201033291 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種賦黏劑、黏著劑/接著劑組成物、 丙稀酸系黏著劑/接著劑組成物及丙烯酸系活性能量射線 硬化型黏著劑/接著劑組成物。 【先前技術】 ❿ 先前’松香酯係被使用於黏著劑/接著劑用的賦黏樹 脂等各種用途。松香酯係松香類與醇的反應生成物。因為 松香類係以松脂等作為原料，所以含有各種不純物。又， 松香的主成分亦即松香酸係在分子中具有雙鍵。該等被認 為係經時劣化或聚合阻礙的原因，而被要求徹底地改善。 藉由使用安定性優良之歧化松香或氫化松香作為松 香類’能夠在某種程度上改善上述缺點。但是，即便是本 方法，亦無法滿足經時劣化或聚合阻礙性。 ^ 因此，本發明者已提案一種含有50重量％以上的四 氫松香酸之松香酿（參照專利文獻1}。使用本松香醋時， 能夠抑制黏著劑/接著劑的耐候性降低。但是，若長時門 曝露於紫外線時，黏著劑/接著劑產生黃變而且黏著劑脆 化’會有喪失膠黏性或黏接力之問題。 不過，近年來，為了降低環境負荷等，有提案一種藉 由將添加有賦黏劑的丙烯酸單體加以聚合，來製造未含有 溶劑的丙烯酸系黏著劑/接著劑之方法（例如參照專利文 3 201033291 獻2) ’但是，該方法因為在聚合系統含有賦黏劑而會 有對聚合反應帶來不良影響之可能性。因此，有提案一種 方法’係將凝膠渗透層析（Gpc)之在254奈米的紫外線分 光计檢測器的檢測輸出功率’除以標準聚苯乙烯的檢測輸 出功率之值设定為聚合阻礙參數α ,並將α設為1〇以 下’來得到聚合率高的Uv硬化型丙烯酸系黏著劑之方法 (參照專利文獻3^ 但是’即便依照該方法，抑制因聚合阻礙性所引起的 丙烯酸聚合物的分子量降低亦不充分，會產生凝集力的降 低。又，依照樹脂的種類，而會有與丙烯酸聚合物的相溶 性變差、黏著性能的平衡變差之問題。 [先前技術文獻] [專利文獻1]特開平1 1-3 35 654號公報 [專利文獻2]美國專利第4181752號說明書 [專利文獻3]特開2003-277695號公報 【發明内容】 [發明所欲解決之問題] 本發明提供一種即便長時間曝露在紫外線照射的情 況下’黏著劑/接著劑亦不會產生黃變或脆化，且與各種 丙烯酸聚合物的相溶性良好之賦黏劑、黏著劑/接著劑組 成物、丙烯酸系黏著劑/接著劑組成物及丙烯酸系活性能 量射線硬化型黏著劑/接著劑組成物。 [解決問題之技術手段] 201033291 本發明者為了解決前述課題而重複專心研討的結 果’發現藉由控制在松香所含有的特定成分量，且將松香 醋類的紫外線吸光光度設為一定以下，則能夠解決前述課 題’而完成了本發明。 亦即，本發明係有關於一種賦黏劑；含有該賦黏劑之 黏著劑/接著劑組成物；含有該賦黏劑之丙烯酸系黏著劑/ 接著劑組成物；及含有該賦黏劑之丙烯酸系活性能量射線 鲁硬化型黏著劑/接著劑組成物，該賦黏劑之特徵係含有松 香醋類（A) ’該松香酯類（A)依照紫外線吸光光度法之在 254奈米以上的區域的最大吸光度A (測定條件：試料濃 度為1 g/dm3、容器長度1公分）為〇 15以下，且水解物 的甲基化處理物依照氣體層析儀質量分析所測定的分子 量320的成分的含量，為分子量314〜3 2〇的成分的合計 量之95%以上。 [功效] 鲁 因為本發明的賦黏劑係耐光性良好，故適合作為光學 構件用黏著劑/接著劑的賦黏劑》又，因為本發明的賦黏 劑係聚合阻礙性低’故適合作為活性能量硬化型丙烯酸系 黏著劑/接著劑的賦黏劑，特別是能夠使用於光學構件用/ 電材用且活性能量硬化型丙烯酸系黏著劑/接著劑係有效 之黏著劑/接著劑。 【實施方式】 本發明的賦黏劑之特徵係含有松香酯類（A)(以下稱 5 201033291 為成分（A))，該松香酯類（A)依照紫外線吸光光度法之在 254奈米以上的區域的最大吸光度A (測定條件：試料濃 度為1 g/dm3、容器長度1公分）為0.15以下，且水解物 的曱基化處理物依照氣體層析儀質量分析所測定的分子 量3 20的成分的含量，為分子量314〜3 20的成分的合計 量之95%以上。 成分（A)係只要是依照紫外線吸光光度法之在254奈 米以上的區域的最大吸光度A (測定條件：試料濃度為1 g/dm3、容器長度1公分）為0.15以下，且水解物的甲基 化處理物依照氣體層析儀質量分析所測定的分子量320 的成分的含量，為分子量314〜320的成分的合計量之 950/。以上時，則沒有特別限定，可使用眾所周知者。當水 解物的曱基化處理物依照氣體層析儀質量分析所測定的 分子量3 20的成分的含量，不是分子量314〜3 20的成分 的合計量之95%以上時，或是依照紫外線吸光光度法之在 _ 254奈米以上的區域的最大吸光度A為大於0.15時，因 為耐光性低落，或是應用於丙烯酸系活性能量射線硬化型 黏著劑/接著劑時，會阻礙所得到的丙烯酸型聚合物的聚 合反應，而無法達成本發明的效果。 在成分（A)，依照紫外線吸光光度法之在254奈米以 上的區域的吸光度’係主要為碳-碳不飽和鍵有關的尖 峰°該值變大係意味著在分子中不飽和鍵增多。又，認為 著色性的不純物增多時，該值變大。因為碳_碳不飽和鍵 容易因紫外線而氧化等，而會成為賦黏劑的色調變差或脆 201033291 化的原因。又，碳-碳不飽和鍵係成為在自由基聚合中的 聚合阻礙性之主要原因。因此，必須將該吸光度值保持為 較低。又，所謂水解物的甲基化處理物的分子量為32〇 的成分，係相當於水解而生成的松香所衍生之樹脂酸成分 被甲基化者之中，分子内的不飽和鍵完全被氫化者。所謂 水解物的甲基化處理物的分子量為314的成分，係相當於 在刀子内具有3個碳-碳不飽和鍵者。因此，分子量為32〇 ❿的成分的含量為分子量314〜320的成分的合計量之95% 以上，係意味著在該成分（A)中所含有之具有碳碳不飽和 鍵的成分為極少β 作為成分（A) ’通常係使松香類（a丨）（以下稱為成分 (al))與醇類（b)(以下稱為成分化））反應，其中該松香 類（al)係：四氳松香酸及四氫海松脂酸等的甲基化處理物 依照氣體層析儀質量分析所測定的分子量32〇的成分的 含量，為分子量314〜32()的成分的合計量之95%以上。 參又’亦可以使松香類（a2)(以下稱為成分（a2))與成分（b) 反應，其中該松香類（a2)係：甲基化處理物依照氣體層析 儀質量分析所測定的分子量32〇的成分的含量，為分子量 3 14〜320的成分的合計量之小於95%，之後，藉由氫化 等操作而成為：水解物的甲基化處理物依照氣體層析儀質 量分析所測定的分子量320的成分的含量，為分子量3 14 〜320的成分的合計量之95%以上。 作為成分（al) ’只要是前述的甲基化處理物依照氣體 層析儀質量分析所測定的分子量32〇的成分的含量，為分 7 201033291 子量3 14〜3 20的成分的合計量之95 %以上之松香類時， 則沒有特別限定，能夠使用眾所周知者。例如，成分（a 1) 亦能夠單獨使用四氳松香酸。又，亦可以在四氳松香酸中 混合松香酸等樹脂酸成分而製備。而且，亦可以藉由後述 的方法’將成分（a2)氫化而成為：曱基化處理物依照氣體 層析儀質量分析所測定的分子量320的成分的含量，為分 子量314〜320的成分的合計量之95%以上。四氫松香酸 ❹係例如能夠藉由在有機化學期刊（Journal of Organic Chemistry)31，4128(1966 年）、有機化學期刊 34, 1550(1969年）所述之方法而得到。 作為成分（a2)，可舉出木松香、妥爾油（tall 〇u)松香、 橡膠松香等天然松香類及歧化松香及成分（a 1)以外的氫 化松香等。 作為製造本發明的賦黏劑所使用的成分（b)的具體 例’可舉出：正辛醇、2_乙基己醇、癸醇、月桂醇等的一 ®元醇；乙二醇、二甘醇、丙二醇、新戊二醇、環己院二甲 醇等的二元醇；甘油、三羥甲基乙烷、三羥甲基丙烷等的 三元醇；新戊四醇、二甘油等的四元醇；二新戊四醇等的 六元醇等。該等可單獨使用一種，亦可混合使用二種以 上。又，作為成分⑻’亦可使用環氧㈣類或去水甘油 類等。 該等之中’因為能夠將所得到的成分⑻或成分（a2) 、、刀（b)的反應生成物的軟化點設為需要的溫度以使 用四70醇及/或三元醇為佳。又，成分⑽或成分⑽及成 201033291 分(b)的使用*，係例如可按照所得到的反應生成物的目 標酸價、經值而決定。通常較佳是將成分⑷）或成分⑽ 中的羧酸基與成分（b)的羥基之莫耳比（〇h/c〇〇h)設為 0.5〜2左右。 成分（A)能夠藉由使成分（al)與成分（b)酯化反應而得 到。又，成分（A)亦可藉由使成分（a2)與成分（1?)醋化反應 後，進行氫化而得到。醋化反應能夠藉由眾所周知的醋化 參方法來進行。具體上’係纟l50〜300。〇左右的高溫條件 下，一邊將所生成的水往系統外去除、一邊進行。又空 氣混入酯化反應中時’所生成的酯化物有著色的可能性。 化反應係以在氮或氦、氬等的惰性氣體下進行為佳。而 且為了縮短反應時間，在酯化反應時亦可使用酯化觸 媒。作為酯化觸媒，能夠使用酸觸媒、鹼金屬的氫氧化物、 金屬氧化物等。作為酸觸媒，可舉出乙酸、對甲苯磺酸等。 作為驗金屬的氫氧化物，可舉出氫氧化約等。作為金屬氧 ® 化物可舉出氧化#5、氧化鎂等。 使成分（a2)與成分（b)酯化反應而得到的反應生成物 或(a2)的氫化能夠採用眾所周知的方法。以下，會有將使 成刀（a2)與&分（b)醋化反應而得到的反應生成物或成分 (a2)稱為氫化對象物之情形。氫化係例如藉由在氫化觸媒 的存在下’通常為1〜25MPa左右、較佳是5〜20MPa的 氫加壓下冑氫化對象物加熱0.5〜7小時左右、較佳是1 5 J時來進行。作為氫化觸媒，能夠使用受載觸媒、金 屬粉末、碘化物等各種眾所周知者。作為受載觸媒，可舉 9 201033291 鈀碳鍺碳、釕碳、麵碳等。作為金屬粉末可舉出錄、 鉑等。作為破化物，可舉出破、破化鐵等。該等之中’就 氫化效率（氫化率良好、氫化時間短）而言，以把、錄、 釕或翻系觸媒為佳。氫化觸媒的使用量係相對於⑽重量 份氫化對象物’通常為〇 〇1〜1〇重量份左右以〇 〇1〜5 重量份為佳。又，氫化溫度為100〜300。(：左右，以150 290 C為佳。又，氫化係按照必要亦可以在將松香溶解 ❹於溶劑的狀態進行。所使用的溶劑係沒有特別限定，只要 是對反應為惰性且原料或生成物容易溶解之溶劑即可。作 為溶劑，例如能夠組合環己烷、正己烷、正庚烷十氫萘、 四氫吱味、二巧燒等之i種或2種以上而使用。溶劑的使 用量沒有特別限制，通常係相對於原料樹脂，以固體成分 為10重量％左纟以上的方式使用。卩10〜7〇重量％的範 圍為佳。 而且，以通常的氫化條件氫化而成之氫化松香酯的情 Ο形中，水解物的甲基化處理物依照氣體層析儀質量分析所 測定的分子量320的成分的含量，只增加至分子量314〜 320的成分的合計量之2〇重量％左右。因此，必須藉由重 複氫化、增加觸媒使用量、選定提高氫化溫度之適當的觸 媒種類等。 如此進行所得到的成分（A)的軟化點（環球法）係通 常以設為50〜120°C左右為佳。藉由將軟化點設為5〇c>c以 上’因為賦黏劑的處理變得容易，故較佳。又，藉由將成 分（A)的色調設為300 Hazen(黑曾）（Jis K 0071-1 )以下 201033291 的無色透明，能夠適合使用於重視色調之光學構件用途、 電材用途。 本發明的賦黏劑係含有前述成分（A)者，但是按照必 要，亦可含有抗氧化劑等的各種添加劑。 本發明的黏著劑/接著劑組成物係含有前述的賦黏劑 者。作為黏著劑/接著劑組成物，沒有特別限定，可舉出 例如丙烯酸系黏著劑/接著劑組成物、苯乙烯-共軛雙稀系 嵌段共聚物黏著劑組成物、乙烯系熱溶接著劑組成物等。 本發明的丙烯酸系黏著劑/接著劑組成物，係至少含 有前述賦黏劑及丙烯酸系聚合物者。 為了得到丙烯酸系聚合物所使用的丙烯酸系單體，係 能夠按照丙烯酸系黏著劑/接著劑組成物所提供的各種用 途’而適當地決定其組成。作為丙烯酸系單體，可舉出各 種丙烯酸酯及/或曱基丙烯酸酯（以下稱為（曱基）丙烯酸 酯）。具體上，例如可舉出：（甲基）丙烯酸甲酯、（甲基） φ 丙烯酸乙酯、（甲基）丙烯酸丁酯、（曱基）丙烯酸2-乙基己 酯等。又’能夠在前述（甲基）丙稀酸酯中並用：（曱基）丙 稀酸、（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸2_羥基乙酯、 N-羥甲基（甲基）丙烯醯胺等作為交聯性的丙烯酸系單 體。而且按照必要，在不損害（甲基）丙烯酸酯聚合物的黏 著特性之程度’亦可並用其他能夠共聚合的單體，例如乙 酸乙烯酯、苯乙烯等。又，亦能夠使用將上述單體的至少 一種聚合而得到之具有烯烴雙鍵的聚合性低聚物作為丙 烯酸系單趙。 201033291 作為前述丙軸系單體的聚合方法沒有特別限制，能 合'㈣聚合、分散聚合乳化聚合等眾所 周知的方法。通常，能夠使用：過氧化苯^醯、過氧化月201033291 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an adhesive, an adhesive/adhesive composition, an acrylic adhesive/adhesive composition, and an acrylic active energy ray hardening type. Adhesive/adhesive composition. [Prior Art] 先前 Previously, 'rosin esters' have been used in various applications such as adhesive resins for adhesives/adhesives. The rosin ester is a reaction product of rosin and alcohol. Since rosin is made of turpentine or the like as a raw material, it contains various impurities. Further, the rosin acid which is a main component of rosin has a double bond in the molecule. These are considered to be causes of deterioration over time or polymerization, and are required to be completely improved. The above disadvantages can be improved to some extent by using disproportionated rosin or hydrogenated rosin which is excellent in stability as a rosin. However, even with this method, it is impossible to satisfy the deterioration with time or the hindrance of polymerization. Therefore, the present inventors have proposed a rosin which contains 50% by weight or more of tetrahydroabietic acid (see Patent Document 1). When the present rosin vinegar is used, the weather resistance of the adhesive/adhesive agent can be suppressed from being lowered. When the long-time door is exposed to ultraviolet light, the adhesive/adhesive is yellowed and the adhesive is embrittled, there is a problem of loss of adhesiveness or adhesion. However, in recent years, in order to reduce the environmental load, etc., there is a proposal for A method of producing an acrylic adhesive/adhesive containing no solvent by polymerizing an acrylic monomer to which a tackifier is added (for example, refer to Patent Document 3 201033291 2) However, the method contains a viscosity in a polymerization system. There may be a possibility of adversely affecting the polymerization reaction. Therefore, a method has been proposed to 'divide the detection output power of the 254 nm ultraviolet spectrometer detector by gel permeation chromatography (Gpc). The value of the detection output power of the standard polystyrene is set to the polymerization inhibition parameter α, and α is set to 1 〇 or less to obtain a Uv-curable acrylic adhesive having a high polymerization rate. (refer to Patent Document 3) However, even if the molecular weight of the acrylic polymer is not sufficiently reduced by the polymerization barrier property, the aggregation strength is reduced, and the cohesive force is lowered. The problem that the compatibility of the acrylic polymer is deteriorated and the balance of the adhesive property is deteriorated. [Prior Art Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. [Patent Document 3] JP-A-2003-277695 SUMMARY OF INVENTION [Problem to be Solved by the Invention] The present invention provides that an adhesive/adhesive does not cause yellowing even when exposed to ultraviolet light for a long period of time. Adhesive, adhesive/adhesive composition, acrylic adhesive/adhesive composition, and acrylic active energy ray-curable adhesive/adhesive composition which are embrittled and have good compatibility with various acrylic polymers [Technical means for solving the problem] 201033291 The inventors of the present invention repeated the results of the intensive study to solve the above problems, and found that it is controlled by the rosin. The present invention has been completed by setting the amount of the specific component and the ultraviolet ray illuminance of the rosin vinegar to be equal to or less than a certain value. That is, the present invention relates to an adhesive; the adhesive containing the adhesive Agent/adhesive composition; acrylic adhesive/subsequent composition containing the adhesive; and acrylic active energy ray-curable adhesive/adhesive composition containing the adhesive, the adhesive It is characterized by containing rosin vinegar (A) 'The maximum absorbance A of the rosin ester (A) in the region of 254 nm or more according to the ultraviolet absorption spectrophotometry (measurement condition: sample concentration is 1 g/dm 3 , container length 1 The centrifugation is 15 or less, and the methylated product of the hydrolyzate is 95% or more of the total amount of the components having a molecular weight of 314 to 3 2 Torr according to the content of the component of the molecular weight of 320 measured by mass spectrometry. [Effect] Lu is suitable as a tackifier for an adhesive for an optical member because the adhesive of the present invention is excellent in light resistance, and further, since the adhesive of the present invention is low in polymerization resistance, it is suitable as The adhesive of the active energy-curable acrylic pressure-sensitive adhesive/adhesive agent can be used particularly for an optical member/electric material and an active energy-curable acrylic pressure-sensitive adhesive/adhesive agent which is effective as an adhesive/adhesive. [Embodiment] The tackifier of the present invention is characterized by containing rosin ester (A) (hereinafter referred to as 5 201033291 as component (A)), and the rosin ester (A) is 254 nm or more according to ultraviolet absorption spectrophotometry. The maximum absorbance A of the region (measurement conditions: sample concentration: 1 g/dm3, container length: 1 cm) is 0.15 or less, and the molecular weight of the hydrolyzate is determined according to the molecular weight of the gas chromatograph. The content of the component is 95% or more of the total amount of the components having a molecular weight of 314 to 3 20 . The component (A) is a maximum absorbance A (measurement condition: sample concentration: 1 g/dm 3 , container length: 1 cm) in a region of 254 nm or more according to ultraviolet absorption spectrometry, and is 0.15 or less, and the hydrolyzate The content of the component of the molecular weight of 320 measured by mass spectrometry of the gas chromatograph is 950/ of the total amount of the components having a molecular weight of 314 to 320. The above is not particularly limited, and those skilled in the art can be used. When the content of the thiolated material of the hydrolyzate is determined according to the mass spectrometer mass spectrometry, the content of the component having a molecular weight of 3 20 is not more than 95% of the total amount of the components having a molecular weight of 314 to 3 20, or according to the ultraviolet absorbing luminosity. When the maximum absorbance A in the region of _ 254 nm or more is greater than 0.15, the obtained acrylic polymerization may be hindered due to low light resistance or application to an acrylic active energy ray-curable adhesive/adhesive. The polymerization of the substance does not achieve the effects of the present invention. In the component (A), the absorbance in the region of 254 nm or more according to the ultraviolet absorption spectrophotometry is mainly a peak associated with a carbon-carbon unsaturated bond. This value means that the number of unsaturated bonds in the molecule increases. Further, when the amount of impurities having coloration is increased, the value is increased. Since the carbon-carbon unsaturated bond is easily oxidized by ultraviolet rays, it may become a cause of deterioration of the color tone of the adhesive or brittleness of 201033291. Further, the carbon-carbon unsaturated bond is a major cause of polymerization inhibition in radical polymerization. Therefore, the absorbance value must be kept low. In addition, the methylated product of the hydrolyzate has a molecular weight of 32 Å, and the resin acid component derived from the rosin produced by hydrolysis is methylated, and the unsaturated bond in the molecule is completely hydrogenated. By. The methylated product of the hydrolyzate has a molecular weight of 314, and corresponds to a carbon-carbon unsaturated bond in the knives. Therefore, the content of the component having a molecular weight of 32 Å is 95% or more of the total amount of the components having a molecular weight of 314 to 320, which means that the component having a carbon-carbon unsaturated bond contained in the component (A) is extremely small. The component (A) 'is usually reacted with rosin (hereinafter referred to as component (al)) and alcohol (b) (hereinafter referred to as component), wherein the rosin (al) system: four The methylated product of rosin acid and tetrahydropalmolic acid is 95% or more of the total of the components having a molecular weight of 314 to 32 () according to the content of the component having a molecular weight of 32 测定 measured by mass spectrometry. . The rosin type (a2) (hereinafter referred to as the component (a2)) may be reacted with the component (b), wherein the rosin (a2) system: the methylation treatment is determined according to the mass spectrometry of the gas chromatograph. The content of the component having a molecular weight of 32 , is less than 95% of the total amount of the components having a molecular weight of 3 14 to 320, and then, by hydrogenation or the like, the methylated product of the hydrolyzate is analyzed according to the mass spectrometer of the gas chromatograph. The content of the component of the measured molecular weight 320 is 95% or more of the total amount of the components having a molecular weight of 3 14 to 320. As the component (al), the content of the component having a molecular weight of 32 测定 measured by gas chromatograph mass spectrometry as described above is a total amount of components of 7 201033291 sub-quantity 3 14 to 3 20 . When 95% or more of the rosin is used, it is not particularly limited, and those skilled in the art can be used. For example, the component (a 1) can also be used alone as tetraterpine abietic acid. Further, it may be prepared by mixing a resin acid component such as rosin acid with tetrakis abietic acid. Further, the component (a2) may be hydrogenated by a method described later to obtain a total of components having a molecular weight of 314 to 320 in accordance with the content of the component of the molecular weight of 320 in the gas chromatograph mass analysis. More than 95% of the amount. The tetrahydroabietic acid lanthanide can be obtained, for example, by the method described in Journal of Organic Chemistry 31, 4128 (1966), Journal of Organic Chemistry 34, 1550 (1969). Examples of the component (a2) include natural rosins such as wood rosin, tall ruin, and rubber rosin, and disproportionated rosin and hydrogenated rosin other than the component (a1). Specific examples of the component (b) used for producing the adhesive of the present invention include: a methoxyl such as n-octanol, 2-ethylhexanol, decyl alcohol or lauryl alcohol; ethylene glycol; Diols such as diethylene glycol, propylene glycol, neopentyl glycol, cycloheximide dimethanol; triols such as glycerin, trimethylolethane, trimethylolpropane; neopentyl alcohol, diglycerin, etc. a tetrahydric alcohol; a hexahydric alcohol such as dipentaerythritol. These may be used alone or in combination of two or more. Further, as the component (8)', an epoxy group (tetra) or a dehydrin can be used. In the above, the softening point of the reaction product of the obtained component (8), component (a2), and knife (b) can be set to a desired temperature, and tetra70 alcohol and/or triol are preferably used. Further, the use of the component (10) or the component (10) and the formation of 201033291 (b) can be determined, for example, according to the target acid value and the value of the obtained reaction product. It is generally preferred to set the molar ratio (〇h/c〇〇h) of the carboxylic acid group in the component (4)) or the component (10) to the hydroxyl group of the component (b) to about 0.5 to 2. The component (A) can be obtained by esterifying the component (al) with the component (b). Further, the component (A) can also be obtained by hydrogenating the component (a2) with the component (1?) and then hydrogenating it. The acetification reaction can be carried out by a well-known vinegar method. Specifically, the system is 纟l50~300. Under the high temperature conditions of the left and right sides, the generated water is removed while being removed from the system. When the air is mixed into the esterification reaction, the esterified product is likely to be colored. The reaction is preferably carried out under an inert gas such as nitrogen or helium or argon. Further, in order to shorten the reaction time, an esterification catalyst can also be used in the esterification reaction. As the esterification catalyst, an acid catalyst, an alkali metal hydroxide, a metal oxide or the like can be used. Examples of the acid catalyst include acetic acid and p-toluenesulfonic acid. The hydroxide of the metal test may be exemplified by hydrogen peroxide or the like. Examples of the metal oxyhydroxide include oxidation #5, magnesium oxide, and the like. The reaction product obtained by esterification reaction of the component (a2) with the component (b) or the hydrogenation of (a2) can be carried out by a known method. In the following, a reaction product or a component (a2) obtained by acetating a knife (a2) and a portion (b) may be referred to as a hydrogenation target. The hydrogenation is carried out, for example, by heating under hydrogen pressure of usually 1 to 25 MPa, preferably 5 to 20 MPa in the presence of a hydrogenation catalyst, for about 0.5 to 7 hours, preferably 1 to 5 J. get on. As the hydrogenation catalyst, various well-known ones such as a supported catalyst, a metal powder, and an iodide can be used. As the supported catalyst, 9 201033291 palladium carbon ruthenium carbon, ruthenium carbon, surface carbon, and the like can be mentioned. Examples of the metal powder include platinum, platinum, and the like. Examples of the broken material include broken or broken iron. Among these, in terms of hydrogenation efficiency (good hydrogenation rate and short hydrogenation time), it is preferred to use a catalyst, a ruthenium or a ruthenium catalyst. The amount of the hydrogenation catalyst used is preferably from about 1 to about 5 parts by weight based on (10) parts by weight of the hydrogenated object. Further, the hydrogenation temperature is from 100 to 300. (The left and right sides are preferably 150 290 C. Further, the hydrogenation may be carried out in a state in which the rosin is dissolved in a solvent as necessary. The solvent to be used is not particularly limited as long as it is inert to the reaction and is a raw material or a product. For the solvent, for example, one or two or more kinds of cyclohexane, n-hexane, n-heptane decahydronaphthalene, tetrahydroanthracene, and bismuth can be used. It is usually used in the form of a solid content of 10% by weight or more based on the raw material resin, and is preferably in the range of 10% by weight to 7% by weight. Further, hydrogenated rosin is hydrogenated under ordinary hydrogenation conditions. In the case of the ester, the methylated product of the hydrolyzate is increased to about 2% by weight of the total amount of the components having a molecular weight of 314 to 320 in accordance with the content of the component of the molecular weight of 320 determined by mass spectrometry. Therefore, it is necessary to repeat hydrogenation, increase the amount of catalyst used, select an appropriate catalyst type to increase the hydrogenation temperature, etc. The softening point of the obtained component (A) is thus performed (ring and ball method). Usually, it is preferably set to about 50 to 120 ° C. By setting the softening point to 5 〇 c > c or more 'because the treatment of the adhesive is easy, it is preferable. Further, by the component (A) The color tone of the present invention is set to 300 Hazen (Jis K 0071-1) and 201033291, which is colorless and transparent, and can be suitably used for optical member applications and electrical materials that emphasize color tone. The adhesive of the present invention contains the aforementioned component (A). However, various additives such as an antioxidant may be contained as necessary. The adhesive/adhesive composition of the present invention contains the above-mentioned adhesive. The adhesive/adhesive composition is not particularly limited, and may be mentioned. For example, an acrylic adhesive/adhesive composition, a styrene-conjugated dilute block copolymer adhesive composition, a vinyl hot melt adhesive composition, etc. The acrylic adhesive/adhesive composition of the present invention The material is at least the above-mentioned binder and acrylic polymer. The acrylic monomer used for obtaining the acrylic polymer can be variously provided in accordance with the acrylic adhesive/adhesive composition. The composition is appropriately determined. The acrylic monomer may be exemplified by various acrylates and/or mercapto acrylates (hereinafter referred to as (fluorenyl) acrylates. Specific examples thereof include: Methyl acrylate, (meth) φ ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. and can be in the aforementioned (meth) acrylate Also used as: (fluorenyl) acrylic acid, (meth)acrylic acid propyl acrylate, (meth)acrylic acid 2-hydroxyethyl ester, N-hydroxymethyl (meth) acrylamide, etc. as cross-linking acrylic acid The monomer may be used, and if necessary, other copolymerizable monomers such as vinyl acetate, styrene, or the like may be used in combination without impairing the adhesive properties of the (meth) acrylate polymer. Further, a polymerizable oligomer having an olefinic double bond obtained by polymerizing at least one of the above monomers can also be used as the acrylic acid. 201033291 The polymerization method of the above-mentioned propylene-based monomer is not particularly limited, and a well-known method such as '()) polymerization or dispersion polymerization emulsion polymerization can be used. Usually, you can use: benzoyl peroxide, peroxide month
桂醯、偶氮雙異丁腈、過硫酸鉀、過硫酸銨等的熱聚合引 發劑作為聚合？丨發劑來進行熱聚合4，亦可使用苯偶 姻、苯偶姻甲基越、二苯基_等光聚合引發劑並藉由照 射紫外線來聚合。而且’能夠㈣地選擇電子射線照射、 過硫酸鉀等過硫酸鹽與三級胺、硫脲等組合之氧化還原引 發系統等。在溶液聚合中之溶劑沒有特別限制能夠使用 通常聚口所使用之眾所周知的溶劑。特別是溶劑型丙烯酸 系聚合物的情形中，能夠按照用途而選擇溶劑。具體上， 可舉出甲苯、乙酸乙酯等。在分散聚合中之分散劑沒有特 另J限制，能夠使用眾所周知者。又在乳化聚合中之乳化 劑係沒有特別限制，能夠使用眾所周知的陰離子系乳化 劑、非離子系乳化劑等通常乳化聚合所使用者。 在本發明的丙烯酸系黏著劑/接著劑組成物中之賦黏 劑的使用量，係相對於i00重量份之丙烯酸系單體以2 40重量份左右的範圍為佳。以設為5〜2〇重量份的範 圍為特佳。藉由設為2〜4〇重量份的範圍，因為除了能夠 得到強力的黏接力之外，膠黏亦變為良好，而較佳。 依·照前述聚合法所得到的丙烯酸系聚合物的分子 量/、要是作為丙烯酸系聚合物組成物而具有充分的凝集 力’則沒有特別限制，通常，在溶劑型丙烯酸系聚合物的 情形中’為了具有充分的凝集力，以將重量平均分子量（依 12 201033291 照凝膠滲透層析法之聚苯乙烯換算值）設為15萬以上為 佳。 … 而且，藉由在所得到的丙烯酸系聚合物組成物中添加 交聯劑’亦能夠進—步提升凝集力、耐熱性。作為交聯劑， 可舉出：聚異氰酸酯化合物、聚胺化合物、三聚氰胺樹脂、 脲樹脂、環氧樹脂等。該等交聯劑之中，以使用聚異氰酸 酯化合物為特佳。聚異氰酸酯化合物的具體例，可舉出： 1,6-六亞F二異氰酸酯、四亞尹二異氛酸酯異佛爾酮二 異氰酸醋、苯二甲基二異氰酸醋、子苯二異氰酸醋、4,4_ 二苯基甲燒二異氰酸醋等。而且，本發明的丙稀酸系黏著 劑/接著劑組成物可按照必要而適當地使用填料抗氧化 劑紫外線吸收劑等。又，本發明的丙稀酸系黏著劑/接 著劑組成物在不脫離本發明之目的之範圍内，亦可並用各 種眾所周知的賦黏劑。 本發明的丙烯酸系活性能量射線硬化型黏著劑/接著 劑組成物，係至少含有前述賦黏劑及作為前述丙烯酸系聚 β物的原料之單體。而且’在該丙稀酸系活性能量射線硬 化型黏著劑/接著劑組成物中，亦可按照必要而添加交聯 劑等在本發明的丙烯酸系活性能量射線硬化型黏著劑/ 接著劑組成物中之成分⑷的使用量，係相對於1〇〇重量 份丙烯酸系單體，以θ 、< 以β又為2〜40重量份左右的範圍為佳， 以設為5〜2〇重量份的範圍為特佳。藉由設為2〜40重量 份的範圍’因為除了能夠得到更強而有力的黏接力之外， 膠黏性亦變為良好，而較佳。 13 201033291 該丙烯酸系活性能量射線硬化型黏著劑/接著劑組成 物’能夠藉由紫外線或電子射線等活性能量線使其硬化。 藉由硬化所得到的丙稀酸系聚合物之重量平均分子量係 通常為50000左右以上。 而且，在該丙烯酸系活性能量射線硬化型黏著劑/接 著劑組成物中，在不會對黏/接著性能帶來不良影響的範 圍内’亦能夠使其適當地含有填料、可塑劑、增黏劑、消 鲁’包劑、抗氧化劑、紫外線吸收劑、耐水化劑、造膜助劑、 防腐劑、防鏽劑、顏料、染料等各種眾所周知的添加劑。 本發明的苯乙烯-共軛二烯系嵌段共聚物黏著劑組成 物，係調配前述賦黏劑、苯乙烯-共軛二烯系嵌段共聚物 及油劑而成者。 所謂的苯乙烯-共軛二烯系嵌段共聚物，係依照使用 目的而適當地選擇苯乙烯、甲基苯乙烯等的苯乙烯類與丁 一烯、異戊二烯等的共輛二烯類，並共聚合而成之嵌段共 ®聚物。通常，苯乙烯類/共輛二烯類的重量比，係10/90 〜50/50。作為此種嵌段共聚物的較佳具體例，可舉出例 如：苯乙烯類（S)/丁二烯（B)的重量比為10/90〜5〇/5〇的 範圍之SBS型嵌段共聚物、苯乙烯類（s)/異戊二烯⑴的重 量比為10/90〜30/70的範圍之SIS型嵌段共聚物等。又， 在本發明的苯乙烯-共軛二烯系嵌段共聚物中，亦可含有 將前述嵌段共聚物的共軛二烯成分加以氫化而成者。作為 氫化而成者之具體例，可舉出所謂SEBS型嵌段共聚物、 SEPS型嵌段共聚物等。 201033291 又，作為油劑，可舉出環烷系油劑、石蠟系油劑或芳 香族系油劑等的可塑化油劑。從凝集力的降低較少的觀點 而言，以環烷系油劑、石蠟系油劑為佳。具體上，可舉出 環烷系加工油劑、石蠟系加工油劑、液狀聚丁烯等。 各成分的使用量，係例如相對於100重量份之笨乙烯 -共軛二烯系嵌段共聚物，而含有15〜21〇重量份左右的 賦黏劑及4〜200重量份左右的油劑。 鲁 賦黏劑少& 15重量份時，黏著劑組成物的溶融黏度 會有變高的可能性，大於210重量份時，會有保持力不充 分的傾向。又，油劑少於4重量份時，黏著劑組成物的溶 融黏度變高，大於200重量份會有保持力不充分的情況。 又，在本發明的苯乙烯-共梃二烯系嵌段共聚物黏著 劑組成物中，可進而按照必要而添加填料、抗氧化劑等添 加劑。 本發明的乙稀系熱溶接著劑組成物，能夠藉由在乙稀 Q 系共聚物中調配前述賦黏劑而得到。 所謂的乙烯系共聚物，係乙烯及能夠與乙烯共聚合的 單競之共聚物’敗》夠使用先前在熱溶接著劑所使用者。所 謂的能夠與乙稀共聚合的單體，可舉出乙酸乙烯酿等。乙 酸乙烯酯的含量’係通常為20〜45重量。/。左右。又，八 子量係以溶融指數（190C、負荷2160克、1〇分鐘）為 10〜400克/10分鐘左右者為佳。 作為蝶’ Bb夠使用在熱溶接著劑中所使用者。壤的具 體例可舉出：石蠟、微晶蠟等的石油系蠟、費托壤 201033291 (Fisher-Tropsch wax)、低分子量聚乙稀蝶等的合成蠟。 本發明的乙烯系熱熔接著劑，係相對於1〇〇重量份之 乙烯系共聚物，而含有50〜15〇重量份左右的前述^劑 及10 100重量伤左右的壤而成者。藉由賦黏劑為^重 量份以上’能夠得到充分的黏接力，又，大於15〇重量份 時，會有無法得到充分的保持力之情形。又蠟少於丄〇 重量份時，所得到的接著劑組成物的溶融黏度變得太高， _又，大於100重量份時，會有無法得到充分的保持力之情 形。又，在本發明的乙烯系熱熔接著劑中，亦可進而按照 必要而添加填料、抗氧化劑等添加劑。 [實施例] 以下’藉由實施例更具體地說明本發明。但是，本發 明未限定於該等實施例。又，實施例中，「％」及「份」 只要未事先告知，則係意味著「重量。/。」、「重量份」。 φ 製造例1 (溶劑型丙烯酸系聚合物的製造） 在具備有攪拌裝置、冷卻管、2座滴加漏斗及氮氣導 入管的反應裝置中，添加5〇份乙酸乙酯後，在氮氣流下 升溫至系統内溫度為約7 5。隨後，從預先混合添加有 48.5份丙烯酸丁酯、48 5份丙稀酸2-乙基己酯、3份丙烯 酸之滴加漏斗及添加有〇〗份偶氮雙異丁腈及30份乙酸 乙酯之滴加漏斗，以大約2小時滴加至系統内’進而保持 在同溫度5小時來使其完成聚合反應。追加乙睃乙醋而調 整固體成分為約50〇/〇,來得到含有丙稀酸系聚合物之組成 201033291 物。 製造例2 (松香酯1的製造） (第1次氫化反應） 在1公升之高壓签中添加200克中國加氫松香、3克 5%鈀氧化鋁粉末（N.E CHEMCAT公司製）及200克環己 烷’並除去系統内的氧後，將系統内加壓至6MPa後，升 溫至200°C。溫度到達後，將系統内再加壓，並保持於 9MPa ’來進行加氫反應4小時，將溶劑過濾分開後，在 減壓下除去環己烷’來得到1 89克酸價為1 74、軟化點為 79°C的加氫松香。 (酯化反應） 隨後，在具備有攪拌裝置、冷卻管及氮氣導入管之反 應裝置’添加180克加氫松香，並溶融至2〇〇°c後，添加 21克甘油並在280°C使其反應1 〇小時《得到175克軟化 點為90°C、酸價為11的加氫松香酯。 〇 (第2次氫化反應） 在1公升之高壓釜中添加170克所得到的加氫松香 酯、1克5%鈀碳（含水率為50%)、170克環己烷，並除去 系統内的氧後’將系統内加壓至6MPa後，升溫至200。〇。 溫度到達後’將系統内再加壓’並保持於9MPa，來進行 加氫反應4小時’將溶劑過濾分開後，在減壓下除去環己 烷’來得到164克的酸價為1〇、軟化點為92〇c、羥值為 18的松香醋1。水解物的甲基化處理物依照氣體層析儀質 量分析所測定的分子量320的成分的含量，為分子量314 17 201033291 〜320的成分的合計量之刚％，色調為細驗心）。 又，軟化點、水解物的甲基化處理物依照氣體層析儀質量 分析所測定的分子量320的成分的含量、色調、酸價，係 依照後述的方法測定。以下，該等值係藉由同樣的方法所 測定的值。 製造例3 (松香醋2的製造） (第1次氫化反應） _ 除了將5%把氧化銘粉末的使用量變更為2克及將加 氫反應時間變更為3小時以外，與製造例2同樣地進行而 得到191克酸價為175、軟化點為79t的松香。 (酯化反應） 除了使用180克在第1次氫化中所得到之酸價為 175、軟化點為79°C的松香以外，與製造例2同樣地進行 而得到175克軟化點為91°C、酸價為12的松香酯。 (第2次氫化反應） ® 除了使用17 0克在酯化中所得到之軟化點為9丨、 酸價為12的松香酯以外，與製造例2同樣地進行而得到 克酸價為12、軟化點為9yc、羥值為is的松香酯2β 水解物的甲基化處理物依照氣體層析儀質量分析所測定 的分子量320的成分的含量，為分子量314〜320的成分 的合計量之99%，色調為200H。 製造例4 (松香酯3的製造） (第1次氫化反應） 除了將5%鈀氧化鋁粉末的使用量變更為1.5克以 18 201033291 外，與製造例3同樣地進行而得到1 94克酸價為1 75、軟 化點為78°C的松香。 (酯化反應） 除了使用180克在第1次氫化中所得到之酸價為 175、軟化點為78°C的松香以外，與製造例2同樣地進行 而得到175克軟化點為90°C、酸價為1 〇的松香醋。 (第2次氫化反應） ❹ 除了使用170克在酯化中所得到之軟化點為9〇»c、 酸價為10的松香酯以外’與製造例2同樣地進行而得到 162克酸價為9、軟化點為91°C、羥值為15的松香酯3。 水解物的曱基化處理物依照氣體層析儀質量分析所測定 的分子量320的成分的含量，為分子量314〜320的成分 的合計量之98%，色調為200H。 製造例5 (松香酯4的製造） (第1次氫化反應） Q 在1公升之高壓釜中添加200克中國加氫松香、4克 5%鈀碳（50%含水、N_E CHEMCAT公司製）及200克環 己烷，並除去系統内的氧後，將系統内加壓至6MPa後， 升溫至200°C。溫度到達後，將系統内再加壓，並保持於 9MPa ’來進行加氫反應3小時，將溶劑過濾分開後，在 減壓下除去環己烷，來得到19〇克酸價為172、軟化點為 79°C的加氫松香。 (酯化反應） 隨後，在具備有攪拌裝置、冷卻管及氮氣導入管之反 19 201033291 應裝置中，添加180松香，並溶熔至2〇〇。〇後，添加2 i 克甘油並在280 C使其反應1 〇小時。得到丨72克軟化點 為90°C、酸價為9的松香醋。 (第2次氫化反應） 在1公升之高壓釜中添加17〇克所得到的松香酯、i 克5%把碳（含水率為50〇/〇) 、17〇克環己烷，並除去系 統内的氧後’將系統内加壓至6MPa後，升溫至2〇0°c。 鲁溫度到達後’將系統内再加壓，並保持於9MPa，來進行 加氫反應4小時，將溶劑過濾分開後，在減壓下除去環己 烷’來得到163克的酸價為8、軟化點為91°C、經值為 14的松香酯4。水解物的甲基化處理物依照氣體層析儀質 量分析所測定的分子量320的成分的含量，為分子量314 〜320的成分的合計量之96%，色調為1 50H。 製造例6 (松香酯5的製造） (第1次氫化反應） Ο 除了將5%鈀碳的使用量變更為2克以外，與製造例 5同樣地進行而得到190克酸價為170、軟化點為80。(：的 松香。 (酯化反應） 除了使用180克在第1次氫化中所得到之酸價為 170、軟化點為80°C的松香以外，與製造例5同樣地進行 而得到172克軟化點為90°C、酸價為8的松香酯。 (第2次氫化反應） 除了使用170克在酯化中所得到之軟化點為90°C、 20 201033291 酸價為8的松香醋以外’與製造例5同樣地進行而得到 161克酸價為7、軟化點為90°C、羥值為16的松香醋5。 水解物的甲基化處理物依照氣體層析儀質量分析所測定 的分子量320的成分的含量，為分子量314〜320的成分 的合計量之94%，色調為150H。 製造例7 (松香酯6的製造） 在具備有攪拌裝置、冷卻管及氮氣導入管的反應裝置 ❿中，添加300克松香，並升溫熔融至2〇(rc後，添加33 克甘油並在2 8 0 C使其反應1 2小時。得到2 9 9克軟化點 為93°C、酸價為6的松香酯。 在1公升之高壓爸中添加250克所得到的松香酯，7 5 克5%鈀碳（含水率50%)，並除去系統内的氧後，將系 統内加壓至6MPa後’升溫至24〇。(：。溫度到達後，將系 統内再加壓，並保持於9MPa，來進行加氫反應3小時， 將溶劑過濾分開後，得到163克酸價為6、軟化點為88 ® C、羥值為14的松香酯6。水解物的甲基化處理物依照 氣體層析儀質量分析所測定.的分子量32〇的成分的含 量’為分子量314〜3 20的成分的合計量之6〇%，色調為 200H。 製造例8 (松香酯7的製造） 除了將5°/❶纪氧化鋁粉末的使用量變更為2克以外， 與製造例7同樣地進行而得到164克酸價為6、軟化點為 90C、經值為12的松香酯7。水解物的甲基化處理物依 照氣體層析儀質量分析所測定的分子量320的成分的含 21 201033291 量，為分子量314〜3 20的成分的合計量之2〇%，色調為 300H。 (軟化點） 依照JIS K 253 1的環球法測定。 (水解物的甲基化處理物依照氣體層析儀質量分析所測 疋的分子量320的成分的含量之定量） 將在製造例2〜8所得到的松香酯加以水解（在正己 φ醇中添加氫氧化鉀，並使其回流反應2小時後，使用鹽酸 而成為中性，將所得到的樹脂酸提供分析）後，使用以下 的氣體層析儀質量分析裝置實施定量。 測定係將0.1克在製造例所得到的松香酯溶解於2 〇 克正己醇，並將0.1克該溶液與0.4克管柱上（〇n c〇iumn) 曱基化劑（氫氧化苯基三甲銨（pTHA)的〇 2莫耳甲醇溶 液、GL Sciences(股））均勻混合，並將i微升注入氣體層 析儀質量分析（GC/MS)，來進行測定。測定相對於分子量 ® 314〜320的成分的合計尖峰面積之分子量32〇的成分之 尖峰面積比，並將其設為分子量32〇的成分之含量。 使用裝置Is a thermal polymerization initiator such as laurel, azobisisobutyronitrile, potassium persulfate or ammonium persulfate as a polymerization? The hair styling agent is used for thermal polymerization 4, and a photopolymerization initiator such as benzoin, benzoin methyl group or diphenyl group may be used and polymerized by irradiation of ultraviolet rays. Further, a redox initiation system in which a persulfate such as electron beam irradiation or potassium persulfate is combined with a tertiary amine or thiourea or the like can be selected. The solvent in the solution polymerization is not particularly limited, and a well-known solvent which is usually used for the polymerization can be used. In particular, in the case of a solvent-based acrylic polymer, a solvent can be selected according to the use. Specifically, toluene, ethyl acetate, etc. are mentioned. The dispersing agent in the dispersion polymerization is not particularly limited, and those skilled in the art can be used. Further, the emulsifier in the emulsion polymerization is not particularly limited, and a user of a general emulsion polymerization such as a well-known anionic emulsifier or a nonionic emulsifier can be used. The amount of the binder used in the acrylic pressure-sensitive adhesive/adhesive composition of the present invention is preferably in the range of about 2 to 40 parts by weight based on 100 parts by weight of the acrylic monomer. It is particularly preferable to set it as a range of 5 to 2 parts by weight. By setting it as a range of 2 to 4 parts by weight, in addition to being able to obtain a strong adhesive force, the adhesiveness becomes good, and it is preferable. The molecular weight of the acrylic polymer obtained by the above polymerization method is not particularly limited as long as it has sufficient cohesive force as the acrylic polymer composition. Usually, in the case of a solvent-based acrylic polymer, In order to have sufficient cohesive force, it is preferred to set the weight average molecular weight (in terms of polystyrene conversion value by gel permeation chromatography according to 12 201033291) to 150,000 or more. Further, by adding a crosslinking agent ' to the obtained acrylic polymer composition, the cohesive force and heat resistance can be further improved. Examples of the crosslinking agent include a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, and an epoxy resin. Among these crosslinking agents, a polyisocyanate compound is particularly preferred. Specific examples of the polyisocyanate compound include 1,6-hexamethylene F diisocyanate, tetraamethylene diiso-succinate isophorone diisocyanate, benzodimethylisocyanate, and benzoic acid. Benzene diisocyanate vinegar, 4,4_ diphenyl ketone diisocyanate vinegar, and the like. Further, the acrylic acid-based adhesive/adhesive composition of the present invention may suitably use a filler antioxidant ultraviolet absorber or the like as necessary. Further, the acrylic acid-based adhesive/adhesive composition of the present invention may be used in combination with various well-known adhesives without departing from the object of the present invention. The acrylic active energy ray-curable adhesive/adhesive composition of the present invention contains at least the above-mentioned tackifier and a monomer which is a raw material of the acrylic polystyrene. Further, in the acrylic acid-based active energy ray-curable adhesive/adhesive composition, a crosslinking agent or the like may be added as necessary in the acrylic active energy ray-curable adhesive/adhesive composition of the present invention. The amount of the component (4) to be used is preferably in the range of θ and < β is about 2 to 40 parts by weight based on 1 part by weight of the acrylic monomer, and is preferably 5 to 2 parts by weight. The range is particularly good. By setting it as a range of 2 to 40 parts by weight, the adhesiveness is also good, and it is preferable, in addition to being able to obtain a stronger and stronger adhesive force. 13 201033291 The acrylic active energy ray-curable adhesive/adhesive composition ' can be cured by an active energy ray such as ultraviolet rays or electron beams. The weight average molecular weight of the acrylic polymer obtained by curing is usually about 50,000 or more. Further, in the acrylic active energy ray-curable adhesive/adhesive composition, it is possible to appropriately contain a filler, a plasticizer, and a viscosity in a range that does not adversely affect the adhesion/adhesive performance. Various known additives such as agent, Xiaolu's package, antioxidant, ultraviolet absorber, water resistance agent, film forming aid, preservative, rust inhibitor, pigment, dye, etc. The styrene-conjugated diene block copolymer adhesive composition of the present invention is prepared by blending the above-mentioned tackifier, styrene-conjugated diene block copolymer and oil agent. The styrene-conjugated diene-based block copolymer is suitably selected from the group consisting of styrene such as styrene or methyl styrene and a total of diene such as butylene or isoprene depending on the purpose of use. Class, and copolymerized block copolymers. Usually, the weight ratio of the styrene/co-diene is 10/90 to 50/50. A preferred example of such a block copolymer is, for example, an SBS type in which the weight ratio of styrene (S) / butadiene (B) is 10/90 to 5 Å / 5 Torr. The SIS type block copolymer having a weight ratio of the segment copolymer, styrene (s) / isoprene (1) of 10/90 to 30/70, or the like. Further, the styrene-conjugated diene block copolymer of the present invention may contain a hydrogenated conjugated diene component of the block copolymer. Specific examples of the hydrogenation product include a SEBS type block copolymer and a SEPS type block copolymer. Further, as the oil agent, a plasticizer such as a naphthenic oil, a paraffin oil or an aromatic oil may be mentioned. From the viewpoint of less reduction in cohesive force, a naphthenic oil or a paraffinic oil is preferred. Specific examples thereof include a naphthenic processing oil, a paraffin-based processing oil, and a liquid polybutene. The amount of each component used is, for example, about 15 to 21 parts by weight of the binder and about 4 to 200 parts by weight of the oil agent per 100 parts by weight of the stupid ethylene-conjugated diene block copolymer. . When the amount of the adhesive is less than 15 parts by weight, the melt viscosity of the adhesive composition may become high, and when it is more than 210 parts by weight, the holding strength tends to be insufficient. Further, when the amount of the oil agent is less than 4 parts by weight, the melt viscosity of the adhesive composition becomes high, and if it is more than 200 parts by weight, the holding strength may be insufficient. Further, in the styrene-conjugated diene-based block copolymer adhesive composition of the present invention, an additive such as a filler or an antioxidant may be further added as necessary. The ethylene-based hot-melt adhesive composition of the present invention can be obtained by blending the above-mentioned tackifier with an ethylene Q-based copolymer. The so-called ethylene-based copolymer, which is a copolymer of ethylene and a copolymerizable copolymer with ethylene, is sufficient for use as a user of a hot-melt adhesive. The monomer which can be copolymerized with ethylene is exemplified by vinyl acetate. The content of vinyl acetate is usually 20 to 45 parts by weight. /. about. Further, the eight-quantity is preferably a melt index (190 C, a load of 2,160 g, 1 minute) of about 10 to 400 g/10 minutes. The butterfly 'Bb is sufficient for use as a user in a hot melt adhesive. Specific examples of the soil include petroleum waxes such as paraffin wax and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax and low molecular weight polyethylene butterfly. The ethylene-based hot-melt adhesive of the present invention contains about 50 to 15 parts by weight of the above-mentioned agent and 10 to 100 parts by weight of the soil of about 1 part by weight of the ethylene-based copolymer. A sufficient adhesive force can be obtained by using the adhesive as a part by weight or more, and when it is more than 15 parts by weight, a sufficient holding force may not be obtained. When the wax is less than 丄〇 by weight, the melt viscosity of the obtained adhesive composition becomes too high, and when it is more than 100 parts by weight, sufficient retaining force may not be obtained. Further, in the ethylene-based hot melt adhesive of the present invention, an additive such as a filler or an antioxidant may be further added as necessary. [Examples] Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited to the embodiments. Further, in the examples, "%" and "parts" mean "weight./." and "parts by weight" unless otherwise notified. φ Production Example 1 (Production of Solvent-Based Acrylic Polymer) In a reaction apparatus equipped with a stirring device, a cooling tube, two dropping funnels, and a nitrogen introduction tube, 5 parts of ethyl acetate was added, and then the temperature was raised under a nitrogen stream. The temperature in the system is about 75. Subsequently, 48.5 parts of butyl acrylate, 48 5 parts of 2-ethylhexyl acrylate, 3 parts of acrylic acid addition funnel, and azo azobisisobutyronitrile and 30 parts of acetic acid were added from the premix. The ester was added dropwise to the funnel and added dropwise to the system in about 2 hours, and then kept at the same temperature for 5 hours to complete the polymerization. The ethyl acetate was added to adjust the solid content to about 50 Å/〇 to obtain a composition containing an acrylic polymer 201033291. Production Example 2 (Production of rosin ester 1) (1st hydrogenation reaction) 200 g of China hydrogenated rosin, 3 g of 5% palladium alumina powder (manufactured by NE CHEMCAT Co., Ltd.), and 200 g of a ring were added to a 1 liter high pressure hand. After hexane was removed and the oxygen in the system was removed, the inside of the system was pressurized to 6 MPa, and then the temperature was raised to 200 °C. After the temperature reached, the system was repressurized and maintained at 9 MPa' for hydrogenation reaction for 4 hours. After separating the solvent by filtration, the cyclohexane was removed under reduced pressure to obtain 1 89 g of an acid value of 1 74. The hydrogenated rosin having a softening point of 79 °C. (Esterification reaction) Subsequently, after adding 180 g of hydrogenated rosin to a reaction apparatus equipped with a stirring device, a cooling tube, and a nitrogen introduction tube, and after melting to 2 ° C, 21 g of glycerin was added and the mixture was added at 280 ° C. The reaction was carried out for 1 hour to obtain 175 g of a hydrogenated rosin ester having a softening point of 90 ° C and an acid value of 11. 〇 (2nd hydrogenation reaction) 170 g of the obtained hydrogenated rosin ester, 1 g of 5% palladium carbon (water content: 50%), 170 g of cyclohexane were added to a 1 liter autoclave, and the system was removed. After the oxygen was pressed into the system to 6 MPa, the temperature was raised to 200. Hey. After the temperature was reached, 'repressurize the system' and maintain it at 9 MPa to carry out the hydrogenation reaction for 4 hours. After the solvent was separated by filtration, the cyclohexane was removed under reduced pressure to obtain 164 g of an acid value of 1 Å. The rosin vinegar having a softening point of 92 〇c and a hydroxyl value of 18. The methylated product of the hydrolyzate is a component of the molecular weight of 320 measured by gas chromatograph mass spectrometry, and is a % of the total amount of the components having a molecular weight of 314 17 201033291 to 320, and the color tone is fineness. Further, the softening point and the methylated product of the hydrolyzate are measured in accordance with the method described later by the content, color tone, and acid value of the component of the molecular weight 320 measured by mass spectrometry. Hereinafter, the equivalent value is a value measured by the same method. Production Example 3 (Production of Rosin Vinegar 2) (First Hydrogenation Reaction) _ The same as Production Example 2 except that 5% of the amount of the oxidized powder was changed to 2 g and the hydrogenation reaction time was changed to 3 hours. The residue was subjected to 191 g of rosin having an acid value of 175 and a softening point of 79 t. (Esterification reaction) A 175 g softening point of 91 ° C was obtained in the same manner as in Production Example 2 except that 180 g of rosin having an acid value of 175 and a softening point of 79 ° C obtained in the first hydrogenation was used. A rosin ester having an acid value of 12. (2nd hydrogenation reaction) ® was obtained in the same manner as in Production Example 2 except that 170 g of a rosin ester having a softening point of 9 Å and an acid value of 12 obtained in the esterification was used. The methylated product of the rosin ester 2β hydrolyzate having a softening point of 9 μc and a hydroxyl value of is a content of the component of the molecular weight of 320 determined by mass spectrometry of the gas chromatograph, and is a total of 99 of the components having a molecular weight of 314 to 320. %, the hue is 200H. Production Example 4 (Production of rosin ester 3) (First hydrogenation reaction) The same procedure as in Production Example 3 was carried out except that the amount of use of 5% palladium alumina powder was changed to 1.5 g to 18 201033291. The rosin has a price of 1 75 and a softening point of 78 °C. (Esterification reaction) A 175 g softening point of 90 ° C was obtained in the same manner as in Production Example 2, except that 180 g of rosin having an acid value of 175 and a softening point of 78 ° C obtained in the first hydrogenation was used. A rosin vinegar with an acid price of 1 。. (2nd hydrogenation reaction) 162 In the same manner as in Production Example 2, except that 170 g of a rosin ester having a softening point of 9 〇»c and an acid value of 10 obtained in the esterification was used, 162 g of an acid value was obtained. 9. Rosin ester 3 having a softening point of 91 ° C and a hydroxyl value of 15. The content of the component of the molecular weight of 320 measured by mass spectrometry of the gas chromatograph was 98% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 200H. Production Example 5 (Production of rosin ester 4) (First hydrogenation reaction) Q 200 g of China hydrogenated rosin and 4 g of 5% palladium carbon (50% aqueous, manufactured by N_E CHEMCAT Co., Ltd.) were placed in a 1 liter autoclave. After 200 g of cyclohexane was removed and the oxygen in the system was removed, the system was pressurized to 6 MPa and then raised to 200 °C. After the temperature reached, the system was repressurized and maintained at 9 MPa' for hydrogenation reaction for 3 hours. After the solvent was separated by filtration, the cyclohexane was removed under reduced pressure to obtain 19 gram acid value of 172, softened. The point is 79 ° C hydrogenated rosin. (Esterification reaction) Subsequently, 180 rosin was added to the apparatus equipped with a stirring device, a cooling tube, and a nitrogen introduction tube, and melted to 2 Torr. After the hydrazine, 2 i g of glycerol was added and allowed to react at 280 C for 1 hr. 72 g of rosin vinegar having a softening point of 90 ° C and an acid value of 9 was obtained. (2nd hydrogenation reaction) 17 g of the obtained rosin ester, 1 g of carbon (water content: 50 〇 / 〇), 17 g of cyclohexane, and a removal system were added to a 1 liter autoclave. After the internal oxygen was pressed into the system to 6 MPa, the temperature was raised to 2 〇 0 °c. After the temperature of Lu is reached, the pressure in the system is repressurized and maintained at 9 MPa to carry out hydrogenation reaction for 4 hours. After the solvent is separated by filtration, the cyclohexane is removed under reduced pressure to obtain an acid value of 163 g. Rosin ester 4 having a softening point of 91 ° C and a pass value of 14. The methylated product of the hydrolyzate was subjected to a gas chromatograph mass analysis to determine the content of the component of the molecular weight of 320, and was 96% of the total amount of the components having a molecular weight of 314 to 320, and the color tone was 150H. Production Example 6 (Production of rosin ester 5) (First hydrogenation reaction) Ο In the same manner as in Production Example 5 except that the amount of use of 5% palladium carbon was changed to 2 g, 190 g of an acid value of 170 was obtained and softened. The point is 80. (Esterification reaction: 172 g softening was carried out in the same manner as in Production Example 5 except that 180 g of rosin having an acid value of 170 and a softening point of 80 ° C obtained in the first hydrogenation was used. A rosin ester having an acid value of 8 at 90 ° C. (2nd hydrogenation reaction) Except that 170 g of a rosin vinegar having a softening point of 90 ° C, 20 201033291 and an acid value of 8 obtained in the esterification is used. In the same manner as in Production Example 5, 161 g of rosin vinegar having an acid value of 7 and a softening point of 90 ° C and a hydroxyl value of 16 was obtained. The methylated product of the hydrolyzate was measured by mass spectrometry. The content of the component of the molecular weight of 320 is 94% of the total amount of the components having a molecular weight of 314 to 320, and the color tone is 150H. Production Example 7 (Production of Rosin Ester 6) A reaction apparatus including a stirring device, a cooling pipe, and a nitrogen gas introduction pipe In the crucible, add 300 g of rosin, and heat to melt to 2 〇 (rc, add 33 g of glycerol and react it at 280 C for 12 hours. Obtain a 2.9 9 g softening point of 93 ° C, and the acid value is 6 rosin ester. Add 250 grams of the obtained rosin ester to 7 liters of high pressure dad, 75 grams of 5% palladium on carbon ( After the moisture content is 50%), and the oxygen in the system is removed, the system is pressurized to 6 MPa and then 'heated to 24 〇. (: After the temperature is reached, the system is repressurized and kept at 9 MPa to add Hydrogen was reacted for 3 hours, and the solvent was separated by filtration to obtain 163 g of rosin ester 6 having an acid value of 6, a softening point of 88 ® C and a hydroxyl value of 14. The methylated product of the hydrolyzate was analyzed according to the mass spectrometer of the gas chromatograph. The content of the component having a molecular weight of 32 测定 measured was 6% by mass of the total amount of the components having a molecular weight of 314 to 3 20, and the color tone was 200H. Production Example 8 (Production of Rosin Ester 7) In addition to oxidation of 5°/❶ The amount of the aluminum powder used was changed to 2 g, and the same procedure as in Production Example 7 was carried out to obtain 164 g of rosin ester 7 having an acid value of 6, a softening point of 90 C and a pass length of 12. The methylated product of the hydrolyzate was The amount of the component of the molecular weight of 320 measured by the mass spectrometer of the gas chromatograph is 21 201033291, which is 2% by weight of the total of the components having a molecular weight of 314 to 3 20, and the color tone is 300 H. (Softening point) Global according to JIS K 253 1 Method determination (Methylation treatment of hydrolysate according to gas chromatograph quality analysis Quantification of the content of the component of the molecular weight of the enthalpy of the enthalpy 320. The rosin ester obtained in the production examples 2 to 8 was hydrolyzed (potassium hydroxide was added to n-hexanol and refluxed for 2 hours, and then hydrochloric acid was used. After neutralization, the obtained resin acid was subjected to analysis, and the quantitative analysis was carried out using the following gas chromatograph mass spectrometer. The measurement was carried out by dissolving 0.1 g of the rosin ester obtained in the production example in 2 g of n-hexanol, and 0.1 g of this solution was uniformly mixed with 0.4 g of 〇nc〇iumn thiolizing agent (pTHA 〇2 molar methanol solution, GL Sciences) i microliter injection gas chromatograph mass analysis (GC/MS) for the determination. The ratio of the peak area of the component having a molecular weight of 32 相对 to the total peak area of the components of the molecular weight of 314 to 320 was measured, and the content of the component having a molecular weight of 32 Å was determined. Using device
GC/MS:氣體層析儀Agilent 6890、質量分析計Agilent 5973、管柱 Advance-DS (色調） 依照JIS K 0071-3並以jjazen單位測定。 (酸價） 依照JIS K 0700之電位差滴定法測定。 22 201033291 (羥值） 依照JIS Κ 0700之電位差滴定法測定。 (吸光度） 將25毫克在製造例所得到的松香酯，精秤於25毫升 量瓶，並使用環己烷熔解後’定容至25毫升的刻線。使 用 UV 分光光度計（HITACHI u-3210 spectrophotometer )， 並藉由 使用容器長度為1公 分的石 英容器 ©來測定吸光度。讀取在254奈米以上的區域中最大的吸光 度。 實施例1 在80份製造例1所得到的溶劑型丙烯酸系聚合物中 添加在製造例2所得到之松香酯1的50%乙酸乙醋溶液， 並添加2.5份聚異氛酸醋系化合物（日本Polyurethane(股） 製、商品名「CORONATE」）作為交聯劑，來得到溶劑 型丙烯酸系黏著劑/接著劑組成物。使用旋轉型塗布器將 Φ 所得到的溶劑型丙烯酸系黏著劑/接著劑組成物以乾燥膜 厚度為30微米左右的方式塗布（塗布寬度25毫米）在厚 度為3 8微米的聚酯薄膜上’隨後’將該黏著劑/接著劑組 成物清漆中的溶劑風乾後，在1〇5。〇的循環風乾燥機中乾 燥5分鐘而製成試料膠黏帶，並在23°C、65%R.H.的條件 下熟化一星期’並實施後述的耐光性試驗。結果係如表2 所示。 (耐光性試驗） 在使用高壓水銀燈對該試料膠黏帶照射一定的累積 23 201033291 光量之前後，評價PROBE TACK (使用NS探針膠黏度測 定器（NICHIBAN(股）公司製），負荷100克/平方公分、停 留時間1秒）的變化。 實施例2〜4、比較例1〜3 除了將在實施例1中使用的松香酯如表1般改變以 外，與實施例1同樣地進行，製造試料膠黏帶，來實施耐 光性試驗。結果係如表2所示。 [表1] 松香酯 分子量320的成分含量 (%) 在254奈米以上的最大吸光度 (dm3/l · cm) 實施例1 松香酯1 100 0.06 實施例2 松香酯2 99 0.07 實施例3 松香酯3 98 0.07 實施例4 松香酯4 96 0.11 比較例1 松香酯5 94 0.19 比較例2 松香醋6 60 0.71 比較例3 松香酯7 20 1.4 ❿[表2] 财光性(探針膠黏度、g/5mm®) 照射水銀燈前 累積光量400J/cm2 累積光量l〇〇〇J/cm2 實施例1 520 500 460 實施例2 540 510 480 實施例3 500 480 450 實施例4 540 510 480 比較例1 490 440 240 比較例2 290 350 30 比較例3 490 30 10 24 201033291 實施例5 將製造例1所得到的溶劑型丙烯酸系聚合物在1051 循環風乾燥機中使其乾燥5小時。在24重量份所得到的 丙烯酸系聚合物中，混合25份丙烯酸2-乙基己酯、25份 丙烯酸丁酯、6份丙烯酸、20份製造例2所得到的松香酿 1，並添加 2.5 份聚異氟酸酯系化合物（日本 Polyurethane(股）製、商品名「CORONATE」）作為交聯劑， ❹及〇·2份DAROCUR 1173(CIBA Japan(股）公司製）作為光 引發劑’來製備性能量射線硬化型黏著劑組成物。 使用旋轉型塗布器將所得到的溶劑型丙烯酸系黏著 劑/接著劑組成物以乾燥膜厚度為30微米右右的方式塗 布（塗布寬度25毫米）在厚度為38微米的聚酯薄膜上， 並照射紫外線來得到試料膠黏帶。 (黏接力） 依照JIS Z 023 7的方法，使用2公斤的橡膝滾輪將上 _述試料膠黏帶以25毫米X125毫米之黏接面積壓黏在被黏 著物亦即聚乙烯板基材後，在2〇〇c放置24小時。隨後， 使用TENSILON拉力試驗機（萬能拉力試驗機）在2〇β(：以 剝離速度300毫米/分鐘進行18〇。剝離試驗，來測定寬 度每25毫米的黏接力（N/25毫米）^結果係如表3所示。 (定負荷剝離性） 使用2公斤的橡膠滾輪將上述試料膠黏帶以乃毫米X ⑽毫米之黏接面積壓黏在㈣著物亦即聚乙烯板基材 後’將2公斤的滾輪進行！次往復而貼合，心分鐘後， 25 201033291 如表3所示 比較例4 在膠黏帶端施加5〇克的負荷，並將聚乙烯板固定以使其 呈90。剝離，來測定在23。(：的環境氣氛中，每！小時的 剝離距離。測定在1小時以内全面剝離時的時 、 如表3所示。 結果係 除了在實施例5中未混合松香酯1以外，啟 同樣地進行，來得到試料膠黏帶。 、實施例 [表3]GC/MS: gas chromatograph Agilent 6890, mass spectrometer Agilent 5973, column Advance-DS (hue) according to JIS K 0071-3 and measured in jjazen units. (Acid value) Measured according to the potentiometric titration method of JIS K 0700. 22 201033291 (Hydroxyl value) Measured according to the potentiometric titration method of JIS Κ 0700. (Absorbance) 25 mg of the rosin ester obtained in the production example was weighed in a 25 ml volumetric flask and melted using cyclohexane to make up to 25 ml of the score line. The absorbance was measured using a UV spectrophotometer (HITACHI u-3210 spectrophotometer) and by using a quartz container of 1 cm in length. Read the maximum absorbance in the area above 254 nm. Example 1 To 80 parts of the solvent-type acrylic polymer obtained in Production Example 1, a 50% ethyl acetate solution of rosin ester 1 obtained in Production Example 2 was added, and 2.5 parts of a polyisophthalic acid-based compound ( A solvent-type acrylic pressure-sensitive adhesive/adhesive composition was obtained as a crosslinking agent by a Japanese Polyurethane Co., Ltd. product under the trade name "CORONATE". The solvent-type acrylic adhesive/adhesive composition obtained by Φ was applied by a rotary coater at a dry film thickness of about 30 μm (coating width 25 mm) on a polyester film having a thickness of 38 μm. Subsequently, the solvent in the adhesive/adhesive composition varnish was air-dried at 1〇5. The sample adhesive tape was dried in a circulating air dryer for 5 minutes, and aged for one week under conditions of 23 ° C and 65% R.H., and the light resistance test described later was carried out. The results are shown in Table 2. (Light resistance test) After using a high-pressure mercury lamp to irradiate the sample adhesive tape with a certain cumulative amount of 23 201033291 light, evaluate PROBE TACK (using NS probe adhesiveness tester (NICHIBAN Co., Ltd.), load 100 g / Changes in square centimeters and dwell time 1 second). Examples 2 to 4 and Comparative Examples 1 to 3 A sample adhesive tape was produced in the same manner as in Example 1 except that the rosin ester used in Example 1 was changed as shown in Table 1, and the light resistance test was carried out. The results are shown in Table 2. [Table 1] Component content (%) of rosin ester molecular weight 320 Maximum absorbance at 254 nm or more (dm3/l·cm) Example 1 Rosin ester 1 100 0.06 Example 2 Rosin ester 2 99 0.07 Example 3 Rosin ester 3 98 0.07 Example 4 Rosin ester 4 96 0.11 Comparative Example 1 Rosin ester 5 94 0.19 Comparative Example 2 Rosin vinegar 6 60 0.71 Comparative Example 3 Rosin ester 7 20 1.4 ❿ [Table 2] Visibility (probe viscosity, g /5mm®) cumulative light amount before irradiation of mercury lamp 400J/cm2 cumulative light amount l〇〇〇J/cm2 Example 1 520 500 460 Example 2 540 510 480 Example 3 500 480 450 Example 4 540 510 480 Comparative Example 1 490 440 240 Comparative Example 2 290 350 30 Comparative Example 3 490 30 10 24 201033291 Example 5 The solvent-type acrylic polymer obtained in Production Example 1 was dried in a 1051 circulating air dryer for 5 hours. 25 parts by weight of the obtained acrylic polymer, 25 parts of 2-ethylhexyl acrylate, 25 parts of butyl acrylate, 6 parts of acrylic acid, 20 parts of rosin 1 obtained in Production Example 2, and 2.5 parts were added. Polyisocyanate-based compound (manufactured by Japan Polyurethane Co., Ltd., trade name "CORONATE") was prepared as a crosslinking agent, and 份2 parts of DAROCUR 1173 (manufactured by CIBA Japan Co., Ltd.) was used as a photoinitiator. Performance amount of radiation hardening adhesive composition. The obtained solvent-type acrylic adhesive/adhesive composition was applied by a rotary coater in a dry film thickness of 30 μm right (coating width 25 mm) on a polyester film having a thickness of 38 μm, and The ultraviolet rays are irradiated to obtain a sample adhesive tape. (Adhesive force) According to the method of JIS Z 023 7, the adhesive tape of the above-mentioned sample is adhered to the adhered material, that is, the polyethylene plate substrate, by using a 2 kg rubber knee roller with a bonding area of 25 mm X 125 mm. , placed at 2〇〇c for 24 hours. Subsequently, using a TENSILON tensile tester (Universal Tensile Tester), 2 〇 β (: 18 剥离 at a peeling speed of 300 mm / min. Peel test to determine the adhesion per 25 mm width (N / 25 mm) ^ Results It is shown in Table 3. (Constant load peeling property) The rubber tape of 2 kg is used to press the above-mentioned sample adhesive tape with a bonding area of mm x (10) mm (4) after the object is also the polyethylene plate substrate. 2 kg of roller is carried out! Reciprocating and fitting, after the heart is minute, 25 201033291 As shown in Table 3, a load of 5 gram is applied to the end of the adhesive tape, and the polyethylene plate is fixed to make it 90. The peeling distance was measured to determine the peeling distance per hour in the ambient atmosphere of 23: The time when the total peeling was measured within 1 hour was as shown in Table 3. The results were except that the rosin was not mixed in Example 5. In addition to the ester 1, the same was carried out to obtain a sample adhesive tape. Examples [Table 3]
無 圖式簡單說明 無 主要元件符號說 明 26Simple illustration of the figure No major component symbol description 26