TW201118129A - Anti-yellowing epoxy resin composition for fixing stone material and its application - Google Patents

Abstract

An anti-yellowing epoxy resin composition for fixing a stone material, including an epoxy resin, an amine curing agent, an amine UV absorbent and an antioxidant having the following formula (1): Formula (I) where R.sub.1 is H, OH, or OR.sub.10, and R.sub.10 is an alkyl group having 1 to 18 carbon atoms. R.sub.2, R.sbu.3, R.sbu.4, and Rsub.5 independently is an alkyl group having 1 to 6 carbon atoms. R.sub.6 is H, an alkyl group having 1 to 6 carbon atoms or NH.sub.2. The invention also provides a method for fixing a stone material and the fixed stone material obtained from the method.

Description

201118129 六、發明說明： 【發明所屬之技術領域】 ^發明是有關於-種耐黃變環氧樹脂組成物的方法 特別疋^日帛用於修補石材的耐黃變環氧樹脂組成物、 種修補石狀方法，及以上述方㈣得的經修補的 【先前技術】 壓使石材由於在自然界中經過經年累月之自然擠 ’使付某二石材表面會呈現天然的細微孔洞與凹面，在 製造商品時為求整體呈現完美，需要藉由研磨或拋光等工 法來録面更加完美。然而，這些研磨工法成效有限，故 業界還會利用環氧樹脂來填補上述缺陷。 不過，環氧樹脂會有黃變問題，亦即環氧樹脂經陽光 臨曬後’易從透明樹脂轉變成黃褐色樹脂，嚴重破壞石材 外觀，特別是在考慮其硬化速度與價格成本的情形下，目 前石材產業最常使用的環氧樹脂組成物為一含有雙酚A環 氧樹脂（diglycidyl ether bisphenol A;簡稱為 DGEBA)及胺 類硬化劑之混合物的反應產物，但是DGEBA上的芳香基團 和胺類硬化劑所提供的胺基在空氣中經過陽光曝曬後^容 易產生呈現黃色的發色基團，而使硬化後之環氧樹脂組成 物呈現黃褐色。現今，由於人們生活水準的提高，消費者 對飾面建材的品質要求曰趨嚴苛，故若無法解決目前以環 氧樹脂組成物修補石材後所造成的黃變問題，將會影響到 部分石材的應用性，特別是白色系列的石材。 一般所認知之劣化機制為當DGEBA受到紫外光或其他 201118129 波長較短的光長期照射時，其苯環上的電子在高能階的機 率增局，而苯環經活化後便易和氧分子產生作用，使其產 生自由基，之後便會產生一連串更複雜的自由基反應，造 成化學鍵斷裂，而使環氧樹脂產生黃變。此外，紫外光波 長在290nm時，光子的能量約為98 6 Kcal /玢旧化匕，但 一般C-C及C-H的鍵能在25t：時，分別為83〜85及96〜99 Kcal / m〇le，因此，较短波之紫外光能量，也可能破壞有機 聚合物中結合力較弱的鍵結，導致有機聚合物的黃化和裂 解（Photolytic Cleavage)。而要抑制環氧樹脂產生降解，可 以紫外線吸收劑抵消由紫外線引起之光氧化老化作用，亦 P如US 6,902,811 -案中所揭示的，添加一般常見之紫外 線吸收劑，如苯甲酮（benz〇phen〇ne)或苯並*** (Benzotriazole)系列之有機物’但是僅使用料線吸收劑， 還是無法有效防護環氧樹脂產生降解，因紫外線吸收劑本 身多半亦帶有苯環，故在有氧之情況下，也會受到含氧之 自由基攻擊，而使其防護失效，因此，人們再進—步添加 杬虱化劑以與自由基產生反應。 現有的抗氧化劑多為添加型試劑，亦即在 =程下不易與環氧樹脂反應，只能^已硬化後的= H如：US2_中所揭示的—㈣候環氧樹 物，其所使用抗氧化劑，雖有分子量大，以及 ^硬化物表面揮發使耐候時間增長之優點，但若是 :::修補石材之表面，最後還是會在因無法鍵結而在自 4化的環境下揮發。此外，以該專利案的實施例5中之 201118129 抗氧化劑的添加量為2 g，及其可與自由基反應之官能基之 莫耳數約為8.32 mmol來看’仍有可降低用量以節嗜成本的 空間’且該專利案巾所揭*之發明實例之反應條件皆無法 應用於目前石材補膠製程。 另，US 4,033,928揭示一種藉由受阻胺光安定劑 (^Iindered Amme Light Stabilizers;簡稱為 HALS)來穩定的201118129 VI. Description of the invention: [Technical field to which the invention pertains] The invention relates to a method for resisting yellowing-resistant epoxy resin composition, in particular, a method for repairing yellowing-resistant epoxy resin composition of stone, and a method for repairing stone And the repaired [previous technique] obtained by the above-mentioned formula (4), the pressure of the stone is naturally squeezed over the years by nature, so that the surface of the surface of the two stones will have natural fine pores and concave surfaces, and the whole product is made in the manufacture of goods. It is perfect and needs to be perfected by grinding or polishing. However, these grinding methods have had limited success, so the industry will use epoxy resin to fill the above defects. However, the epoxy resin will have a yellowing problem, that is, the epoxy resin will change from a transparent resin to a yellow-brown resin after being exposed to sunlight, which seriously damages the appearance of the stone, especially considering the hardening speed and the cost of the product. At present, the most commonly used epoxy resin composition in the stone industry is a reaction product containing a mixture of diglycidyl ether bisphenol A (DGEBA) and an amine hardener, but an aromatic group on DGEBA. And the amine group provided by the amine hardener is easily exposed to sunlight in the air to produce a yellow chromophoric group, and the hardened epoxy resin composition is yellowish brown. Nowadays, due to the improvement of people's living standards, consumers' demand for quality of decorative building materials is becoming more and more stringent. Therefore, if the yellowing problem caused by the repair of stone with epoxy resin composition cannot be solved, it will affect some stone materials. The applicability, especially the white series of stone. The generally recognized degradation mechanism is that when DGEBA is exposed to ultraviolet light or other short-wavelength light of 201118129, the electrons on the benzene ring increase in the high-energy order, and the benzene ring is easily activated and oxygen molecules are generated. The effect is to generate free radicals, which then produce a series of more complex free radical reactions, causing chemical bond cleavage and yellowing of the epoxy resin. In addition, when the wavelength of ultraviolet light is 290 nm, the energy of photons is about 98 6 Kcal / 玢, but the bond energy of CC and CH is usually 83 to 85 and 96 to 99 Kcal / m〇le at 25t: Therefore, the shorter wavelength ultraviolet light energy may also destroy the weak bonding bond in the organic polymer, resulting in yellowing and cleavage of the organic polymer (Photolytic Cleavage). In order to suppress the degradation of the epoxy resin, the ultraviolet absorbing agent can counteract the oxidative aging effect caused by the ultraviolet ray. Also, as disclosed in the case of US 6,902,811, a common ultraviolet absorbing agent such as benzophenone (benz 〇) is added. Phen〇ne) or Benzotriazole series of organic matter' but only the use of wire absorbent, can not effectively protect the epoxy resin from degradation, because most of the UV absorber itself also has a benzene ring, so in the aerobic In this case, it is also attacked by oxygen-containing free radicals, which renders its protection ineffective. Therefore, people further add deuteration agents to react with free radicals. The existing antioxidants are mostly additive-type reagents, that is, it is not easy to react with the epoxy resin under the range of the process, and can only be cured after the hardened = H such as: (4) the epoxy tree, which is disclosed in US 2 The use of an antioxidant has the advantages of a large molecular weight and an increase in the weathering time due to the volatilization of the surface of the cured product. However, if the surface of the stone is repaired, the surface of the stone is finally volatilized in a self-contained environment due to the inability to bond. In addition, the amount of the antioxidant added to the 201118129 in Example 5 of the patent is 2 g, and the number of moles of the functional group reactive with the radical is about 8.32 mmol. The reaction conditions of the inventive example of the "cost-effective space" and the patented towel can not be applied to the current stone filling process. In addition, US 4,033,928 discloses a stabilization by a hindered amine light stabilizer (HALS).

環氧樹脂，不過，該專㈣未揭示任何㈣修補石材缺陷 的應用’㈣專利案之實施例—巾所狀受阻胺光安定劑 =先溶於對二甲苯(Xylene)中才能均勻分散於環氧樹脂中， 若用於石材補膠製程’其溶_發物易對施作卫人造成身 體上之傷害，且該環氧組錢之硬化時間過長 :環保與效率的今日已不適用，特別是若是要應用於Γ材 :、上因為通常石材所佔的放置面積較大，倘若硬化時間 =長:則需要很大的空間來置放尚未完成硬化的石材，相 田不符成本。而㊅專利案之實施例2至實施例4不但存在 Ά缺點’且其所使用之環氧主劍在室溫下為固體，在 施作時兩要17G°C之高溫，因此無法應用於石材上。 因^’仍有需要發展出__種成本低且能降低黃變問題 、衣氧树脂組成物及修補石材的方法。 【發明内容】 ’本發明之第 目的，即在提供一種成本低且能 降低^相題的用於修補石材的耐黃變環氧樹脂組成物。 %氧樹脂、一胺類硬化劍 .發明t用於修補石材的耐黃變環氧樹脂組成物係包括 胺類紫外線吸收劑及一具 201118129 有如下式α)所示的抗氡化 劑 R:Epoxy resin, however, this special (4) does not reveal any (4) application of repairing stone defects' (4) Patent Example - towel-type hindered amine light stabilizer = first dissolved in paraxylene (Xylene) to be evenly dispersed in the ring In the oxygen resin, if it is used in the stone refining process, its solvent is easy to cause physical damage to the Guardian, and the hardening time of the epoxy group is too long: environmental protection and efficiency are not applicable today, especially If it is to be applied to the coffin:, because the stone usually occupies a large area, if the hardening time = long: it requires a lot of space to place the stone that has not yet been hardened, and the field does not conform to the cost. However, in Embodiments 2 to 4 of the six patents, there are not only defects, but the epoxy main sword used is solid at room temperature, and at the time of application, the temperature is high at 17 G ° C, so it cannot be applied to stone. on. There is still a need to develop a low cost and can reduce the yellowing problem, the composition of the oxy-resin and the method of repairing the stone. SUMMARY OF THE INVENTION The object of the present invention is to provide a yellowing resistant epoxy resin composition for repairing stone materials which is low in cost and capable of reducing the problem. % Oxygen Resin, Monoamine Hardening Sword. Inventive t The yellowing resistant epoxy resin composition for repairing stone includes an amine ultraviolet absorbent and a chemical resistant agent R as shown in the following formula:

^5 其中’ Ri為Η、〇Η赤ηρ ( D ρ ^ 次0Rig，且 Rio 為一（：丨-(：18 烷基 I /A I各1獨立地為一 C,_C6院基；及〜為H 一 11_匕6烷基或nh2。 本發明之坌_ 弟—目的，即在提供一種成本低且能降低$ 變問題的修補_石材的方法。 2明修補_石#的方法，該石材具有至少—缺陷， 將—咐黃變環氧樹脂組成物填入該石材的缺陷内 ，並使該耐黃變環氧樹脂組成物進行硬化反應，該财黃變 環氧樹脂組成物包括一 虱樹月曰、一胺類硬化劑、一胺類 i外線吸收劑及—具有如 令如下式（I)所示的抗氧化齊j : r3^5 where ' Ri is Η, 〇Η η ηρ ( D ρ ^ times 0Rig, and Rio is one (: 丨-(: 18 alkyl I / AI each 1 is independently a C, _C6 yard base; and ~ is H 11 11 匕 6 alkyl or nh 2. The 坌 — — 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的 目的Having at least a defect, the epoxy resin composition is filled into the defect of the stone, and the yellowing resistant epoxy resin composition is subjected to a hardening reaction, and the yellowing epoxy resin composition comprises a eucalyptus, an amine a hardener-like, an amine-based external absorbent, and having an antioxidant as shown in the following formula (I): r3

R6 nh2 (I) 其中，Ri 為 H、_ H 〇R10，且r10為一 c广Ci8炫基 R2、R3、R4及R5各自獨立地為_R6 nh2 (I) where Ri is H, _ H 〇 R10, and r10 is a c-wide Ci8 sleek R2, R3, R4 and R5 are each independently _

^ Ci-C6烷基；及尺6為H —CVC6烷基或nh2 β 本發明之第三目的，即A担仰 即在棱供一種利用上述方法製4 的成本低且财黃變性佳的經修補的石材。 201118129 本發明之功效在於··本案發明人將具有式⑴之特殊結 構的抗氧化劑添加至用以修補石材的環氧樹脂組成物中， 由於其分子量小、價格便宜’且可與環氧樹脂產生交聯硬 化並具有純化的功能’進而提昇硬化後的環氧樹脂組合 物的耐肖變性’尤其適用於室内大理石、&岗石等天然石 材线陷修補’再者’本案耐黃變環氧樹脂組成物中的胺 ^ i外線吸收劑及胺類硬化劑也都能與環氧樹脂快速進行 反應’故確實能達到本發明之目的。^ Ci-C6 alkyl; and 6 is H-CVC6 alkyl or nh2 β. The third object of the present invention is that A is used in the rib to provide a low cost and good yellowness of the yellow by the above method. Repaired stone. 201118129 The effect of the present invention is that the inventor of the present invention adds an antioxidant having a special structure of the formula (1) to an epoxy resin composition for repairing a stone, because of its small molecular weight and low cost, and can be produced with an epoxy resin. Cross-linking hardening and purifying function 'and thus improving the resistance of the epoxy resin composition after hardening' is especially suitable for indoor marble, & granite stone and other natural stone line trap repair 'again' this case yellowing resistant epoxy resin composition The amine-based external absorbent and the amine-based hardener can also react rapidly with the epoxy resin, so that the object of the present invention can be achieved.

【實施方式】 本發明用於修補石材的耐黃變環氧樹脂組成物係包括 一環氧樹脂、一胺類硬化劑、一胺類紫外線吸收劑及一具 有如下式（I)所示的抗氧化劑： R3[Embodiment] The yellowing resistant epoxy resin composition for repairing stone materials comprises an epoxy resin, an amine hardener, an amine ultraviolet absorber, and an antioxidant having the following formula (I): R3

(I) 且Rig為一 Ci-C18烷基； Ci_C6烷基；及r6為η、(I) and Rig is a Ci-C18 alkyl group; Ci_C6 alkyl group; and r6 is η,

其中’ R!為Η、oh或〇R10， R2、R3、R4及R5各自獨立地為一 一 CVC6烷基或NH2。 較佳地，該環氧樹脂是雙盼型環氧樹脂。選擇性地， 該雙盼型環氧樹脂是雙紛Α之二縮水甘油峻，例如，長春 人造樹脂礙股份有限公司製造之BE韻、Μ·ΐ86，或南亞 塑膠工業股份有限公司製造之128 ’或是美國翰森化工製造 之Epon 825都適用於本案。然，上面僅是列舉出_般常用 201118129 於石材修補且易有黃變問題的環氧樹脂種類，故不應此上 述環氧樹脂為限，原則上只要是能與本案所使用的抗氧化 劑產生交聯者皆可。 選擇性地，該胺類硬化劑是一雙胺型硬化劑，例如二 乙基三胺（diethylenetriamine ;簡稱DETA)、三乙基三胺 (triethylenetriamine ；簡稱 TETA)、二乙氨基丙胺 (diethylaminopropylamine ；簡稱 DEAPA)及四乙烯戊胺 (tetraethylenepentamine ;簡稱 ΤΕΡΑ)等等。 該胺類紫外線吸收劑是一含有胺基的化合物，例如， 與雙鍵化工提供之對二烧基胺基苯曱6旨（dialkylaminobenzoic ester) ° 較佳地，用以表示該抗氧化劑的式（I)中的R6為Η。在 本案之一具體實施例中，該抗氧化劑為4-胺基-2,2,6,6-四甲 略0定（4-amino-2,2,6,6-tetramethylpiperidine ;簡稱 TAD)。 較佳地，以該耐黃變環氧樹脂組成物總重量計，該抗 氧化劑的含量是介於0.074 wt%至0.5 wt%之間。更佳地， 該抗氧化劑的含量是介於0.074 wt%至0.3wt%之間。當該 抗氧化劑的含量低於0.074 wt%時，該耐黃變環氧樹脂組成 物的耐黃變性不夠好；當該抗氧化劑的含量高於0.5 wt%時 ，該耐黃變環氧樹脂組成物的機械性質會受到影響。 較佳地，以該耐黃變環氧樹脂組成物總重量計，該環 氧樹脂的含量是介於74 wt%至88 wt%之間。更佳地，該 環氧樹脂的含量是介於74.1 wt%至74.4 wt%之間。 較佳地，以該耐黃變環氧樹脂組成物總重量計，該胺 201118129 類硬化劑的含量是介於22 wt%至26 wt%之間。更佳地， 該胺類硬化劑的含量是介於23.1 wt%至25.8 wt%之間。 較佳地’以該耐黃變環氧樹脂組成物總重量計，該胺 類紫外線吸收劑的含量是介於〇 2 wt%至〇.8 wt%之間。更 佳地’該胺類紫外線吸收劑的含量是介於〇6 wt%至〇.75 wt%之間。Wherein 'R! is Η, oh or 〇R10, and R2, R3, R4 and R5 are each independently a CVC6 alkyl group or NH2. Preferably, the epoxy resin is a double-pressure epoxy resin. Optionally, the double-presence type epoxy resin is a double condensed diglycol, for example, BE Yun, Μ·ΐ86 manufactured by Changchun Artificial Resin Co., Ltd., or 128 ' manufactured by Nanya Plastic Industry Co., Ltd. Epon 825 manufactured by Hansen Chemical Co., Ltd. is applicable to this case. However, the above only lists the types of epoxy resins that are commonly used in 201118129 for stone repair and are prone to yellowing problems. Therefore, it should not be limited to the above epoxy resins. In principle, as long as it can be used with the antioxidants used in this case. Crosslinkers are fine. Optionally, the amine hardener is a diamine type hardener, such as diethylenetriamine (DETA), triethylenetriamine (TETA), diethylaminopropylamine (abbreviated as diethylaminopropylamine). DEAPA) and tetraethylenepentamine (referred to as ΤΕΡΑ) and the like. The amine-based ultraviolet absorber is an amine group-containing compound, for example, a dialkylaminobenzoic ester provided by a double bond chemical. Preferably, the antioxidant is used to represent the antioxidant ( R6 in I) is Η. In a specific embodiment of the present invention, the antioxidant is 4-amino-2,2,6,6-tetramethylpiperidine (abbreviated as TAD). Preferably, the antioxidant is present in an amount between 0.074 wt% and 0.5 wt% based on the total weight of the yellowing resistant epoxy resin composition. More preferably, the antioxidant is present in an amount between 0.074 wt% and 0.3 wt%. When the content of the antioxidant is less than 0.074 wt%, the yellowing resistance of the yellowing resistant epoxy resin composition is not good enough; when the content of the antioxidant is more than 0.5 wt%, the mechanical properties of the yellowing resistant epoxy resin composition Will be affected. Preferably, the epoxy resin is present in an amount of between 74% by weight and 88% by weight based on the total weight of the yellowing resistant epoxy resin composition. More preferably, the epoxy resin is present in an amount between 74.1 wt% and 74.4 wt%. Preferably, the amine 201118129 hardener is present in an amount between 22 wt% and 26 wt% based on the total weight of the yellowing resistant epoxy resin composition. More preferably, the amine hardener is present in an amount between 23.1 wt% and 25.8 wt%. Preferably, the amine-based ultraviolet absorber is present in an amount of from 〇 2 wt% to 〇. 8 wt%, based on the total weight of the yellowing resistant epoxy resin composition. More preferably, the content of the amine-based ultraviolet absorber is between 〇6 wt% and 〇.75 wt%.

本發明用於修補石材的耐黃變環氧樹脂組成物的製備 方法即是將該環氧樹脂、該胺類硬化劑、該胺類紫外線吸 收劑及該具有式（I)所示的抗氧化劑均勻混合。 本發明修補一石材的方法，該石材具有至少一缺陷， 該方法係將一耐黃變環氧樹脂組成物填入該石材的缺陷内 ，並使該耐育變環氧樹脂組成物進行硬化反應，該耐黃變 %氧樹脂組成物包括一環氧樹脂、一胺類硬化劑、一胺類 紫外線吸收劑及一具有如下式⑴所示的抗氧化劑：The preparation method for repairing the yellowing resistant epoxy resin composition of the stone material comprises uniformly mixing the epoxy resin, the amine hardener, the amine ultraviolet absorber and the antioxidant represented by the formula (I) . The method for repairing a stone having at least one defect, wherein the method comprises filling a yellowing resistant epoxy resin composition into a defect of the stone material, and subjecting the resistant epoxy resin composition to a hardening reaction, The yellowing resistant % oxygen resin composition comprises an epoxy resin, an amine hardener, an amine ultraviolet absorber, and an antioxidant having the following formula (1):

其中，Ri為Η、OH或〇R10，且Ri〇為一 Ci_Ci8烷基； R2、r3u r5各自獨立地為一 Ci_C6烷基；及心為H、 一 Ci-Cg 烧基或 NH2。 在本案中，發明人是藉由將該財黃變環氧樹脂組成物 倒入該石材的缺陷内，並以白鐵鏝刀施以壓力來回均勻塗 抹來完成填入的動作，製作者也可以在輕輕塗抹後，將其 201118129 f:一真空設備中抽真空來完成填入動作。事實上，只要 疋此使該石材的缺陷被該耐黃變環氧樹脂組成 式皆可。 該方法中所提到的環氧樹脂、胺類硬化劑、胺類紫外 線吸收劑及抗氧化劑的較佳的種類及含量範圍，皆與上述 用於修補石材的耐黃變環氧樹脂組成物中的環氧樹脂、胺 類硬化劑、紫外線吸收劑及該抗氧化劑的較佳的種類及含 量範圍相同，故不在賢述。 較佳地，該石材是選自於花崗石、大理石、化石、石 灰石、砂岩或洞石。 另，通常該石材中會存在水分，故在進行填入動作前 較佳地，對該石材施予一烘乾處理，例如使用瓦斯噴燈 加熱，或是使用溫度介於40。(:〜120。(：之間的隧道式或塔式 烘乾設備進行烘乾處理。 本發明經修補的石材係由如上所述之修補一石材的方 法所製得的。 實施例 本發明將就以下實施例來作進一步說明，但應瞭解的 疋，忒等實施例僅為例示說明之用，而不應被解釋為本發 明實施之限制。 <化學品來源> 1 氧樹脂.購自於長春人造樹脂廠股份有限公司；型號 為 ΒΕ-188。 2.胺類硬化劑a :購自於允德；型號為9〇3，為一種變性環 10 201118129 狀脂肪族胺類。 3. 胺類硬化劑B:購自於美國陶氏化學；型號為de h.tm 24’有效成々為二乙基三胺（簡稱teta)。 4. 紫外線吸收fi A:購自於雙鍵化卫，有效成分為對二烧 基胺基苯曱酯。 5. 紫外線吸收劑B :購自於雙鍵化卫；型號為肌，有效成 分為對二烷基胺基苯甲酯及一未知其確切結構的hals。 6. 4-胺基-2,2,6,6-四曱哌啶（簡稱TAD):購自於購自於德國 Degussa ;型號為 TAD。 [製備耐黃變環氧樹脂組成物] <實施例1 > 本貫把例疋將50.5033 g的環氧樹脂（be-188)與16.8676 g的胺類硬化劑（903)混合，再加入〇·4613 g的紫外線吸收 劑A與0.12 g的4-胺基-2,2,6,6-四甲哌啶（TAD)均勻混合， 進而製得一本發明耐黃變環氧樹脂組成物，以該耐黃變環 氧樹脂組成物總重量計，該環氧樹脂的含量為74 386 wt% ;該胺類硬化劑的含量為24.795 wt% ;該紫外線吸收劑A 的含量為0.669 wt% ，及TAD的含量為0.149 wt% 。 <實施例2及3 > 實施例2及3是以與實施例1相同的步驟製備本發明 耐黃變環氧樹脂組成物，其不同之處在於：各實施例中所 使用的環氧樹脂（BE-188)、胺類硬化劑（903)、紫外線吸收 劑A與抗氧化劑（TAD)的用量，而該等操作參數如下表1所 201118129 <比較例1至4 > 比較例1至4是以與實施例1相同的步驟製備環氧樹 脂組成物’其不同之處在於：比較例1至4中並未添加 TAD ’且各比較例中所使用的環氧樹脂、胺類硬化劑與紫外 線吸收劑的用量’以及胺類硬化劑與紫外線吸收劑的種類 也不盡相同’該等操作參數如下表1所示。 表1 環氧樹脂 胺類硬化劑 紫外線吸收劑 抗氧化劑 (BE-188) A B A B (TAD) 實施例1 74.386 24.795 - 0.669 0.149 實施例2 74.166 24.722 0.667 0.445 實施例3 74.4 24.8 - 0.7 - 0.1 比較例1 75 25 - - 比較例2 74.45 24.81 - - 0.74 --- 比較例3 74.45 24.81 - 0.74 - 比較例4 你計1 : ? 88.9 - 11.1 - - ※5主2.「-J代表未添加。 [製備經修補的石材] <實施例4 > 本貫施例是將一尺寸為7.5 cm X 30 cm的千層玉（取自 於煌奇石業，是一種大理石）以水洗淨後，以瓦斯噴燈加熱 進行烘乾處理，以去除該千層玉中的水份，再比照目前石 材廠補膠強化現場的施作條件，在45。(：〜60°C的溫度下，將 貫施例1的耐育變味氧樹脂組成物倒在該千層玉之表面上 ，並以白鐵鏝刀施以壓力來回均勻塗抹，使該耐黃變環氧 樹脂組成物滲入該千層玉的裂縫或孔洞處以填補該等缺陷 ’約歷經1小時之硬化過程，即可使其中的耐黃變環氧樹 12 201118129 ^ Sa組成物硬化’進而得到一經修補的千層玉。 <實施例5及6 > 貫施例5及6是以與實施例4相同的步驟製備該經修 補的石材，其不同之處在於：實施例5及6中所使用的耐 黃變環氧樹脂組成物依序為實施例2及3之耐黃變環氧樹 脂組成物，且實施例6所使用的石材為一和平白（取自於煌 奇石業’亦是一種大理石）。 <比較例5至8 > • 比較例5至8是以與實施例4相同的步驟製備該經修 補的石材，其不同之處在於：比較例5至8中所使用的環 氧樹脂組成物依序為比較例丨至4之環氧樹脂組成物，且 比較例5至7所使用的石材為一銀狐（取自於煙奇石業，亦 是一種大理石）；比較例8所使用的石材為一白大理（取自於 煙奇石業’亦是一種大理石）。 [耐黃變之測試] 將實施例4至6及比較例5至8之經修補的石材養生（ φ 即硬化凡成後再靜置）48小時’接著置於-耐候試驗機（簡稱 QUV，購自於廣柏實業股份有限公司；型號為QUV-spray) 中，在50t：的溫度下，以功率0.68 w/m2之紫外光照射， 觀察八中的％氧樹脂組成物的黃變情形，並每隔小時（即 2〇小時、40小時、60小時及8〇小時）以色差計測量X、γ 、ζ 三刺激值（tristimulus vahles)，並根據 astm Ε3ΐ3 轉換 成黃色指數(Yellow Index; 來判定对黃變性，Λγι 值越小，耐黃變性越好·，該等數據如表2所示。Wherein Ri is hydrazine, OH or hydrazine R10, and Ri 〇 is a Ci_Ci8 alkyl group; R2 and r3u r5 are each independently a Ci_C6 alkyl group; and the heart is H, a Ci-Cg alkyl group or NH2. In the present case, the inventor is able to perform the filling action by pouring the yellowing-reducing epoxy resin composition into the defect of the stone, and applying a pressure to the white iron squeegee to apply the filling back and forth, and the maker can also gently After smearing, the 201118129 f: vacuum device is vacuumed to complete the filling action. In fact, as long as the defects of the stone are made up of the yellowing resistant epoxy resin. The preferred types and content ranges of the epoxy resin, the amine hardener, the amine ultraviolet absorber and the antioxidant mentioned in the method are the same as those of the above-mentioned yellowing resistant epoxy resin composition for repairing stone. Oxygen resins, amine hardeners, ultraviolet absorbers, and the antioxidants have the same preferred types and contents, and are therefore not described. Preferably, the stone is selected from the group consisting of granite, marble, fossil, limestone, sandstone or travertine. Further, in general, moisture is present in the stone, so that it is preferable to subject the stone to a drying treatment, for example, using a gas burner, or a temperature of 40, before the filling operation. (: ~ 120. (: between the tunnel or tower drying equipment for drying treatment. The repaired stone of the present invention is made by the method of repairing a stone as described above. Embodiments of the present invention The following examples are given for further explanation, but the examples are to be construed as illustrative only and should not be construed as limiting the invention. <Chemical Source> 1 Oxygen Resin From Changchun Artificial Resin Factory Co., Ltd.; model is ΒΕ-188. 2. Amine hardener a: purchased from Yunde; model is 9〇3, which is a denatured ring 10 201118129 aliphatic amine. Amine hardener B: purchased from Dow Chemical of the United States; model de h.tm 24' effective bismuth is diethyltriamine (referred to as teta). 4. UV absorption fi A: purchased from double bond The active ingredient is p-dialkylaminophenyl benzoate. 5. UV absorber B: purchased from double bond deficiency; model is muscle, the active ingredient is p-dialkylamino phenyl methyl ester and one is unknown Structure of hals. 6. 4-Amino-2,2,6,6-tetrahydropiperidine (TAD): purchased from Degussa, Germany The model number is TAD. [Preparation of yellowing resistant epoxy resin composition] <Example 1 > This example is to mix 50.5033 g of epoxy resin (be-188) with 16.8676 g of amine hardener (903). And further adding 46·4613 g of ultraviolet absorber A and 0.12 g of 4-amino-2,2,6,6-tetramethylpiperidine (TAD) to uniformly mix, thereby obtaining a yellowing resistant epoxy resin composition of the invention. The content of the epoxy resin is 74 386 wt%, the content of the amine hardener is 24.795 wt%, and the content of the ultraviolet absorber A is 0.669 wt%, based on the total weight of the yellowing resistant epoxy resin composition. And the content of TAD was 0.149 wt%. <Examples 2 and 3 > Examples 2 and 3 were prepared in the same manner as in Example 1 to prepare the yellowing resistant epoxy resin composition of the present invention, which was different in each implementation. The amount of epoxy resin (BE-188), amine hardener (903), ultraviolet absorber A and antioxidant (TAD) used in the examples, and the operating parameters are as follows: Table 18, 201118129 <Comparative Example 1 To 4 > Comparative Examples 1 to 4 are the same steps as in Example 1 to prepare an epoxy resin composition', except that In Comparative Examples 1 to 4, TAD' was not added and the amount of the epoxy resin, the amine hardener and the ultraviolet absorber used in each of the comparative examples was different, and the types of the amine hardener and the ultraviolet absorber were not the same. The operating parameters are shown in Table 1. Table 1 Epoxy resin amine hardener UV absorber antioxidant (BE-188) ABAB (TAD) Example 1 74.386 24.795 - 0.669 0.149 Example 2 74.166 24.722 0.667 0.445 Example 3 74.4 24.8 - 0.7 - 0.1 Comparative Example 1 75 25 - - Comparative Example 2 74.45 24.81 - - 0.74 --- Comparative Example 3 74.45 24.81 - 0.74 - Comparative Example 4 Your calculation 1 : ? 88.9 - 11.1 - - *5 Main 2 "-J stands for not added. [Preparation of repaired stone] <Example 4 > The present embodiment is a layer of jade (taken from Huangqi Stone, which is a kind of marble) having a size of 7.5 cm X 30 cm, washed with water, The drying process is carried out by heating with a gas burner to remove the water in the layer of jade, and then according to the current application conditions of the rubber plant to strengthen the site, at 45. (: at a temperature of ~60 ° C, the resistant and odor-resistant oxygen resin composition of Example 1 was poured on the surface of the layer of jade, and the pressure was applied uniformly by a white iron trowel to make the yellowing resistant epoxy The resin composition penetrates into the crack or hole of the layer of jade to fill the defects. After about 1 hour of hardening process, the yellowing resistant epoxy tree 12 201118129 ^ Sa composition can be hardened to obtain a repaired layer. <Examples 5 and 6> The repaired stone materials were prepared in the same manner as in Example 4, except that the yellowing resistant rings used in Examples 5 and 6 were used. The oxy-resin composition was in the order of the yellowing-resistant epoxy resin compositions of Examples 2 and 3, and the stone used in Example 6 was a peaceful white (taken from Huangqi Stone Industry, also a kind of marble). <Comparative Example 5 to 8 > • Comparative Examples 5 to 8 were prepared in the same manner as in Example 4, except that the epoxy resin compositions used in Comparative Examples 5 to 8 were sequentially Comparative examples to 4 epoxy resin compositions, and comparison The stone used in 5 to 7 is a silver fox (taken from the Yanqi Stone Industry, also a kind of marble); the stone used in Comparative Example 8 is a white Dali (taken from the Yanqi Stone Industry 'is also a kind of marble). Test for resistance to yellowing] The repaired stone of Examples 4 to 6 and Comparative Examples 5 to 8 was cured (φ is hardened and then allowed to stand for 48 hours) and then placed in a weathering test machine (referred to as QUV, purchased) From Guangbo Industrial Co., Ltd.; model number: QUV-spray), at a temperature of 50t:, irradiated with ultraviolet light at a power of 0.68 w/m2, and observed the yellowing of the % oxygen resin composition in the eighth. X, γ, ζ tristimulus vahles are measured by colorimeter every hour (ie 2 hours, 40 hours, 60 hours and 8 hours) and converted to yellow index (Yellow Index; according to astm Ε3ΐ3) For yellowing, the smaller the value of Λγι, the better the yellowing resistance. The data are shown in Table 2.

13 201118129 表2 ΔΥ.Ι 實施 例4 實施 例5 實施 例6 比較 例5 比較 例6 比較 例7 丨比較 例8 20小時 1.23 1.75 Γ 0.43 6.13 1.36 2.76 38.92 | 40小時 4.66 3.25 3.22 9.30 4.25 5.78 45 52 60小時 7.52 5.53 4.94 13.75 6.49 9.38 80小時 10.60 | 7.95 10.25 15 11.03 13.96 - 由表2的ΛΥ.ι值可知，以TETA為硬化劑且沒有添加 1外線吸收劑與抗氧化劑的比較例8的八丫】值最大，代表 其耐貝變性最差’其次是沒有添加紫外線吸收劑與抗氧化 劑的比較例5,再者為未添加抗氧化劑或使用市售含有 HALS之紫外線吸收劑商品的比較例6及7，而使用本案如 式（I)所示之抗氧化_實施例4至6的ΔΥΙ值相對比較小 ’雖然實施例4在6G小時後的耐黃變性猶比比較例6差一 些，然經過80小時後的耐黃變性就優於比較例6，故本案 、、二L補的石材上的經硬化的環氧樹脂組成物確實有較佳的 耐黃變性。 综上所述，本案實施例中所使用的抗氧化劑確實具有 分子量小及價格便宜的優點，且添加了該抗氧化劑的實施 例所製得的經修補的石材上的經硬化的環氧樹脂組成物的 耐黃變性都優於比較例，若與us 2〇〇9/〇〇23843 —案的實例 5相比，改用本發明所揭示之抗氧化劑，僅需的添加 量即可達到相當好的效果，可以節省下35 %之添加量，故 本發明確實適用於修補室内大理石、花崗石等天然石材之 缺陷，再者，所使用的胺類紫外線吸收劑及胺類硬化劑也 都能與環氧樹脂快速騎反應，縮短石材鄉製程需要耗 14 201118129 •費可降低成本，故確實能達到本發明之目的。 处、1所述者，僅為本發明之較佳實施例而已，當不 =乂此限&本發明實施之範@，即大凡依本發明_請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 益。 【主要元件符號說明】 • i&. 〇13 201118129 Table 2 ΔΥ.Ι Example 4 Example 5 Example 6 Comparative Example 5 Comparative Example 6 Comparative Example 7 丨Comparative Example 8 20 hours 1.23 1.75 Γ 0.43 6.13 1.36 2.76 38.92 | 40 hours 4.66 3.25 3.22 9.30 4.25 5.78 45 52 60 hours 7.52 5.53 4.94 13.75 6.49 9.38 80 hours 10.60 | 7.95 10.25 15 11.03 13.96 - From the ΛΥ.ι of Table 2, the gossip of Comparative Example 8 with TETA as the hardener and no external absorbent and antioxidant added The value is the largest, which represents the worst resistance to shelling, and the second is the comparative example 5 in which no ultraviolet absorber and antioxidant are added, and the comparative example 6 in which no antioxidant is added or a commercially available ultraviolet absorbent containing HALS is used. 7, and using the present invention as shown in formula (I), the antioxidant values of Examples 4 to 6 are relatively small, although the yellowing resistance of Example 4 after 6G hours is still worse than that of Comparative Example 6, but after The yellowing resistance after 80 hours is better than that of Comparative Example 6, so the hardened epoxy resin composition on the stone of this case and the second L has a better yellowing resistance. In summary, the antioxidant used in the examples of the present invention does have the advantages of small molecular weight and low cost, and the cured epoxy resin on the repaired stone prepared by the embodiment in which the antioxidant is added. The yellowing resistance of the material is superior to that of the comparative example. If the antioxidant disclosed in the present invention is used in comparison with the example 5 of the case of us 2〇〇9/〇〇23843, only the required addition amount can be achieved quite well. The effect can save the amount of addition of 35%, so the invention is indeed suitable for repairing defects of natural stone such as indoor marble, granite, etc. Further, the amine ultraviolet absorber and the amine hardener used can also be used. Fast reaction with epoxy resin, shortening the stone industry process requires 14 201118129 • The fee can reduce the cost, so it can achieve the purpose of the invention. The above is only the preferred embodiment of the present invention, and is not limited to the limit of the present invention, that is, the simpleness of the invention according to the invention and the content of the invention. Equivalent variations and modifications are still within the scope of the invention. [Simple description of the schema] Benefits. [Main component symbol description] • i&. 〇

1515

Claims (1)

201118129 七、申請專利範圍： L 一種用於修 /補材的耐黃變環氧樹脂組成物，係包括一 妝痛硬化劑、一胺類紫外線吸收劑及一具 如下式（I)所示的抗氡化劑： R3201118129 VII. Patent application scope: L A yellowing resistant epoxy resin composition for repairing/repairing, comprising a makeup pain hardening agent, an amine ultraviolet absorbent and an anti-caries represented by the following formula (I) Chemical: R3 衣氧樹脂、一 # ϋ ί® π # f (I) ”中 ’ h 為 Η、OH 或 〇R1〇，且 Ri。為一 Ci_Ci8 烧 土 2 R3、R4及R5各自獨立地為一 Ci-C6烷基；及 R6 為 Η、一 Cl_c6 烷基或 nh2。 2.依據巾請專利範㈣丨項所述之耐黃變環氧樹脂組成物 ，其中，該環氧樹脂是雙酚型環氧樹脂。 3 ·依據申請專利範圍第1頂所械 J现固笫i項所述之耐黃變環氧樹脂組成物 ，其中，用以表示該抗氧化劑的式⑴中的&為H。 4. 依射請專㈣㈣3额述之耐黃變環論脂組成物 ，其中，該抗氧化劑為4-胺基-2,2,6,6-四甲哌啶。 5. 依據申請專利範圍第丨項所述之耐黃變環氧樹脂組成物 ，其中，以該耐黃變環氧樹脂組成物總重量計，該抗氧 化劑的含量是介於0.074 wt%至〇.5 wt%之間。 6. 依據申請專利範圍第1項所述之耐音鐵 』s义％虱樹脂組成物 ，其中，以該耐黃變環氧樹脂組成物總重量計，該環氧 樹脂的含量是介於74 wt%至88 wt%之μ。 16 201118129 依據申請專利範圍第1項所述之耐黃變環氧樹脂組成物 ’其中’以該耐黃變環氧樹脂組成物總重量計，該胺類 硬化劑的含量是介於22 wt%至26 wt%之間。 8. 9. 依據申請專利範圍第1項所述之耐黃變環氧樹脂組成物 ，其中，以該耐黃變環氧樹脂組成物總重量計，該胺類 紫外線吸收劑的含量是介於〇 2 wt%至〇 8 wt%之間。 一種修補一石材的方法，該石材具有至少一缺陷，該方 法係將一耐黃變環氧樹脂組成物填入該石材的缺陷内， 並使該财κ變％氧樹脂組成物進行硬化反應，該耐黃變 環氧樹腊組成物包括—環氧樹脂、—胺類硬化劑、一胺 類紫外線吸㈣及-具有如下式⑴所示的抗氧化劑： R, 鲁 10. 11In the epoxy resin, a # ϋ ί® π # f (I) ”, 'h is Η, OH or 〇R1〇, and Ri is a Ci_Ci8 burnt soil 2 R3, R4 and R5 are each independently a Ci-C6 The alkyl group; and R6 is ruthenium, a Cl_c6 alkyl group or nh2. 2. The yellowing resistant epoxy resin composition according to the patent application (4), wherein the epoxy resin is a bisphenol type epoxy resin. The yellowing-resistant epoxy resin composition according to the first application of the first application of the present invention, wherein the & in the formula (1) for indicating the antioxidant is H. (4) (4) The amount of the anti-yellowing ring of the lipid composition, wherein the antioxidant is 4-amino-2,2,6,6-tetramethylpiperidine. 5. The yellowing resistant epoxy according to the scope of the patent application. a resin composition, wherein the antioxidant is contained in an amount of from 0.074 wt% to 0.5 wt% based on the total weight of the yellowing resistant epoxy resin composition. a sound-resistant iron s%% resin composition, wherein the epoxy resin is based on the total weight of the yellowing resistant epoxy resin composition The amount is between 74 wt% and 88 wt%. 16 201118129 The yellowing resistant epoxy resin composition according to claim 1, wherein the amine is based on the total weight of the yellowing resistant epoxy resin composition. The content of the hardener is between 22 wt% and 26 wt%. 8. The yellowing resistant epoxy resin composition according to claim 1, wherein the total weight of the yellowing resistant epoxy resin composition is The content of the amine ultraviolet absorber is between wt2 wt% and 〇8 wt%. A method for repairing a stone having at least one defect, the method is a yellowing resistant epoxy resin composition Filling in the defects of the stone material, and causing the hardening reaction of the yttrium-reducing epoxy resin composition, the epoxy resin-resistant epoxy resin composition includes an epoxy resin, an amine hardener, an amine ultraviolet absorber (4), and - an antioxidant having the following formula (1): R, Lu 10.11 ⑴ 其中’ Ri為Η、OH或〇r _ 基 1〇,且吣為一 C&8，I、R3、R4及R5各自獨立地 R盔 兩 C!-C6燒基； 6 马 η、一 Cl-C6 烷基或 NH2。 依據申請專利範圍第9項所述之修補 中’該環氧樹脂是雙酚型環氧樹脂。 :據申請專利範圍第9項所述之修補一石材 ，用以表示該抗氧化劑的式（1)巾μ ^ 依嬙占 ⑴干的R6為Η。 據申請專利範圍第U項所述 修補一石材的方法 石材的方法 石材的方法 17 12. 201118129 中，該抗氧化劑為4_胺基_2,2,6,6-四甲娘咬。 依射請專利範圍第9項所述之修補:材的方法，盆 中丄以㈣黃變環氧樹脂組成物總重量計，該抗氧化劑 的含S：是介於0.074 wt%至0.5 wt%之間。 14. 依據申請專利範圍第9項所述之修補一石材的方法，其 中，㈣耐黃變環氧樹脂組㈣總f量計，該環氧樹脂 的含:S：疋介於74 wt%至88 wt%之間。 15. 依據申請專利範圍第9項所述之修補一石材的方法，苴 中，以該耐黃變環㈣脂組㈣總重量計，該胺類硬: 劑的含量是介於22 wt%至26 wt%之間。 16. 依據申請專利範圍第9項所述之修補一石材的方法，盆 中’以該耐黃變環氧樹脂組成物總重量計，該胺類紫外 線吸收劑的含量是介於〇2 wt% i 〇8 4之間。 17. 依據申請專利範圍第9項所述之修補一石材的方法，其 中°玄石材是選自於花岗石、大理石、蛇紋石、化石 、石灰石、砂岩或洞石。 18· 一種經修補的石材，其係由如申請專利範圍第9項至第 17項所述之修補一石材的方法所製得的。 18(1) where ' Ri is Η, OH or 〇r _ base 1〇, and 吣 is a C&8, I, R3, R4 and R5 are each independently R-helmet two C!-C6 alkyl; 6 horse η, a Cl -C6 alkyl or NH2. According to the repair described in claim 9 of the patent application, the epoxy resin is a bisphenol type epoxy resin. The repairing stone according to item 9 of the patent application scope, wherein the formula (1) of the antioxidant is used to represent (1) the dry R6 is Η. According to the application scope of the patent scope U to repair a stone method stone method stone method 17 12. 201118129, the antioxidant is 4_amine 2,2,6,6-tetramethrin bite. According to the method of repairing material according to item 9 of the patent scope, the antimony containing S: is between 0.074 wt% and 0.5 wt%, based on the total weight of the (iv) yellowing epoxy resin composition. . 14. The method for repairing a stone according to claim 9, wherein (4) the yellowing resistant epoxy resin group (four) total f amount, the epoxy resin contains: S: 疋 between 74 wt% and 88 wt %between. 15. The method of repairing a stone according to claim 9 of the patent application, wherein the amine hard content is from 22 wt% to 26 wt% based on the total weight of the yellowing resistant ring (iv) lipid group (IV) %between. 16. The method of repairing a stone according to claim 9 of the patent application, wherein the content of the amine ultraviolet absorber is 〇2 wt% i 盆 based on the total weight of the yellowing resistant epoxy resin composition. Between 8 and 4. 17. The method of repairing a stone according to claim 9, wherein the stone is selected from the group consisting of granite, marble, serpentine, fossil, limestone, sandstone or travertine. 18. A repaired stone material obtained by the method of repairing a stone as described in claims 9 to 17. 18