4195 14 經濟部中央標準局貝工消費合作社印装 A7 B7 五、發明説明（（） Γ本發明之領域】 本發明係關於一種塗料用防火组成物，尤指_種適用 於添加在水性基或油性基合成樹脂塗料中，使其於受熱火 焰時膨脹具有防火效果之組成物，其可應用於鋼構、室内 裝潢、電線電纜或其他需要防火場合使用之塗料。 【本發明之背景】 傳統作為防火用途之膨脹型防火塗料，多係於塗料基 材（Base，如水性壓克力系、油性壓克力系等合成樹脂） 中’加入碳層形成劑（如多元醇類、多醣類…等）、竣層 催化劑（如磷酸化合物等）及發泡劑（如蜜胺、尿素系、 氯化墦、有機胺系等），並輔以其他有關助劑以塗覆於結 構材上，利用其受熱時形成碳質膨服層，用以阻絕熱源傳 遞以達到防火效果。 然而，這種直接由碳層形成劑形成之碳質膨脹層，係 屬非結晶體結構（amorphous)之硬質碳（hard carbon)所組成，強度弱且鬆散，易被高溫吹燒之火焰 氣流衝破、掉落，以致喪失防火效能。而且，此種非結晶 體硬質碳膨脹層在高溫下容易與空氣中之氧原子反應形成 一氧化碳、二氧化碳…，以及其他不易燃燒之灰燼，造成 所謂灰化現象，其耐熱特性遠較結晶結構之軟質碳（s〇ft carbon )來得差。因此，上述傳統膨脹型防火塗料之應 用領域受到相當大的限制。 晚近，雖有美國專利第3,574,644號、日本專利特 I-；-------- 裝----.--訂 ------線 (請先Η讀背面之注意^項再填寫本頁) 開昭55-1 1 8987、特開昭56-95 94 1、特開平5-4195 14 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A7 B7 V. Description of the invention (() Γ Field of the invention] The present invention relates to a fire-resistant composition for coatings, especially _ In oil-based synthetic resin coatings, a composition that makes it expand when heated by a flame and has a fireproof effect, which can be applied to steel structures, interior decoration, wires and cables, or other coatings that require fire protection. [Background of the invention] Traditionally used as Fire-resistant intumescent fire-resistant coatings are mostly based on coating substrates (such as synthetic resins such as water-based acrylics and oil-based acrylics) with the addition of carbon layer forming agents (such as polyols, polysaccharides ... Etc.), layered catalysts (such as phosphoric acid compounds, etc.) and foaming agents (such as melamine, urea-based, thallium chloride, organic amine-based, etc.), and supplemented with other related additives to coat structural materials, use When it is heated, it forms a carbonaceous swelling layer, which is used to block the transmission of heat sources to achieve a fireproof effect. However, the carbonaceous swelling layer directly formed by the carbon layer forming agent has an amorphous structure ( It is composed of hard carbon, which has weak strength and looseness. It is easy to be broken and dropped by the high-temperature blown flame airflow, which results in loss of fire resistance. In addition, this amorphous hard carbon expansion layer is easy to contact with at high temperature. The oxygen atoms in the air react to form carbon monoxide, carbon dioxide, etc., and other non-combustible ashes, resulting in the so-called ashing phenomenon. Its heat resistance is far worse than that of the soft carbon (sft carbon) of the crystalline structure. Therefore, the above conventional expansion type The application fields of fire-resistant coatings are quite limited. Recently, although there are US Patent No. 3,574,644 and Japanese Patent No. I-; ------------------------------------ Line (Please read the notes on the back ^ before filling in this page) Kai Sho 55-1 1 8987, JP Sho 56-95 94 1, Tek Hira 5-
4195 14 A7 B7 經濟部中央標率局貝工消费合作社印製 五、發明説明（）） 70540、特開平9-1 83 978、特開平10·1 7796等專利 案，陸續揭露將具有軟質碳結構之膨脹性石墨添加於油漆 塗料、發泡材中，使分別具有抗拒火焰，刷塗性、防火性 較佳之效果。然而， 1.該膨脹性石墨因石墨層間插入的酸根分子受熱膨脹急 速向外溢散，促使各石墨層間的距離拉開而形成蠕蟲 狀物，致使膨脹後的蠕蟲狀石墨體積增加了 100〜200倍，比重減輕、強度降低，極易因火力作 用或熱對流而四處飛散，降低了對内部被塗覆物及基 材（Base)的阻燃效果，在上述美、日專利中均未 有有效解決辦法。 2·前述曰本專利特開平9_ 1 83 97S雖曾提出膨脹性石墨 與磷酸化合物之配比為1〇%-25% ;日本專利特開平 1 0-1 7796亦將膨脹性石墨與塗料基材之重量配比限 制在1 % -3 0 %。但上述美、曰專利對整體防火組成 物之其他成分並未提及調配比例，其究應以何種比例 調配始得製成？是否能形成高強度、高耐溫性、不易 灰化、不易龜裂、不會飛散之軟質碳膨脹層不得而 知，致使上述專利僅止於理論階段，業界難以據以實 施，難為產業所利用。 3.膨脹性石墨粉本身係以強酸氧化天然鱗片狀石墨製得 之層間化合物，常帶有PH3 - 5之酸性特質，上述 美、曰專利將此粉末加入防火塗料或發泡材中，將會 造成塗料基材（Base)合成樹脂的質變，影響塗料的 請 聞 面 之 注4195 14 A7 B7 Printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Inventory () The expanded graphite is added to paints and coatings and foamed materials, so that they have the effects of flame resistance, better paintability and fire resistance. However, 1. The expansive graphite swelled out due to the thermal expansion of the acidic molecules inserted between the graphite layers, which promoted the distance between the graphite layers to form worms, which increased the volume of the expanded worm-like graphite by 100 ~ 200 times, reduced specific gravity, reduced strength, easily scattered around due to fire or thermal convection, reducing the flame retardant effect on the inner coating and substrate (Base), which are not found in the above US and Japanese patents Effective solutions. 2. The aforementioned Japanese Patent Laid-open No. 9_ 1 83 97S has proposed that the ratio of expandable graphite and phosphoric acid compound is 10% -25%; Japanese Patent Laid-open No. 1 0-1 7796 also uses expandable graphite and coating substrate The weight ratio is limited to 1%-30%. However, the above-mentioned US and Japanese patents do not mention the blending ratio for the other components of the overall fire-resistant composition. What proportion should they be made before they are blended? Whether it can form a soft carbon expansion layer with high strength, high temperature resistance, non-ashing, non-cracking, and non-scattering is unknown. As a result, the above-mentioned patents are limited to the theoretical stage, which is difficult for the industry to implement and to be used by the industry. . 3.Expansive graphite powder itself is an interlayer compound made by oxidizing natural flake graphite with strong acid, often with acidic properties of PH3-5. The above US and Japanese patents add this powder to fireproof coatings or foaming materials. Cause the qualitative change of paint base material (Base) synthetic resin.
I 旁 本紙張尺度逋用中固困家梂隼（CNS > A4洗格{ 210X297公釐） 83,3.1〇,〇〇〇I Next to this paper size, use Zhonggu sleepy furniture (CNS > A4 wash grid {210X297 mm) 83,3.1〇, 〇〇〇
4 195 U A7 B7 經濟部中央梯準局貝工消費合作社印製 五、發明説明（今） 基本物性與化性，又此種帶有酸性之防火塗料塗覆於 鋼構上，極易引起鋼材的銹化現象，對塗料或被塗覆 物而言均易造成傷害。 4. 一般市售的膨脹性石墨粉之粒徑約在目_1〇〇目， 混合入防火塗料中塗覆，會形成表面凹凸不平的紋 路，造成不平整亦不美觀的表面；又於喷塗作業時， 噴塗口徑極易被較大之石墨粒徑堵塞，造成施工曠時 不便。 發明人聋因於此，本於積極發明之精神，亟思一種可 以解決上述問題之「塗料用防火組成物」，幾經研究實驗 終至完成此項嘉惠世人之發明。 【本發明之概述】 本發明之主要目的係在提供一種塗料用防火組成物， 俾能有效抑制受熱膨脹之蠕蟲狀軟質碳四處飛散情形。 本發明之另一目的係在提供一種防火组成物，俾能依 其重量配比添加於塗料中，當受熱火焰時能迅速建立一種 高強度、高韌性、高附著性，且不易灰化、不易龜裂、發 煙量少之膨脹層，用以阻絕熱源傳遞達到防火效果。 本發明之再一目的係在提供一種塗料用防火組成物， 俾以PH値介於6.5-8之膨脹性軟質碳添加於塗料中，.促使 塗料基材不會產生質變，並可避免塗覆之鋼構銹化。 本發明之又一目的係在提供一種塗料用防火組成物， 俾具有細粒徑之膨脹性軟質碳，藉以獲得表面平整、塗敷 美觀、容易喷塗的效果。 nt ml HI i·^— - n . <請先聞讀背面之注意事項再填寫本頁} -訂 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） 83. 3.10,000 419514 A7 -----B7 五、發明説明（+ ) ~ — ." ' 為達成上述目的，本發明之主要成分包括有：膨脹# 軟質碳、碳層形成劑、碳層催化劑、以及發泡劑，其重量 比例為 1 : 2.5 4 : 4 - 5 : 1 . 5 - 2。 依據上述各成分重量比例關係混練好之防火組成物， 將其以1份膨脹性軟質碳對應3·5_4份塗料基材（Base)之 比例摻和，如下表所載。 \ 膨脹性 軟質碳 破層 形成物 碳層 催化劑 發泡劑 塗料基材 重量比例 1份 2.5 - 4 份 4-5份 1.5-2 份 3.5-4 份 經濟部中央標率局貞工消費合作社印裝 --------- -f:-- (請先W讀背面之注意事項再填寫本頁) 刷塗或噴塗上述摻和好之防火塗料於被塗覆物上，當 芡熱火焰大於200。(：時，由於碳層催化劑之催化反應及發 泡劑之發泡作用，促使碳層形成劑於表面受熱脱水膨脹形 成厚實乏碳殼層，而膨脹性軟質碳亦受熱膨脹5〇倍〜3〇〇 倍成為纖維狀軟質碳材並摻插於碳殼層内，有如於碳殼層 内混以含短纖維之軟質碳而強化了碳殼層内部結構，形成 一種類似碳纖維強化的膨脹層，由於軟質碳對氧的穩定性 向，故可有效阻絕火焰吹襲長達丨小時以上，幾無灰化損 壞發生，被塗覆物背面溫度低於3〇〇β(：以下；並且，表面 長成蠕蟲狀之石墨將被碳殼層牢牢地固持住，可抑制蠕蟲 狀石墨四處飛散情形，達成本發明之目的。 本發明之防火組成物可用以添加於水性基合成樹脂塗 料中，亦可'泰加於油性基合成樹脂塗料中，均可達成上述 目的。 本紙張从制t國國家榡準（〇叫六4胁（210父297公# ) 4195 14 經濟部中央標準局負工消費合作社印^ A7 B7 五、發明説明（$ ) 本發明之膨脹性軟質碳可選擇純度在80%以上之天 然鱗片狀石墨、石油碳系人工石墨、煤焦碳系人工石墨、 kish石墨、熱分解石墨，或其他等效石墨原材中之至少一 種，在強氧化劑作用下將硫酸根離子、磷酸根離子、醋酸 根離子，或其他等效離子中之至少一種插入石墨原材之層 間結構中，促使其具有遇熱膨脹之特性。為了中和該膨脹 性軟質碳之酸性，可將其再以氨水、或鹼金屬或鹼土金屬 之或乳化合物中和，使其PH値介於6.5-8.0，使摻入塗料 基材後不會產生質變，並可避免塗覆之鋼構銹化發生。膨 脹性軟質碳之粒徑選擇，可控制在8 〇目_ 2 5 〇目，較佳的 是120目_200目，有利於噴塗不會堵塞噴口，並可獲得表 面平整、塗敷美觀之效果。 本發明採用之破層形成劑可為異戊四醇、二異戊四 醇、聚異戊四醇、丙三醇、三羥曱基甲烷、三羥甲基丙 垸、乙二醇、丙二醇、環己二醇或其他等效多元醇類，或 山梨糖醇、葡萄糖、半乳糖、果糖、阿拉伯糖、蔗糖、擬 粉、糊轉、果膠、果酸或其他等效多酷類中之至少—種。 碳層形成劑之重量須大於碳層催化劑的1/3，較佳的是大 於碳層催化劑的1 /2，以利形成厚實碳殼層牢牢地固持住 螺蟲狀石墨’克服螺蟲狀石墨受熱飛散之問題。 ， 碳層催化劑可為紅磷、三聚氰胺焦磷酸、磷酸胍尿 素、正磷酸、三聚磷酸、偏磷酸、聚磷酸、亞磷酸、六偏 磷酸、聚磷酸銨、磷酸二氫銨、磷酸氫銨、偏磷酸銨、亞 私紙張尺度適用中國固家標準（CNS ) A4規格（210X297公羹） --.--1---d------訂·------i (锖先閲讀背面之注項再填寫本頁) 4 tftS t4 五、發明説明（厶） 磷酸銨、焦磷酸銨、六偏磷酸銨、氯化磷、氣氧化磷、磷 酸酐或其他等效含磷化合物中之至少一種。 發泡劑可為尿素、蜜胺、有機胺系或其他等效含氮化 合物、或氯化蠟中之至少一種。發泡劑之重量不可大於碳 層形成劑，較佳的是為碳層形成劑的5 〇 % _ 8 〇 %，以利形 成高耐熱且不鳧裂之高強度膨脹層。 由於本發明所揭露之組成物重量比例明確、技術新類 且確有進步性，確能提供產業上利用，故依法申請發明專 利〇 【較佳具體實施例之詳細説明】 為能讓貴審查委員能更瞭解本發明之技術内容，特 舉二較佳具體實施例説明如下。以下各實施例所舉之各成 分份數配比係指重量配比。 實施例一 經濟部中央標準局貝工消费合作社印裝 ----------^-------.π - * . (請先閲讀背面之注意事項再填寫本頁) 取純度大於98 %、PH値7.5、粒徑1〇〇〜150目、 膨脹倍率140倍之膨脹性石墨粉is克、聚鱗酸铵93 克、蜜胺33.5克、異戍四醇50克、水性基壓克力樹脂 7 〇克，並輔以適當份量之水、分散劑、消泡劑、顏料、 沈膜助劑等調製$成防火塗料，喷塗於3 〇 c m X 3 0 c m X 0.12cm之鋼板的一面上，表面美觀，喷塗厚度1 mm。置 於空氣中25°C〜30°C自然陰乾，待塗料乾燥後在距離火 焰噴燈口 8cm處豎立本鋼板，並於鋼板背面正對噴燈口 處壓貼熱電偶以量測溫度。 本紙張尺度適用t國國家標準（CNS ) A4規格（210x2974^ ) 4195 14 A7 B74 195 U A7 B7 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of the invention (today) Basic physical and chemical properties, and this type of acid-containing fireproof coating is applied to steel structures, which is very likely to cause steel The rusting phenomenon is easy to cause damage to the coating or the coated object. 4. Generally, the particle size of the commercially available expanded graphite powder is about 100 mesh. When mixed into the fire-resistant coating, it will form uneven texture on the surface, resulting in an uneven and unsightly surface. During operation, the spraying caliber is easily blocked by the larger graphite particle size, causing inconvenience when the construction is open. Because of this, the inventor is deaf. In the spirit of active invention, he is thinking about a "fire-resistant composition for coatings" that can solve the above problems. After several research and experiments, he finally completed this invention that benefits the world. [Summary of the Invention] The main purpose of the present invention is to provide a fire-resistant composition for coatings, which can effectively inhibit the worm-like soft carbon from being scattered around by thermal expansion. Another object of the present invention is to provide a fire-resistant composition, which can be added to a coating according to its weight ratio, and can quickly establish a high strength, high toughness, and high adhesion when heated by a flame, and is not easy to ash and difficult to The cracked and less smoked expansion layer is used to prevent heat source transmission to achieve fire prevention effect. Another object of the present invention is to provide a fireproof composition for coatings, which is added to the coating with an intumescent soft carbon having a pH of between 6.5 and 8 to promote the coating substrate to avoid qualitative changes and avoid coating. The steel structure is rusted. Another object of the present invention is to provide a fire-resistant composition for coatings, which is an expandable soft carbon with a fine particle size, so as to obtain the effects of flat surface, beautiful coating and easy spraying. nt ml HI i · ^ —-n. < Please read the notes on the reverse side before filling out this page} -The size of the paper is applicable to China National Standard (CNS) A4 (210X297mm) 83. 3.10,000 419514 A7 ----- B7 V. Description of the Invention (+) ~ —. &Quot; 'In order to achieve the above purpose, the main components of the present invention include: expanded # soft carbon, carbon layer forming agent, carbon layer catalyst, and hair The foaming agent has a weight ratio of 1: 2.5 4: 4-5: 1.5. The fireproof composition that has been well-kneaded according to the weight-to-weight relationship of the above components is blended in a proportion of 1 part of intumescent soft carbon corresponding to 3 · 5-4 parts of the coating substrate (Base), as shown in the following table. \ Expansive soft carbon layer formation carbon layer catalyst foaming agent coating material weight ratio 1 part 2.5-4 parts 4-5 parts 1.5-2 parts 3.5-4 parts Printed by Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs --------- -f:-(Please read the precautions on the reverse side before filling out this page) Brush or spray the above-mentioned blended fireproof coating on the coated object. Greater than 200. (: At the time, due to the catalytic reaction of the carbon layer catalyst and the foaming effect of the foaming agent, the carbon layer-forming agent is heated to dehydrate and expand on the surface to form a thick and depleted carbon shell layer, and the expandable soft carbon is also expanded by 50 times to 3 times. 〇 × becomes fibrous soft carbon material and is inserted into the carbon shell layer, as if the carbon shell layer is mixed with soft carbon containing short fibers to strengthen the internal structure of the carbon shell layer, forming an expansion layer similar to carbon fiber reinforcement, Due to the stability of soft carbon to oxygen, it can effectively prevent the flame from blowing for more than one hour, and there is almost no ashing damage. The temperature of the back surface of the coated object is lower than 300 β (: or less; and the surface grows into The worm-like graphite will be firmly held by the carbon shell layer, which can inhibit the worm-like graphite from flying around and achieve the purpose of the present invention. The fireproof composition of the present invention can be used to add to water-based synthetic resin coatings. It can be used in oil-based synthetic resin coatings to achieve the above purpose. This paper is manufactured in accordance with the national standard of the country (0 called six 4 threats (210 father 297 public #) 4195 14 Central Ministry of Economic Affairs, Ministry of Economic Affairs, off-work consumption Cooperation India ^ A7 B7 V. Description of the invention ($) The expansive soft carbon of the present invention can be selected from natural flake graphite, petroleum carbon artificial graphite, coal coke artificial graphite, kish graphite, and thermal decomposition graphite with a purity of 80% or more. Or at least one of other equivalent graphite raw materials, under the action of a strong oxidant, at least one of sulfate ion, phosphate ion, acetate ion, or other equivalent ion is inserted into the interlayer structure of the graphite raw material to promote It has the characteristics of thermal expansion. In order to neutralize the acidity of the expansive soft carbon, it can be neutralized with ammonia water, or alkali metal or alkaline earth metal or milk compound to make its pH 値 6.5-8.0, so that After entering the coating substrate, no qualitative change will occur, and the rusting of the coated steel structure can be avoided. The particle size selection of the expandable soft carbon can be controlled between 80 mesh_250 mesh, preferably 120 mesh_ 200 mesh, which is beneficial to spraying without clogging the spout, and can obtain the effects of flat surface and beautiful coating. The layer-forming agent used in the present invention may be isoprene tetraol, diisoprene tetraol, polyisoprene tetraol, Glycerol Methane, trimethylolpropane, ethylene glycol, propylene glycol, cyclohexanediol, or other equivalent polyols, or sorbitol, glucose, galactose, fructose, arabinose, sucrose, pseudopowder, paste, At least one of pectin, fruit acid, or other equivalent types. The weight of the carbon layer forming agent must be greater than 1/3 of the carbon layer catalyst, preferably greater than 1/2 of the carbon layer catalyst to facilitate formation. The thick carbon shell layer firmly holds the snail-shaped graphite 'to overcome the problem of snail-shaped graphite being heated and scattered. The carbon layer catalyst can be red phosphorus, melamine pyrophosphate, guanidine phosphate, orthophosphoric acid, tripolyphosphoric acid, metaphosphoric acid , Polyphosphoric acid, phosphorous acid, hexametaphosphoric acid, ammonium polyphosphate, ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium metaphosphate, substandard paper standards are applicable to China National Standard (CNS) A4 specifications (210X297). --1 --- d ------ Order · ------ i (锖 Please read the notes on the back before filling this page) 4 tftS t4 5. Description of the invention (厶) Ammonium phosphate, pyrophosphate Ammonium, ammonium hexametaphosphate, phosphorus chloride, aerobic phosphorus oxide, phosphoric anhydride, or other equivalent phosphorus-containing compounds One kind. The foaming agent may be at least one of urea, melamine, organic amine-based or other equivalent nitride-containing compounds, or chlorinated wax. The weight of the foaming agent may not be greater than that of the carbon layer forming agent, preferably 50% to 80% of the carbon layer forming agent, in order to form a high-strength expansion layer with high heat resistance and no cracking. Because the weight ratio of the composition disclosed in the present invention is clear, the technology is new, and it is indeed progressive, it can indeed provide industrial use. Therefore, the invention patent is applied in accordance with the law. [Detailed description of the preferred embodiment] To better understand the technical content of the present invention, the second preferred embodiment is described below. The proportions of the components in the following examples refer to the proportions by weight. Example 1 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ---------- ^ -------. Π-*. (Please read the precautions on the back before filling this page) Take swollen graphite powder with a purity of more than 98%, pH 7.5, particle size 100-150 mesh, and 140-fold expansion ratio, is grams, 93 grams of polyammonium phosphonate, 33.5 grams of melamine, 50 grams of isotetraol, 70 grams of water-based acrylic resin, supplemented with an appropriate amount of water, dispersant, defoamer, pigment, film deposition additive, etc. to prepare a fire-resistant coating, sprayed on 30 cm X 30 cm X 0.12 One side of the steel plate of cm, the surface is beautiful, and the thickness is 1 mm. Place it in the air at 25 ° C ~ 30 ° C to dry naturally in the shade. After the paint is dried, stand up the steel plate 8cm away from the flame torch, and press the thermocouple on the back of the steel plate directly facing the torch to measure the temperature. This paper size applies to the national standard (CNS) A4 size (210x2974 ^) 4195 14 A7 B7