200302803 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關熱硬化型及/或紫外線硬化型各種光阻 油墨、粘合劑、塗料、印刷油墨等自由基聚合性組成物之 包裝形態者，有關可確保自由基聚合性組成物之經時安定 性’同時確保輸送時之安全性，對於環境亦評估考量之良 好包裝形態者。 【先前技術】 先行技術中，做爲光阻油墨者，如：焊接光阻油墨、 蝕刻光阻油墨、電鍍光阻油墨等例，一般使用自由基聚合 性組成物者。 先行熱硬化型及/或紫外線硬化型之光阻油墨材料、 粘合劑、塗料、印刷油墨等自由基聚合性組成物包裝時， 鋼罐或塑膠容器被廣範使用之。 鋼罐使用上，如：爲不使含於光阻油墨之溶劑等揮發 性成份不外漏’避免內容物之流出，務必使上蓋與本體部 份完全密封至無任何隙縫方可。惟，在完全無隙縫密封下 ，易出現鋼相互磨擦剝落，混入光阻油墨中，保管時外側 生銹影響作業環境惡化等問題點產生。 另外，塑膠容器爲防止含於光阻油墨中之溶劑、內容 成份後容器之膨脹、或爲不使於可視光、紫外光下內容物 之變質，而設計增加容器厚度，著色內蓋以確保強度，密 閉性。惟，塑膠容器長期保管、高溫放置後，易使容器變 -6 - (2) (2)200302803 形、溶劑蒸發、內容物產生外漏等問題點出現。 又，目前所使用之光阻油墨其適用對象之基板配線極 細微複雜，因此，印刷性之曝光，顯像亦被要求高精細化 ，由容器產生微小碎片等之不良原因，造成問題點。 更且，近年對環境之考量被重視，要求使用後之廢棄 物的削減。被考慮鋼罐使用後加壓壓碎，進行溶解後再行 利用，惟，附著於罐中之光阻油墨有機、無機成份造成障 礙導致無法循環利用。另外，塑膠容器其廢棄容量之體積 膨脹，爲使廢棄容量減量化考量做成顆粒後再行利用。惟 ，粉碎容器時，務必充份洗淨殘留於容器之光阻油墨，而 洗淨時所使用之溶劑又增加廢棄物。且，粉碎時被抱怨噪 音問題造成困擾。此等問題與熱硬化型及/或紫外線硬化 型之粘著劑、塗料、印刷油墨等其他自由基聚合性組成物 相同。 此熱硬化型及/或紫外線硬化型之光阻油墨、粘著劑 、塗料、印刷油墨等自由基聚合性組成物之容器所要求之 牛寸性、環境對應逐年嚴格受限，先行的鋼罐、塑膠容器漸 漸難以應付。 又，自由基聚合性組成物容器中被要求可避免溶劑揮 發、內容物流出 '內容物變質者、可安定保管、同時可運 送者。 更被要求儘可能減少容器所產生之垃圾，要求高精度 之製品、環保蒽識、減少容器之廢棄量者。 (3) (3)200302803 【發明內容】 本發明爲解決先行容器之課題，主要目的係爲提供一 種做爲光阻油墨、粘著劑、塗料、印刷油墨等自由基聚合 性組成物之包裝形態者爲特別理想之包裝方法者，可確保 保管時自由基聚合性組成物之經時安定性，同時，確保運 送時之安定性，使用後之廢棄容易，且可減少廢棄量，環 境對策佳之包裝形態者。 爲達成該目的，本發明提供一種利用可加熱密封之合 成樹脂薄片之包裝袋內收容自由基聚合性組成物與空氣爲 其特徵之包裝形態者。 理想形態係該包裝袋爲至少具有1層至少阻斷1種溶 劑、氣體、可視光及紫外線層者，該層爲合成樹脂薄片層 及/或金屬層者。包裝袋內之空氣量爲自由基聚合性組成 物容量之1% 〜50%者宜，且，該包裝袋爲至少具有1 層至少阻斷1種溶劑、氣體、可視光及紫外線層之合成結 構薄片者佳，該薄片總厚度爲50〜3〇〇// m，其至少阻斷 1種溶劑、氣體，可視光及紫外線層之厚度以5 // m以上 者宜。 特別是，該自由基聚合性組成物爲二液型組成物時， 該包裝袋內被畫分爲2個以上之區域，至少1區中被收容 自由基聚合性組成物及空氣之型態者宜。例如，該包裝袋 內被晝分爲2個區域，該自由基聚合性組成物爲主劑與硬 化劑組成二液型之光阻油墨者，一區爲主劑，另一區爲硬 化劑被收容之包裝形態者。 -8- (4) (4)200302803 又，該包裝袋可於複數個鋼罐或塑膠容器中做成捆包 之包裝形態者。 [發明實施之形態] 本發明者爲開發一種滿足光阻油墨等自由基聚合性組 成物所使用容器之要求特性的包裝形態，進行精密硏封後 結果發現於使用可加熱密封之合成樹脂薄片的包裝袋中同 時收容自由基聚合性組成物與空氣之包裝形態後，藉由氧 阻斷抑制自由基聚合性組成物之聚合，保管中其自由基聚 合性組成物不會產生凝膠化，可確保光阻油墨等自由基聚 合性組成物之經時安定性，同時，由於爲可撓性袋狀者， 因此於使用時不致有運送時疏忽之破損，內容物漏出、或 混入微小異物等均不會產生，更且，使用後廢棄時無體積 膨脹現象爲環保最佳之包裝形態者，進而完成本發明。 以下，針對本發明進行詳細說明，首先，本發明基本 特徵係於使用該可加熱密封之合成樹脂薄片包裝袋內塡充 光阻油墨等自由基聚合性組成物時滲入空氣，藉此可確保 自由基聚合性組成物之保存安定性。此乃藉由熱、紫外線 、等控制所產生自由基反應含於空氣中之氧自由基後，妨 礙組成物中硬化性樹脂、單體成份之聚合，而防止高分子 化者。做爲空氣之量者，針對所塡充自由基聚合性組成物 容量爲1%以上者，效果雖顯現，惟，若超出50%則包 裝體本身容積增加，則不適於捆包而不理想。理想之空氣 量爲5% 〜30% 者^ (5) (5)200302803 做爲包裝袋之構成者可使可加熱密封之合成樹脂薄片 之周邊進行加熱密封後，做成袋狀者，而，爲提昇氣體隔 離性，耐透濕性，以熔融或粘合劑接合2片以上之合成樹 脂薄片之層合物做成袋狀者，更佳者爲提昇遮光性，使鋁 箔、鋁蒸鍍層等金屬層介於層間之層合薄片做成袋狀物者 ，更於使用前爲確定內容物之變質等時，介著具有可以手 剝離內層材料所成合成樹脂薄片之粘合強度的粘合層進行 層合後之層合薄片做成袋狀者等爲理想者。另外，藉由設 · 置至少1層阻斷至少1種溶劑、氣體、可視光及紫外線之 合成樹脂薄片層及/或金屬後，可防止內容物之變質、變 色等。 更藉由層合薄片各層組合與厚度可提昇運送時之耐摩 損性。先行稱Pouch之包裝袋必須隔開外容器，而，本發 明之包裝袋則使用做成外容器之鋼罐、塑膠容器後，其中 以本包裝袋單位之複數個任意擠壓後，於運送中仍可取得 充份之安全性與耐摩損性。 · 又，做爲該合成樹脂薄片者可使用聚烯烴、聚酯、聚 醯胺等，而，合成樹脂薄片之至少任一個爲聚酯時，於搬 · 運時，可取得防止鋁箔等金屬層之損傷效果，特別是於與 金屬層接觸面配合聚酯薄片層則效果更大。 做爲該包裝袋之形狀者可爲平裝、立型、角撐板型等 任意形狀均可’ 一般又以易於擠出之平袋形狀爲較佳者。 又，爲易於擠出亦可使噴出口 （突起狀排出口部份）等進 行加熱做成粘合物者。更於二液型之光阻油墨、粘合劑等 -10- (6) (6)200302803 時，包裝袋做成畫分爲2個區域之結構後，同時擠出二液 ，可立即混煉，作業性爲良好者。 做爲該合成樹脂薄片者只要可加熱密封者均可使用之 ，困應所期待之強度、撕裂性可使用單軸或雙軸延伸薄膜 。其材質例如··聚乙烯、聚丙烯、聚丁烯、聚戊烯等聚烯 烴；聚乙烯對苯二甲酸酯、聚丁烯對苯二甲酸酯等聚酯； 尼龍等聚醯胺等高分子量之熱塑性樹脂例者。此等合成樹 脂薄片可自由組合使用之。又，此等合成樹脂於樹脂合成 時可作成具低、中、高密度或結晶性之物者，亦可任意使 用之。又’此等合成樹脂幾乎呈透明者，而，於外容器使 用具遮光性者則可確保內容物之經時安定性。 另外’藉由添加顏料等具紫外像遮掩能力之物質後， 做成遮光性合成樹脂薄片後，以包裝袋單體可使內容物具 經時女疋性。包裝袋可由單一合成樹脂薄片進行製作之， 而，此時務必添加具紫外線遮掩能力之物質者。又，亦可 以各種合成樹脂薄片之層合薄片製作之，而，此時，至少 1層務必3有具糸外線遮掩能之物質者。做爲具紫外線遮 掩能之物質者不僅吸收紫外線物質者，亦可藉由反射、散 射後遮掩紫外線之透光者。如：氧化鈦、氧化鋁、氧化矽 、氯化鐵、鋅、碳酸鈣' 碳酸鎂、石墨等無機頻料、水楊 酸衍生物、二苯甲酮衍生物、苯並三唑衍生物、氰基丙烯 酸酯衍生物等有機系紫外線吸收劑例者。 理想者係藉由設置如上述之金屬層後，附與或提昇其 m㈣離I生及遮光性，可防止藉由紫外線等引起自由基聚 -11 - (7) (7)200302803 合性組成物之聚合，溶劑揮劑造成凝膠化、變質、變色者 。做爲所使用之金屬層者以鋁箔、鋁蒸鍍層者宜。設置金 屬層時，合成樹脂薄片無須含有具紫外線遮掩能之物質者 ，惟，藉由倂用遮光性合成樹脂薄片後當然可更提昇其遮 光性者。 用於該包裝袋之薄片（單薄片或層合薄片）其厚度愈 厚氣體遮掩性、遮光性、耐摩損性愈佳，惟，大於300 // m之厚度時，則薄片變硬，不易使用，反之，低於50 // m φ 之厚度太薄時，將降低耐摩損性、運送時出現洞孔等不適 於光阻油墨等自由基聚合性組成物之包裝。因此，用於該 包裝袋之薄片總厚度以50〜300 // m者宜。 又，用於該包裝袋之金屬層厚度愈厚其氣體隔離性， 遮光性、耐摩損性愈佳，惟，用於該包裝袋薄片之總厚度 其本身上限被限定之。另外，金屬層厚度低於5 // m太薄 時’於運送時易於金屬箔本身出現洞孔，而無法取得所期 待使用效果。 着 以下針對添附圖面所示本發明包裝袋幾個理想形態進 行說明。 - 圖1代表自內側往外側由合成樹脂薄片1/粘合層2/合 · 成樹脂薄片3/金屬層4/合成樹脂薄片5之5層層合結構薄 片所製作之包裝袋截面結構者。做爲該內側之合成樹脂薄 片】之材料者爲具有加熱密封性之可延伸性合成樹脂，如 ··聚乙烯、聚酯等爲宜，而，做爲中間層之合成樹脂薄片 3及外側之合成樹脂薄片5之材料例者只要具某種程度之 -12- (8) (8)200302803 強度者均可使用之，如：聚乙烯、聚酯、聚醯胺等爲理想 使用者。金屬層4爲設有絕范或錦蒸鍍層之薄片者，又， 粘著層2係其兩側之合成樹脂薄片1，3間被調整爲具有 以手可剝離之粘著強度者，如：環氧基樹脂系粘合劑，熱 熔粘合劑等者可使用之。 該形態製袋後於合成樹脂薄片1與合成樹脂薄片3之 間的粘合層2做成可以手剝離之結構後，萬一於搬運中該 層間之金屬層4破損時，剝離外側之金屬層4之薄片部份 後’可易於確定內容物不會混入金屬層4之破損部份。又 ’包裝袋廢棄時，可分開金屬層4之部份與樹脂部份，易 於再循環利用，呈更環保之形態者。 以下圖2係代表周圍1 2被加熱密封形成袋狀，同時 沿著2分之中心線形成加熱密封部份後，包裝袋1 〇之內 部晝分成2個區域n a，n b之形態。 此包裝袋其自由基聚合性組成物適用於二液型組成物 者。如：自由基聚合性組成物由主劑與硬化劑所成之二液 型光阻油墨時，其一區丨i a收容主劑，另一區1 1 b收容硬 化劑者。藉此，同時擠出2液後，可立即進行混煉，作業 性爲理想者。又，藉由收容之內容物亦可畫分爲3區以上 【實施方式】 以下以實施例及試驗例爲例，針對本發明效果進行具 體說明，惟，本發明並未限於以下實施例。 -13- 200302803 Ο) [試驗例1 ] 以太陽油墨製造（股份）製光阻油墨之主劑（PSR-4000 Z26)與硬化劑（CA- 40Z26K)及下記溶劑分別塡 入由下記薄片所製作之平袋內，於50 °C下進行保管後， 測定重量變化（減量％ )。其結果示於表1〜表3。 使用溶劑： · 〈溶劑A〉Ipsol #150 (出光石油化學公司製）， 〈溶劑 B> Dawanol DPM (二丙二醇單甲醚，Dawchemi-cal公司製） <溶劑C>甲氧基丙醇（丙二醇單甲醚Daicell化學工 業公司製） <溶劑D> Dukisol CA (二乙二醇單乙醚乙酸酯，大阪 有機化擧公司製） 包裝袋材質： <薄膜A>聚乙烯薄膜4〇 # m - <薄膜B>聚乙烯薄膜55 " m . <薄膜C>聚乙烯/聚酯雙層薄膜，總厚度60 // m <薄膜D>聚酯/鋁箔/聚酯/粘著劑/聚乙烯、總厚度 9〇/i m之薄膜 -14 - (10) 200302803 表1 50°C下之 溶劑A 溶劑B 減量(％) 1曰後 2日後 5日後 8日後 1日後 2日後 5曰後 8日後 薄膜A 破損 破損 破損 破損 -1.4% -2.1% -4.3% -6.6% 薄膜B -4.1% -8.0% -9.5% -12.2% -0.4% -1.1% -1.3% -2.6% 薄膜C -1.3% -2.8% -3.6% -4.8% -0.2% -0.8% -1.1% -1.9% 薄膜D 0.0% 0.0% -0.1% -0.1% 0.0% 0.0% 0.0% 0.0%200302803 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to packaging of radically polymerizable compositions such as various types of photocurable inks, adhesives, coatings, and printing inks that are thermosetting and / or ultraviolet curing. For those who are in shape, those who can ensure the stability of the radically polymerizable composition over time and at the same time ensure the safety during transportation, and evaluate the environment in a good packaging form. [Prior technology] In the prior art, as the photoresist ink, such as welding photoresist ink, etching photoresist ink, plating photoresist ink, etc., generally use radical polymerizable composition. Steel cans or plastic containers are widely used when packaging thermally-curable and / or ultraviolet-curable photoresist ink materials, adhesives, coatings, printing inks, and other radically polymerizable compositions. For use of steel cans, for example, in order to prevent the volatile components such as solvents contained in photoresist ink from leaking out 'to prevent the contents from flowing out, the upper cover and the body must be completely sealed without any gaps. However, under the complete gap-free sealing, it is easy for the steel to rub and peel off each other, and mix into the photoresist ink, which causes problems such as rust on the outside and deterioration of the working environment during storage. In addition, the plastic container is designed to prevent the solvent contained in the photoresist ink, the container from swelling after its content, or to prevent the contents from being deteriorated under visible light and ultraviolet light. The thickness of the container is increased, and the inner cover is colored to ensure strength. , Hermeticity. However, after long-term storage of plastic containers and storage at high temperatures, it is easy to make the containers -6-(2) (2) 200302803 shape, solvent evaporation, and leakage of contents. In addition, currently used photoresist inks have extremely delicate and complicated substrate wiring. Therefore, printable exposure and development are also required to be high-definition, resulting in problems such as the occurrence of tiny fragments in containers. In addition, environmental considerations have been taken seriously in recent years, and reduction of waste after use is required. It is considered that the steel cans are crushed under pressure after use and dissolved before reuse. However, the organic and inorganic components of the photoresist ink attached to the cans cause obstacles and cannot be recycled. In addition, the volume of the waste volume of the plastic container is expanded, and it is made into pellets for the purpose of reducing the waste capacity and then used. However, when crushing the container, be sure to fully wash the photoresist ink remaining in the container, and the solvent used in the cleaning will increase waste. In addition, it is troubled by complaining about noise when crushing. These problems are the same as those of other radical polymerizable compositions such as heat-curable and / or ultraviolet-curable adhesives, paints, and printing inks. The thermal resistance and / or ultraviolet curing type of the photoresist ink, adhesive, coating, printing ink and other containers of radically polymerizable composition containers are strictly restricted year by year. The leading steel tanks , Plastic containers are gradually difficult to cope. In addition, the radically polymerizable composition container is required to prevent solvent volatilization and content flow-out. “People who have deteriorated content can be stored safely and transported at the same time. It is also required to reduce the waste generated by the container as much as possible, those who require high-precision products, environmentally friendly anthracene, and reduce the amount of waste of the container. (3) (3) 200302803 [Summary of the invention] To solve the problem of advanced containers, the main purpose of the present invention is to provide a packaging form of a radical polymerizable composition such as photoresist ink, adhesive, coating, printing ink, etc. It is a particularly ideal packaging method, which can ensure the stability of the radical polymerizable composition over time during storage, and at the same time ensure the stability during transportation. It is easy to dispose after use, and can reduce the amount of waste. Shapers. In order to achieve the object, the present invention provides a packaging form characterized by containing a radically polymerizable composition and air in a packaging bag using a heat-sealable synthetic resin sheet. Ideally, the packaging bag has at least one layer that blocks at least one solvent, gas, visible light, and ultraviolet light, and the layer is a synthetic resin sheet layer and / or a metal layer. The amount of air in the packaging bag is preferably 1% to 50% of the capacity of the radical polymerizable composition, and the packaging bag has a synthetic structure with at least one layer blocking at least one solvent, gas, visible light, and ultraviolet layer A thin sheet is preferred. The total thickness of the thin sheet is 50 ~ 300 // m. It should block at least one solvent, gas, and the thickness of visible light and ultraviolet layer should be 5 // m or more. In particular, when the radical polymerizable composition is a two-liquid type composition, the inside of the packaging bag is divided into two or more regions, and at least one of the regions contains the type of the radical polymerizable composition and air. should. For example, the packaging bag is divided into two areas by day. The radical polymerizable composition is a two-component type photoresist ink composed of a main agent and a hardener. One area is a main agent and the other is a hardener. Contained in packaging form. -8- (4) (4) 200302803 In addition, the packaging bag can be packaged in a plurality of steel cans or plastic containers. [Forms of the Invention] The present inventors developed a packaging form that satisfies the required characteristics of a container for a radically polymerizable composition such as photoresist ink. After precise sealing, the result was found in a heat-sealable synthetic resin sheet. After the packaging form of the radically polymerizable composition and air is contained in the packaging bag, the polymerization of the radically polymerizable composition is inhibited by oxygen blocking, and the radically polymerizable composition does not gel during storage. It ensures the stability over time of radical polymerizable compositions such as photoresist inks, and it is a flexible bag, so it will not be neglected during transportation, the contents will leak out, or small foreign matter will be mixed. It will not be produced, and moreover, there is no volume expansion phenomenon when it is discarded after use, which is the best environmentally friendly packaging form, and then the present invention is completed. Hereinafter, the present invention will be described in detail. First, the basic feature of the present invention is that when the heat-sealable synthetic resin sheet packaging bag is filled with a radically polymerizable composition such as photoresist ink, it can penetrate into the air to ensure freedom. Storage stability of the base polymerizable composition. This is because the free radicals generated in the air are controlled by the control of heat, ultraviolet rays, etc., and the oxygen radicals contained in the air can hinder the polymerization of the hardening resin and monomer components in the composition and prevent the polymer from being polymerized. As for the amount of air, the effect is apparent for the capacity of the charged radical polymerizable composition of 1% or more, but if it exceeds 50%, the volume of the package itself increases, which is not suitable for packing. The ideal amount of air is 5% to 30% ^ (5) (5) 200302803 As the component of the packaging bag, the periphery of the heat-sealable synthetic resin sheet can be heat-sealed to form a bag shape, and, In order to improve the gas barrier property and moisture permeability, the laminate of two or more synthetic resin sheets made by melting or adhesive is made into a bag shape. The better one is to improve the light-shielding property, such as aluminum foil, aluminum vapor deposition layer, etc. If the laminated sheet with the metal layer between the layers is made into a pouch, it is more necessary to determine the deterioration of the contents before use. It is preferable that the laminated sheet in which layers are laminated is formed into a bag shape or the like. In addition, by providing at least one layer of synthetic resin sheet and / or metal that blocks at least one solvent, gas, visible light, and ultraviolet light, the content can be prevented from being deteriorated or discolored. Furthermore, the combination and thickness of the layers of the laminated sheet can improve the abrasion resistance during transportation. It was first stated that the packaging bag of Pouch must be separated from the outer container, and the packaging bag of the present invention is made of steel cans and plastic containers made of outer containers. Among them, a plurality of the bags are arbitrarily squeezed and then transported. Still get full safety and abrasion resistance. · Also, as the synthetic resin sheet, polyolefin, polyester, polyamide, etc. can be used. When at least one of the synthetic resin sheets is polyester, a metal layer such as aluminum foil can be obtained during transportation and transportation. The damage effect, especially when the polyester sheet layer is in contact with the metal layer, is more effective. The shape of the packaging bag may be any shape such as a flat pack, a vertical type, a gusset type, and the like. Generally, a flat bag shape that is easy to squeeze out is preferred. In addition, for easy extrusion, a discharge port (projected discharge port portion) or the like can be heated to form an adherend. More than two-liquid type photoresist inks, adhesives, etc. (10) (6) (6) 200302803, after the packaging bag is made into a structure divided into two areas, the two liquids are simultaneously squeezed out and can be immediately mixed , The workability is good. As the synthetic resin sheet, it can be used as long as it can be heat-sealed, and uniaxial or biaxially stretched film can be used for the desired strength and tearability. Its materials are, for example, polyolefins such as polyethylene, polypropylene, polybutene, and polypentene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon Examples of high molecular weight thermoplastic resins. These synthetic resin sheets can be used in combination freely. In addition, these synthetic resins can be made into low, medium, high density or crystalline materials during resin synthesis, and can also be used arbitrarily. In addition, those synthetic resins are almost transparent, and those that make the appliance light-shielding in the outer container can ensure the stability of the contents over time. In addition, by adding a substance having a UV image hiding ability such as a pigment, and then forming a light-shielding synthetic resin sheet, the content of the bag can be used to make the contents aging. The packaging bag can be made of a single synthetic resin sheet, and at this time, it is necessary to add a substance having a UV shielding ability. In addition, it can be made of laminated sheets of various synthetic resin sheets, and at this time, at least one layer must be provided with a substance having an external line shielding ability. As a substance with ultraviolet shielding energy, not only those who absorb ultraviolet substances, but also those who shield the ultraviolet light through reflection and scattering. Such as: titanium oxide, alumina, silica, ferric chloride, zinc, calcium carbonate, magnesium carbonate, graphite and other inorganic materials, salicylic acid derivatives, benzophenone derivatives, benzotriazole derivatives, cyanide Examples of organic ultraviolet absorbers such as acrylate derivatives. Ideally, by providing a metal layer as described above, by attaching or improving its ionization and light shielding properties, it is possible to prevent free radical polymerization caused by ultraviolet rays and the like. 11-(7) (7) 200302803 Synthetic composition Polymerization, solvent evaporation caused gelation, deterioration, discoloration. As the metal layer to be used, aluminum foil or aluminum vapor deposition is preferred. When the metal layer is provided, the synthetic resin sheet does not need to contain a substance having ultraviolet shielding energy. However, by using a light-shielding synthetic resin sheet, the light-shielding property can be improved. The thickness of the sheet (single sheet or laminated sheet) used in the packaging bag is thicker, and the gas shielding, light shielding and abrasion resistance are better. However, when the thickness is greater than 300 // m, the sheet becomes hard and difficult to use. Conversely, if the thickness is less than 50 // m φ, the abrasion resistance will be reduced, and holes such as holes during transportation will not be suitable for packaging of radical polymerizable compositions such as photoresist inks. Therefore, the total thickness of the sheet used in this packaging bag should be 50 ~ 300 // m. In addition, the thicker the metal layer used in the packaging bag is, the better the gas barrier property, the light-shielding property and the abrasion resistance are, but the upper limit of the total thickness of the film used in the packaging bag is limited. In addition, when the thickness of the metal layer is less than 5 // m, if the thickness is too thin, holes in the metal foil are likely to occur during transportation, and the desired effect cannot be obtained. Hereinbelow, several desirable forms of the packaging bag of the present invention shown in the drawings are described. -Figure 1 represents the cross-sectional structure of a packaging bag made from a synthetic resin sheet 1 / adhesive layer 2 / composite from the inside to the outside and a 5-layer laminated structure sheet made of resin sheet 3 / metal layer 4 / synthetic resin sheet 5. As the material of the inner synthetic resin sheet], it is an extensible synthetic resin having heat-sealing properties, such as polyethylene, polyester, etc., and the synthetic resin sheet 3 as the middle layer and the outer layer The material example of the synthetic resin sheet 5 can be used as long as it has a certain degree of -12- (8) (8) 200302803, such as polyethylene, polyester, polyamide, etc. are ideal users. The metal layer 4 is a sheet provided with an extraordinary or brocade-plated layer, and the adhesive layer 2 is a sheet of synthetic resin sheets 1 and 3 on both sides of which are adjusted to have adhesive strength that can be peeled by hand, such as: Epoxy resin-based adhesives, hot-melt adhesives, etc. can be used. After the bag is made in this form, the adhesive layer 2 between the synthetic resin sheet 1 and the synthetic resin sheet 3 is made into a structure that can be peeled by hand. In case the metal layer 4 between the layers is damaged during transportation, the outer metal layer is peeled off. After the sheet portion of 4 ', it can be easily determined that the contents will not be mixed into the damaged portion of the metal layer 4. Also, when the packaging bag is discarded, the metal layer 4 and the resin portion can be separated, which is easy to recycle and has a more environmentally friendly form. The following figure 2 represents the shape in which the surrounding 12 is heat-sealed to form a bag shape, and the heat-sealed portion is formed along the center line of the second half. The inner portion of the packaging bag 10 is divided into two areas n a, n b during the day. In this packaging bag, the radical polymerizable composition is suitable for a two-liquid composition. For example, when the radically polymerizable composition is a two-liquid photoresist ink composed of a main agent and a hardener, one area i a contains the main agent, and the other area 1 1 b contains the hardener. Thereby, after two liquids are simultaneously squeezed out, kneading can be performed immediately, and workability is desirable. In addition, the contents to be contained can be divided into three or more areas. [Embodiment] The following describes the effects of the present invention with examples and test examples as examples, but the present invention is not limited to the following examples. -13- 200302803 〇) [Test Example 1] The main agent (PSR-4000 Z26), hardener (CA-40Z26K), and the solvent described below for the photoresist ink manufactured by Sun Ink Manufacturing Co., Ltd. were separately prepared from the following sheet After storage in a flat bag at 50 ° C, the weight change (% reduction) was measured. The results are shown in Tables 1 to 3. Solvents used: <Solvent A> Ipsol # 150 (manufactured by Idemitsu Petrochemical Co., Ltd.), <solvent B> Dawanol DPM (dipropylene glycol monomethyl ether, manufactured by Dawchemi-cal) < solvent C> methoxypropanol (propylene glycol Monomethyl ether Daicell Chemical Industry Co., Ltd.) < Solvent D > Dukisol CA (diethylene glycol monoethyl ether acetate, manufactured by Osaka Organic Chemicals Co., Ltd.) Material of the bag: < Film A > Polyethylene film 4〇 # m -< Film B > Polyethylene film 55 " m. < Film C > Polyethylene / polyester double-layer film, total thickness 60 // m < Film D > Polyester / aluminum foil / polyester / adhesive / Polyethylene, film with a total thickness of 90 / im-14-(10) 200302803 Table 1 Solvent A at 50 ° C Solvent B Loss (%) 1 day after 2 days 5 days after 8 days 1 day after 2 days 5 days after 5 days After 8 days, the film A was damaged. Damaged and damaged -1.4% -2.1% -4.3% -6.6% % -2.8% -3.6% -4.8% -0.2% -0.8% -1.1% -1.9% Film D 0.0% 0.0% -0.1% -0.1% 0.0% 0.0% 0.0% 0.0%
表2 50°C下之 溶劑C 溶劑D 減量(％) 1曰後 2日後 5日後 8日後 1日後 2日後 5曰後 8日後 薄膜A -1.0% -2.0% -3.3% -5.4% -0.8% -1.2% -3.0% -4.4% 薄膜B -0.4% -1.5% -1.3% -3.0% -0.3% -1.1% -1.8% -2.6% 薄膜C -0.1% -0.4% -1.1% -1.7% -0.1% -0.4% -1.0% -1.4% 薄膜D 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 表3 50°C下之 主劑 硬{ 匕劑 減量(％) 1曰後 2日後 5曰後 8曰後 1日後 2日後 5曰後 8曰後 薄膜A -0.7% -1.1% -2.2% 破損 -0.1% -0.2% > 0.4% -0.7% 薄膜B -0.3% -0.5% -0.8% -1.2% 0.0% 0.0% -0.1% -0.3% 薄膜C- -0.1% -0.2% -0.3% -0.3% 0.0% 0.0% -0.1% -0.1% 薄膜D 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0%Table 2 Solvent C at 50 ° C Solvent D Loss (%) 1 day after 2 days 5 days after 8 days 1 day after 2 days 2 days after 5 days 8 days after film A -1.0% -2.0% -3.3% -5.4% -0.8% -1.2% -3.0% -4.4% Film B -0.4% -1.5% -1.3% -3.0% -0.3% -1.1% -1.8% -2.6% Film C -0.1% -0.4% -1.1% -1.7%- 0.1% -0.4% -1.0% -1.4% Thin film D 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Table 3 The main agent at 50 ° C is hard {Dagger reduction (%) 1 after 2 5 days later 8 days later 1 day later 2 days later 5 days later 8 days later Film A -0.7% -1.1% -2.2% Damage -0.1% -0.2% > 0.4% -0.7% Film B -0.3% -0.5% -0.8% -1.2% 0.0% 0.0% -0.1% -0.3% Film C- -0.1% -0.2% -0.3% -0.3% 0.0% 0.0% -0.1% -0.1% Film D 0.0% 0.0% 0.0% 0.0 % 0.0% 0.0% 0.0% 0.0%
-15- (11) (11)200302803 [實施例1 ] 使用聚酯/銘范/聚酯/粘著劑/聚乙儀之層結構所成總 &度爲9 0 // m之薄膜製成平袋後，將太陽油墨製造（股 份）製之自由基聚合性光阻油墨之主劑（PSR_ 4〇〇〇 Z26) 及硬化劑（CA- 40Z26)分別塡入，進行密封時殘留空氣 。又，製成複數個各種殘留空氣量者。 [試驗例2] · 將收容該實施例1之自由基聚合性光阻油墨之各包裝 袋於5 0 °C下進行放置’所定日數後，以注射器吸出留於 其中之空氣，進行記錄其容量。隨後開封後，以EHD型 粘度計測定光阻油墨之粘度。取得空氣量與增粘率之關係 如表4所示。 -16- (12) 200302803 表4 1曰後 2日後 5曰後 8日後 空氣量 0.75% 0.62% 0.80% 0.77% 主 增粘率 20% 42% 87% 100% 空氣量 3.00% 1.30% 2.70% 4.10% 劑 增粘率 7.0% 15% 22% 24% 空氣量 3 1.1% 2 8.5% 4 0.0% 4 8.0% 增粘率 6.30% 12.3% 18.0% 20.0% 空氣量 0.45% 0.62% 0.77% 0.99% 硬 增粘率 3.88% 5.77% 13.20% 21.10% 化 空氣量 1.98% 2.23% 3.12% 3.34% 劑 增粘率 0.33% 0.43% 2.30% 2.20% 空氣量 31.10% 2 8.50 % 40.00% 48.00% 增粘率 0.21% 2.30% 1.99% 2.20%-15- (11) (11) 200302803 [Example 1] Made of thin film made of polyester / Mingfan / polyester / adhesive / polyethylene layer with a total & degree of 9 0 // m After forming into a flat bag, the main agent (PSR_4000Z26) and the hardener (CA-40Z26) of the radical polymerizable photoresist ink made by Sun Ink Manufacturing Co., Ltd. were respectively injected, and air remained during sealing. In addition, a plurality of various types of residual air were produced. [Experimental Example 2] · After placing each packaging bag containing the radically polymerizable photoresist ink of Example 1 at 50 ° C for a predetermined number of days, aspirate the air held in it with a syringe and record it. capacity. After subsequent unsealing, the viscosity of the photoresist ink was measured with an EHD-type viscometer. The relationship between the amount of air obtained and the viscosity increase ratio is shown in Table 4. -16- (12) 200302803 Table 4 Air volume 0.75% 0.62% 0.80% 0.77% after 1 day 2 days 5 days later 8 days Main viscosity increase rate 20% 42% 87% 100% air volume 3.00% 1.30% 2.70% 4.10 % Agent viscosity increase 7.0% 15% 22% 24% air volume 3 1.1% 2 8.5% 4 0.0% 4 8.0% viscosity increase rate 6.30% 12.3% 18.0% 20.0% air volume 0.45% 0.62% 0.77% 0.99% hard increase Viscosity 3.88% 5.77% 13.20% 21.10% Air volume 1.98% 2.23% 3.12% 3.34% Additive viscosity increase rate 0.33% 0.43% 2.30% 2.20% Air volume 31.10% 2 8.50% 40.00% 48.00% Viscosity increase rate 0.21% 2.30 % 1.99% 2.20%
由表4所示結果證明空氣量不足1%時，增粘率爲極 高者。 [實施例2] 於下記各平袋中，分別塡入1.6kg之太陽油墨製造（ 股份）製之自由基聚合性光阻油墨之主劑 （PSR-4000Z26)與0.6kg硬化劑 （CA- 40Z26)後，各準備7袋 ，塡入20 <之塑膠包裝罐。 -17- (13) (13)200302803 使用平袋： 〈薄膜D>聚酯/錦范（7 聚酯/粘著劑/聚乙烯 總厚度90 // m之薄膜使聚酯於內側製成之平袋。 . 〈薄膜E>聚乙烯/銘箔（7/Zm)/聚乙烯之總厚度ο // m之薄膜所製成之平袋。 〈薄膜F>聚乙烯/錦箔（4//m)/聚乙烯之總厚度54 β m之薄膜所製成之平袋。 〈薄膜G>聚乙烯/錦箔（7// m) /聚乙烯之總厚度55 φ // m之薄膜所製成之平袋。 〈薄膜H>聚酯/尼龍/銘箔（9/zm)/聚乙烯之總厚度 1 5 5 μ m之薄膜使聚酯於內側製成之平袋。 [試驗例3 ] 該實施例2之塑膠包裝罐由埼玉縣比企郡至大阪市中 央區進行往返運送試驗。其結果該鋁箔損傷情況如下，均 未有內容物漏出狀況。 Φ 2次往返均無損傷： < 薄膜D>與 < 薄膜h> 2次往返鋁箔出現洞孔： < 薄膜G> - 1次往返鋁箔出現洞孔： < 薄膜E>與 < 薄膜F> [發明效果] 如以上說明，本發明自由基聚合性組成物之包裝形態 係於使用可加熱密封之合成樹脂薄片之包裝袋內同時收容 自由基聚合性組成物與空氣，因此，藉由氧阻礙後控制自 -18- (14) (14)200302803 由基聚合性組成物之聚合，保管中自由基聚合性組成物不 會產生凝膠化’可確保自由基聚合性組成物之經時安定性 ，同時，爲可撓性袋狀，因此，其使用，運送時不致出現 ~ 不慎之破損，內容物之漏出、混入微小異物等，更且，使 用後廢棄時體積不會膨脹，具環保爲最理想之包裝形態者 。因此，最適合做爲光阻油墨等自由基聚合性組成物之包 裝形態者。 【圖式簡單說明】 圖1係代表本發明所使用包裝袋之截面結構的理想例 之一的部份槪略截面圖者。 圖2係代表本發明自由基聚合性組成物包裝形態之理 想例之一槪略平面圖者。 元件對照表 5 :合成樹脂薄片 ^ 4:金屬層 1，3 :合成樹脂薄片 — 2:粘合層 - 12:周圍 1〇:包裝袋 1 3 :加熱密封部份 1 1 a ^ lib:區 -19-From the results shown in Table 4, it was confirmed that when the amount of air is less than 1%, the viscosity increase ratio is extremely high. [Example 2] In each flat bag described below, 1.6 kg of a main agent (PSR-4000Z26) and 0.6 kg of a hardener (CA-40Z26) of a radical polymerizable photoresist made by Sun Ink Manufacturing (stock) were respectively charged. ), Prepare 7 bags each and pour into 20 < plastic packaging cans. -17- (13) (13) 200302803 Use a flat bag: <Film D> Polyester / Jinfan (7 Polyester / Adhesive / Polyethylene with a thickness of 90 // m The film is made of polyester on the inside Flat bag .. <Film E > Polyethylene / Ming foil (7 / Zm) / Polyethylene film with a total thickness ο // m. Flat bag made of film. <Film F > Polyethylene / Nylon foil (4 // m) / Polyethylene film with a thickness of 54 β m. 〈Film G > Polyethylene / nylon foil (7 // m) / Polyethylene film with a total thickness of 55 φ // m Flat bag. <Film H> Polyester / Nylon / Foil (9 / zm) / Polyethylene film with a total thickness of 155 μm. Flat bag made of polyester inside. [Test Example 3] The plastic packaging can of Example 2 was subjected to a round-trip transportation test from Hibi-gun, Saitama Prefecture to Chuo-ku, Osaka City. As a result, the damage of the aluminum foil was as follows, and no leakage of the contents was found. Φ No damage during 2 round trips: D > and < Film h > Holes appear in 2 rounds of aluminum foil: < Film G >-Holes appear in 1 round of aluminum foil: < Film E > and < Film F > [Inventive effect] As explained above, this invention The packaging form of the radically polymerizable composition is that the radically polymerizable composition and air are simultaneously contained in a packaging bag using a heat-sealable synthetic resin sheet. Therefore, it is controlled from -18- (14) ( 14) 200302803 Polymerization of the base polymerizable composition, the radical polymerizable composition will not gel during storage. It can ensure the stability of the radical polymerizable composition over time, and is a flexible bag. Therefore, during use, it will not appear during transportation ~ accidental damage, leakage of contents, mixing with small foreign matter, etc. Moreover, the volume will not swell when discarded after use, and it is the most ideal packaging form for environmental protection. It is a packaging form of a radical polymerizable composition such as a photoresist ink. [Brief Description of the Drawings] FIG. 1 is a partial cross-sectional view showing one of the ideal examples of the cross-sectional structure of the packaging bag used in the present invention. 2 is a schematic plan view showing one of the ideal examples of the packaging form of the radical polymerizable composition of the present invention. Element comparison table 5: Synthetic resin sheet ^ 4: Metal layer 1, 3: Synthetic resin thin - 2: adhesive layer --12: around 1〇: bag 13: heat-sealing portion 1 1 a ^ lib: zone -19-