48 76 1.10 16.2 110 1.10 35.65 3 0 0.99 0.99 21 0.98 1.21 76 0.97 1.64 110 0.97 1.89 4 0 0.88 0.88 20 0.95 5.85 76 1.24 31.27 110 1.54 Solid 5 0 0.90 0.90 20 0.90 1.08 76 0.87 1.46 110 0.88 1.71 6 0 0.89 245 3.15 7 0 0.89 0.89 20 0.95 7.11 76 1.22 64.98 110 1.40 Viscosity at 65 ° C at 25 ° C when solids are stored (Pa-s) 8 0 0.93 0.93 21 0.96 1.22 76 0.95 2.12 110 0.95 2.94 9 0 0.86 0.86 21 1.04 9.72 76 1.51 34.23 110 1.831 Solid 10 0 0.89 21 0.90 76 0.91 110 0.93 11 0 0.89 0.89 14 3.46 8.26 22 4.51 16.52 76 2.87 Solid 12 0 0.85 0.85 14 Solid solid 13 0 0.84 0.84 14 23.63 Solid 14 0 0.90 0.90 14 1.74 Solid 22 Solid solids Table III A : Table II A Viscosity at 25 ° C with composition of different phenolic components as a function of ageing at 25 ° C and 65 ° C. 201249880 Example Storage time at 65eC (days) Viscosity (Pa-s) 1 0 0.92 -^=1==4 1.35 / 1.90 Example No. 丨1 〇' s~~ / 1.05 / 19 u_xm / 1.35 26 ~~ 1.32 79 I 1.41 0 1 1.15 I 20 , 5 1.60 1 26~~~ 1 1.45 1 79 1.73 I 21 5 1.78 1 26 1.46 79 1 1.76 1 0 ---- 1.41 22 5 1.95 1.59 79 1.67 0 | 1.50 23 5 1.96 1.40 1 1.76 Table III C : Table II C Having a different 10 I 9 ^ 2 hours after 3 Table III B · · Table 11 B has a phosphine and a composition without phosphonic acid at a viscosity of 25 : 的 at 25 Γ Τ The composition of the cerium concentration varies with the aging time under 32 201249880 Example number storage time at 65eC (days) Viscosity (Pa-s) Example number at 65 ° C time (days) Viscosity ( Pa · s ) 0 0.14 ~ 0 ~~~ 0.065 24 5 0.14 29 5 0.11 26 0.19 26 0.11 79 0.21 79 0.15 0 0.91 0 0.016 25 5 1.19 30 5 0.017 26 1.08 26 0.020 79 1.05 79 0.058 0 1.3 0 0.37 26 5 1.36 31 5 0.79 26 1.48 26 0.73 79 1.71 79 1.17 32 0 0.016 Table III D : Table II D differs 1 The composition of the gelled thiol with a change in the aging time of allylation at 65 °C in Table III F: Table π F at a temperature of 25 ° C under ether or alkyne or enephthyl The viscosity of the group is carried out at 25 °C at 65 °C at 65 °C. The storage time (days) is the next viscosity (Pa's) 0 1.84 1.84 20 1.84 2.35 27 76 1.82 4.01 110 1.85 6.30 0 ~T85l 1.89 20 1.84 2.40 28 76 1.83 3.64 110 l.B5_ 4.97 varies between 2 5 .匚"T's viscosity table III Ε : Table II Ε different in the 曱 (曱) acrylate composition with the viscosity at 25 ° C and 65 Ό under the age of 25 之 viscosity 33 201249880 [Simple description of the diagram] No [Main component symbol description] None

34 S34 S

Claims

201249880 VII. Patent application scope: 1 · A curable composition comprising: A) to J-olefinic or acetylenically unsaturated monomers or mixtures thereof; B) at least one thiol; D) at least one phosphine An acid; a benzene or naphthalene series component exhibiting at least one phenylcyclophthalene ring containing at least two hydroxy substituents. 2_ The curable composition of claim 1, preferably a photocurable composition comprising: A) at least one ethylenically or acetylenically unsaturated monomer or a mixture thereof; B) at least one mercaptan; C) at least one free radical photoinitiator; D) at least one phosphonic acid; E) a component of the benzene or naphthalene series exhibiting at least one benzene or naphthalene ring, the at least two hydroxy substituents being attached to the phenyl ring or On the naphthalene ring. Society 3. Such as Shen. The curable composition of claim 1 or 2, preferably a photocurable composition, wherein component E exhibits the following structure (1): R „(〇H)n (1) wherein η is an integer of 6, m is an integer of 〇 to (6_η), and independently of each other, is an organic group, preferably a C1-C6 alkyl group. 4 · A curable composition according to any one of the aforementioned patents. Preferably, 5 35 201249880 a photocurable composition comprising: A) 25-98 wt. /, preferably 5 〇 95 wt% of component a;

Each is based on the total weight of the composition. Component B; F gui 1-7 wt% of component C; preferably 0.5-5 wt% of component D; preferably 0.01 to 3% by weight of component E; 5. Any of the foregoing patent claims A curable composition comprising A) 60-90 wt% of component a; B) 5-40 wt% of component b; C) 1 - 5 wt% of component c; D) 1- 4 wt% of component D; E) 0.05-2 wt% of component e; each based on the total weight of the composition. 6. The curable composition according to any one of the preceding claims, wherein the component Ε exhibits at least one benzene ring or a naphthalene ring having two, three or four hydroxy substituents bonded directly to the benzene ring Or on a naphthalene ring. 7. The curable composition of claim 3, wherein in the structure (1) of the component ,, η is 2, 3 or 4 and m is 0 or 1. 8. The curable composition of any of the claims, wherein component E comprises optionally substituted benzenediol, benzenetriol or quinone. 36 201249880 9. The curable composition according to any one of the preceding claims, wherein component D comprises phenylphosphonic acid, vinylphosphonic acid, octodiphosphonic acid or 2-acrylic acid 2-[(2_phosphonium ethoxylate) ) 曱 base] _ ethyl ester. A curable composition according to any one of the preceding claims, wherein component B is a polythiol exhibiting 2 to 4 SH groups. 11. A curable composition according to any one of the preceding claims, wherein component B comprises pentaerythritol tetrakis(3,mercaptopropionate), ethylene glycol di-3-mercaptopropionate, trioxindole Propane tri-3-indolyl propionate or pentaerythritol tetrakis(3-succinylbutyrate). 12. A curable composition according to any one of the preceding claims, wherein component A comprises diacrylate or dimethacrylate, especially 1.6-hexanol diacrylate or bisphenol a ethoxylated Di(meth)acrylic acid 6 is intended. 13. The curable composition of any one of the claims, wherein after 76 or 110 days at 65-C, the viscosity of the composition is still less than the initial viscosity of the composition 纟2rc. Μ times, preferably 2.5 times. 14. A method of manufacturing a three-dimensional article in a continuous section according to an article model, comprising the steps of: forming a first layer of a composition according to any one of the preceding claims; securing the first layer to a corresponding model The respective cross-sectional views are used to harden the actinic radiation of the first layer in the image region; forming a second layer of the photocurable composition according to any one of the preceding claims 37 201249880; Exposing the second layer to actinic radiation sufficient to harden the second layer in the image region in a pattern corresponding to the respective cross-section of the model; and repeating the previous two steps as needed to form a continuous layer to form the three-dimensional article . 15. A three-dimensional article made in accordance with the method of claim 14 of the patent application. Eight, schema. Benefit 38