TWI313704B - Aromatic petroleum resin for hot-melt adhesive, aromatic petroleum resin composition for hot-melt adhesive, and holt-melt adhesive composition - Google Patents

Aromatic petroleum resin for hot-melt adhesive, aromatic petroleum resin composition for hot-melt adhesive, and holt-melt adhesive composition Download PDF

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TWI313704B
TWI313704B TW093111995A TW93111995A TWI313704B TW I313704 B TWI313704 B TW I313704B TW 093111995 A TW093111995 A TW 093111995A TW 93111995 A TW93111995 A TW 93111995A TW I313704 B TWI313704 B TW I313704B
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Taiwan
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hot
melt adhesive
petroleum resin
composition
aromatic petroleum
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TW093111995A
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Chinese (zh)
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TW200506024A (en
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Teruyuki Hattori
Hiroaki Horie
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Tosoh Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

1313704 五、發明說明（1) 【發明所屬之技術領域】 本發明係有關於熱熔接著劑用芳香族石油樹脂與熱炫 接著劑用芳香族石油樹脂組成物、以及使用此石油樹脂或 石油樹脂組成物所形成的加熱穩定性與耐熱黏著性相當優 異的熱熔接著劑組成物。 【先前 對 脂，依 酯系或 —稀共 笨乙烯 體為主 熔接著 烯酯共 廉，並 調配處 劑，故 等的領 黏著性 適合各 對 熱熔接 加熱穩 技術】 於熱溶接著劑，作為主成分所使用者係熱塑性樹 此熱塑性樹脂的種類之不同而稱之為聚稀烴系、聚 聚酿胺系的熱熔接著劑。並且，使用以苯乙烯丁 聚t(SBS)、或苯乙烯.異戊二烯共聚物（SIS)等的 嵌段共聚物為主成分之熱塑性彈性體，而以此彈性 成分的熱熔接著劑亦為習知者。其中聚烯烴系的熱 劑、特別是調配具黏著性樹脂及蠟於乙烯·乙酸乙 下稱為EVA)之熱熔接著劑，由於價格低 藉由為主成分的EVA的乙酸乙烯酯含量、分子量、 :二：Ϊ ’而可調製能適於廣範用途的熱熔接著 在包裝用途、製祚當兹a ^ m & ^ m 乍書藉用途、合板•木工黏合用途 域廣為使用。目前為土 槲浐、趟哲 別兩止藉由用於調配的EVA、具 樹月曰、蠟4的種類與調配 ._ ,, ^ 種用途的熱炼接著劑。彡最適化’U配製 ϊ ί用工I=油樹脂作為具黏著性樹脂之E V A系 定性與耐熱黏著性=到指摘的問題點’可舉出 /咸低* °力Π熱穩定性的減低係，1313704 V. Technical Field of the Invention (1) The present invention relates to an aromatic petroleum resin composition for an aromatic petroleum resin and a heat dinking agent for a hot-melt adhesive, and the use of the petroleum resin or petroleum resin. A hot-melt adhesive composition which is excellent in heat stability and heat-resistant adhesiveness formed by the composition. [Previously, the fat, the ester-based or the dilute-complexed vinyl is mainly melted and the olefin ester is cheap, and the agent is formulated, so the collar adhesiveness is suitable for each pair of heat-sealing heating stabilization technology] in the hot-melt adhesive, The thermoplastic resin used as the main component is referred to as a hot-melt adhesive of a polyolefin-based or polyacrylamide-based type. Further, a thermoplastic elastomer containing a block copolymer such as styrene butadiene t (SBS) or styrene.isoprene copolymer (SIS) as a main component is used, and a hot-melt adhesive of the elastic component is used. Also known as a learner. Among them, a polyolefin-based heat agent, in particular, a hot-melt adhesive which is prepared by attaching an adhesive resin and a wax to ethylene and acetic acid (hereinafter referred to as EVA), has a vinyl acetate content and a molecular weight of EVA which are mainly composed of a low price. , : 2: Ϊ 'And can be modulated for a wide range of applications of hot melt and then widely used in packaging applications, system, az m & ^ m 借 book use, plywood • woodworking bonding applications. At present, it is a heat-curing adhesive for the use of EVA, arborvitae, wax 4, and blending for the use of 土, 趟, 哲.彡Optimization of 'U preparation ϊ ί I = oleoresin as the adhesive resin E V A system Qualitative and heat-resistant adhesive = to the point of picking point ‘ can be mentioned / salty low * ° force Π thermal stability reduction,

7042-6319-PF(N2);Tcshiau.ptd 第7頁 1313704 五、發明說明（2) 產具=::”:變質栽成為碳化·不稼融成分而在表面 在塗布時導致：障“以著=布機的喷嘴堵塞等， 於黏=軟一起；品保管於倉庫時，由 _A的乙酸乙烯醋量：以:主，對用於熱熔組成物 量等來進行最適化的研討著性樹月曰、以及蠟的種類、 獻種: = : =物(例如參照專利文 上的Em〇〇重量份，包含著= 含量為30請以 ^^0^200 t * „ , 1；〇 Λν?Λ" ^ ^ ^ 未進行使具黏著性樹脂最適化之研討刀。成。…而’並 昭專：ί if,著性樹脂方面來研討則有提案(例如，參 二藉由具^ ^之範圍、乙稀基甲苯含有率、節含有 =石=烴類的熱分解所得到的熱分解㈣分的可聚合 德：二Λ特土定的松節油；以及(3)以特定比率並使用弗里 1 # 夫次型催化劑對於苯酚化合物施行共聚合之改 石油樹脂，作為具黏著性樹脂。然、而，相較於熱 刀/刀，由於使用昂貴的松節油故並不符經濟效益‘Γ 又有提案（例如，參照專利文獻5):在石 =阻胺化合物，以改良加熱穩定性的方法'然：，中二 市售的石油樹脂僅是單純地添加受阻胺化合物則加熱穩定 第8頁 7042-6319-PF(N2);Tcshiau.ptd 1313704 、發明說明（3) 性的改良效果並不夠。 另一方面’使用氫化的芳香族石油樹脂（以下稱為氫 化1油樹脂）作為具黏著性樹脂來改良加熱穩定性的方法 係=知者（例如，參照專利文獻6)。然而，由於本樹脂係 進一步對芳香族石油樹脂加以氫化而製得’相較於未氫化 石油樹脂，則需要氫化用設備、以及氫化用原料（氫、溶 劑、催化劑），而使成本高昂。 【專利文獻1】特開200 1 —590 78號公報（第1頁） 【專利文獻2】特開2002 — 694 08號公報（第1頁）7042-6319-PF(N2);Tcshiau.ptd Page 7 1313704 V. Description of invention (2) Tooling =::": Metamorphism is made into carbonized and non-fragmented ingredients and causes on the surface when coating: If the nozzle of the cloth machine is clogged, etc., the viscosity is soft; when the product is stored in the warehouse, the amount of vinyl acetate vinegar of _A is: Mainly, the research for optimizing the amount of the hot melt composition, etc. Tree scorpion, and the type and contribution of wax: = : = (for example, refer to the Em 〇〇 part of the patent, including = content 30, please ^^0^200 t * „ , 1; 〇Λν ?Λ" ^ ^ ^ The research tool for optimizing the adhesive resin has not been carried out.... and 'and the special: ί if, the research on the resin is a proposal (for example, the reference is by ^^ Range, ethylene toluene content, section containing = stone = thermal decomposition of hydrocarbons, thermal decomposition (four) of polymerizable de: diterpene turpentine; and (3) use of a specific ratio里1# Fu-type catalyst for the phenolic compound to be copolymerized with petroleum resin as an adhesive resin. However, compared to hot knife/knife Due to the use of expensive turpentine, it is not economical. 'There is also a proposal (for example, refer to Patent Document 5): In the stone = amine-blocking compound, to improve the heating stability of the method 'Ran:, the second commercially available petroleum resin only It is not enough to simply add a hindered amine compound to heat and stabilize the improvement effect on the 8th page 7042-6319-PF (N2); Tcshiau.ptd 1313704, and the invention description (3). On the other hand, 'the hydrogenated aromatic petroleum resin is used. (Hereinafter, it is referred to as a hydrogenated oleooleic resin) as a method of improving the heating stability with an adhesive resin (see, for example, Patent Document 6). However, this resin is further produced by hydrogenating an aromatic petroleum resin. In comparison with the unhydrogenated petroleum resin, the equipment for hydrogenation and the raw material for hydrogenation (hydrogen, solvent, and catalyst) are required, and the cost is high. [Patent Document 1] JP-A-200-59078 (1) [Patent Document 2] JP-A-2002-694 08 (Page 1)

【專利文獻3】特開平9 — 31 62 94號公報（第1頁） 【專利文獻4】特開昭55 — 65248號公報（第1頁） 【專利文獻5】特公平3 — 3533 5號公報（第1頁） 【專利文獻6】特開2〇〇〇_1〇382〇號公報（第1頁） 【發明内容】 發明所欲解決的課題： 本發明的課題係提供熱熔接著劑用芳香族石油樹脂與 ^熔接著劑用芳香族石油樹脂組成物、以及使用此石油樹 =或石油樹脂組成物所形成的加熱穩定性、耐熱黏著性相 §優異的熱溶接著劑。 用以解決課題的手段： 諸位本發明者為了解決上述課題，經專心致志研究的 結果發現，藉由將使用於熱熔接著劑組成物之熱熔接著劑 用芳香族石油樹脂的組成與分子量分布等予以最適化，而[Patent Document 3] Japanese Patent Laid-Open No. Hei No. Hei No. Hei 55-65248 (P.1) [Patent Document 5] Japanese Patent Laid-Open No. Hei 55-65248 (page 1) [Patent Document 5] Special Fair 3 - 3533 (Patent 1) [Patent Document 6] Japanese Laid-Open Patent Publication No. Hei. No. 2, No. 3, No. 3, No. 3, pp. (1). SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The problem of the present invention is to provide a hot melt adhesive. The aromatic petroleum resin and the aromatic petroleum resin composition for the fluxing agent, and the hot-melt adhesive which is excellent in heat stability and heat-resistant adhesiveness by using the petroleum tree= or petroleum resin composition. Means for Solving the Problem: In order to solve the above-mentioned problems, the present inventors have found that the composition and molecular weight distribution of an aromatic petroleum resin for a hot-melt adhesive used for a hot-melt adhesive composition have been found by a result of intensive research. Optimize, and

1313704 五、發明說明（4) 接著劑組成物的加熱穩定性、及繼， 與熱：：著$ m關於熱熔接著劑用芳香族石油樹脂 樹^ $石、山拟方香族石油樹脂組成物、以及使用此石油 ΐϊί::成物所形成的熱熔接著劑組成物，其中 :捃光υ 3、香族石油樹脂之特徵在於：利用質子核磁 :雙i:=玄芳香族性氫面積比率為39〜復、⑺烯烴 =鍵二面積比率為0·7%以下、⑴來自經基的氫面積比 …°以下，且分子量分布（Mw/Mn)為1·75以下。 以詳：ί明對於本發明的熱溶接著劑用芳香族石油樹脂加 本發明的熱熔接著劑用芳香族石油樹脂的組成必需滿 足在測疋質子核磁共振時所觀測的光谱之面積百分率為 •(1)~(3)的條件。 亦即為（1)於7. 0〜8. 0ppm所觀測的芳香族性氫的面積 ，率為39〜43%、（2)於5. 0〜6. Oppm所觀測的烯烴性雙鍵性 氫的面積比率為0. 7%以下、（3)於3. 5〜5. 0ppm所觀測的來 自羥基的氫之面積比率為〇· 5%以下。 (1)芳香族性氳的面積比率若在上述範圍外（小於 3 9%、或超過43%)，則會導致和本發明的熱熔接著劑組成 物所使用的乙烯.不飽和酯共聚物之互混性減低，而引起 熱穩定性及耐熱黏著性降低。並且（2 )的烯烴性雙鍵性 氫、以及（3)的來自羥基的氫同時易遭受氧化變質，各別 的面積百分率若超過上述範圍的情形（亦即，烯烴性雙鍵1313704 V. INSTRUCTIONS (4) The heating stability of the composition of the following agent, and the heat and:: m m about the hot-melt adhesive with aromatic petroleum resin tree ^ $ stone, Yamatake Fangxiang petroleum resin And the use of the petroleum ΐϊί:: composition of the hot-melt adhesive composition, wherein: 捃 υ 3, the fragrant petroleum resin is characterized by: the use of proton NMR: double i: = mysterious aromatic hydrogen area The ratio is 39 to complex, (7) olefin = bond 2 area ratio is 0.7% or less, (1) the hydrogen area ratio from the radical is ... or less, and the molecular weight distribution (Mw/Mn) is 1.75 or less. Specifically, the composition of the aromatic petroleum resin for the hot-melt adhesive of the present invention and the aromatic petroleum resin for the hot-melt adhesive of the present invention must satisfy the area percentage of the spectrum observed when measuring proton nuclear magnetic resonance. • Conditions of (1) to (3). O. The observed olefinic double bond is observed in the range of 7. 0 to 8. 0 ppm of the aromatic hydrogen. The area ratio of hydrogen is 0.7% or less, and (3) is 3. 5 to 5. The area ratio of hydrogen derived from a hydroxyl group observed at 0 ppm is 〇·5% or less. (1) If the area ratio of the aromatic cerium is outside the above range (less than 3 9%, or more than 43%), the ethylene-unsaturated ester copolymer used in the hot-melt adhesive composition of the present invention may be caused. The mutual compatibility is reduced, resulting in a decrease in thermal stability and heat-resistant adhesion. Further, the olefinic double bond hydrogen of (2) and the hydrogen derived from the hydroxyl group of (3) are simultaneously susceptible to oxidative deterioration, and the respective area percentages exceed the above range (i.e., olefinic double bonds).

7042-6319-PF(N2);Tcshiau.ptd 第10頁 Ϊ313704 五、發明說明（5) 性氫的面積比率超過〇. 7%時、 過㈣，熱穩定性會減低，m基的虱之面積比率超 本發明的熱熔接著劑用笔条 (Mw/Mn)必需在i 75以下。 、石油樹脂之分子量分布 之分子量分布（Mw/Mn)若超過/^著劑用芳香族石油樹脂 ，減低。再者，M一，分子則量熱:接 *加定接5著劑用芳香族石油樹脂的經值 本發明的用5;;:，g以下 的條件則其他的物性雖盔特別 爲足上达 °C、Mw係500~3000較佳Γ特別限疋，但軟化溫度係5〇〜200 類的ί發Γ的熱炼接著劑用芳香族石油樹月旨係，藉由石油 類的熱分解所得到的分紘 m a,A(] 9Qn 〇r, 刀解油作為其原料油之中對於沸點範 = 140〜280 C的範圍之館分’例如苯乙稀、其烧基衍生 甲基苯乙烯或^甲基苯乙烯、乙稀基甲苯、節及 二衍生物、雙環戊二烯及其衍生物等的可聚合成分施 二均聚或共聚者。通常係藉由在聚合後進一步以驗分解催 匕劑，其次，去除未反應油及低聚物而製得。 本發明的熱熔接著劑用芳香族石油樹脂係，可藉由適 虽地選擇可聚合成分組成、聚合條件（催化劑、聚合溫 度、分子量調節方法等）而得到。 可聚合成分組成係’茚含有率為3〇〜7〇%較佳、而 40~60%更佳；雙環戊二烯含有率為小於5%較佳。此處，所 第11頁 7042-6319-PF(N2);Tcshiau.ptd 1313704 ---- 五、發明說明（6) — 有率係表示相對於可聚合成分之茚及其烷基衍生物 臂11、之重量％;所謂雙環戊二烯含有率係表示相對於可 該$平1之雙環戊二烯及其烷基衍生物的合計之重量％。 成。再:成分組成的調整係藉由蒸餾來精製熱分解油而達 氣相層折法合ΐ分的組成及上述含有率可利用習知的 曰析法來加以分析、測定。 型催：：聚f催化齊丨’可使用習知的弗里德爾-克拉夫茨 idr ’可舉出：三氯化銘、三漠化銘、三ΐ二 之等。尤其是由聚合後的後處理之容易：产翻 以二氟化硼的氣體；或者三氟化硼 又 =、醇類、有機酸等的錯合物為 寺;:醚J '苯 疋，^對於原料油，則以〇^〇重量％2別加以限 聚S溫度係50〜90 t較佳、6〇 8〇 溫度若小於5G t：則分子量增大，# ，範固更佳。聚合 的互混性降低；若超過g 〇 〇c，則所 ' 不飽和酯共聚物 變差’故不佳。並_!_，聚合時間雖未別：油樹脂的色調 卜10小時較佳。 特別加以限定，但0. 而不主要係以聚合溫度的調節來進-个优用刀子量調節劑。不使用分 々门卽來進仃， 例如一般以苯酚、或甲酚、二 5周卽劑的理由係， 二、壬基苯盼等的院基置換苯盼；：：：-八第三丁基苯 谷易被氧所氧化，使石油樹脂的加埶:…刀子量調節劑很 其次，對於本發明的熱溶接著^ ^减低之故。 則用方香埃石油樹脂組 第12頁 7042-6319-PF(N2);Tcshiau.ptd 1313704 五、發明說明（7) ------- 成物加以詳細說明。 本發明的熱炫接著劑用芳香族石油樹脂組成物係， 對於該熱熔接著劑用芳香族石油樹脂1〇〇重量份，則 目 受阻胺化合物〇. 〇 3〜2重量份較佳、0. 〇 3〜. 5重量份=配 形成者。 尺佳而 此處，受阻胺化合物的調配量若小於〇 . 〇 3重量份時 則所得到的芳香族石油樹脂組成物的加熱穩定性惡化i故 不佳。另一方面，受阻胺化合物的調配量若超過2重量份 時’則未見所得到的芳香族石油樹脂組成物的加熱穩77 有所改善，故不佳。 … 作為本發明所使用的受阻胺化合物，若屬稱為受限胺 化合物的範疇之化合物，則可不受限制地加以使用，其中 特別是由於可得到加熱穩定性相當優異的熱熔接著劑用芳 香族石油樹脂組成物，故表示下述一般式的具有2,2,6,6_ 四燒基-4-哌咬基之化合物為較佳。 【化1】7042-6319-PF(N2);Tcshiau.ptd Page 10Ϊ313704 V. Description of invention (5) The area ratio of hydrogen is more than 〇. 7%, over (4), the thermal stability is reduced, and the area of m-based 虱The ratio of the hot-melt adhesive pen (Mw/Mn) exceeding the present invention must be below i 75. The molecular weight distribution (Mw/Mn) of the molecular weight distribution of the petroleum resin is reduced if it exceeds the aromatic petroleum resin. Furthermore, M1, the molecule is calorimetric: the value of the aromatic petroleum resin used for the addition of 5 agents is 5;;:, g or less, the other physical properties are especially for the helmet. ～°C, Mw is 500~3000, Γ is particularly limited, but the softening temperature is 5〇~200. The thermal refining adhesive is made of aromatic petroleum tree, which is thermally decomposed by petroleum. The obtained bifurcated ma, A(] 9Qn 〇r, Knife oil as its raw material oil for the range of boiling point range = 140~280 C, such as styrene, its alkyl-derived methyl styrene Or homopolymerization or copolymerization of a polymerizable component such as methylstyrene, ethylidene toluene, a nodal derivative, dicyclopentadiene or a derivative thereof, usually by further decomposition after polymerization The catalyzed agent is obtained by removing the unreacted oil and the oligomer. The aromatic petroleum resin of the hot-melt adhesive of the present invention can be selected by appropriately selecting a polymerizable component composition, polymerization conditions (catalyst, polymerization). The temperature, molecular weight adjustment method, etc. are obtained. The polymerizable component composition is '茚 content rate is 3〇~7〇% Preferably, 40 to 60% is more preferable; the content of dicyclopentadiene is preferably less than 5%. Here, page 11 7042-6319-PF(N2); Tcshiau.ptd 1313704 ---- V. Invention Description (6) - The ratio indicates the weight % of the oxime and its alkyl derivative arm 11 relative to the polymerizable component; the so-called dicyclopentadiene content ratio indicates the dicyclopentadiene relative to the valence of 1 And the total weight % of the alkyl derivative thereof. The composition of the component is adjusted by distillation to purify the thermally decomposable oil to obtain the composition of the gas phase layer and the above content. The analysis method is used to analyze and measure. Type reminder:: The polyf-catalyzed Qi can be used in the well-known Friedel-Crafts Idr': three-chlorination, three desertification, three-two In particular, it is easy to post-process after polymerization: a gas that turns over boron difluoride; or a complex of boron trifluoride = alcohol, organic acid, etc.;: ether J 'benzene疋, ^ For the raw material oil, 〇 〇 〇 〇 2 2 2 2 S S S S S S S S S S S S 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度 温度# ,范固更佳. The intermixing property of the polymerization is lowered; if it exceeds g 〇〇c, the 'unsaturated ester copolymer deteriorates' is not good. And _!_, although the polymerization time is different: oleoresin The color tone is preferably 10 hours. It is particularly limited, but 0. It is not mainly used to adjust the polymerization temperature to use a knife amount regulator. It is not used for the enthalpy, for example, phenol, or The reason for the cresol, the two-week bismuth agent, the second, the thiophene phthalate and other hospital-based replacement benzene hope;:::- octa-butyl benzyl benzene is easily oxidized by oxygen, so that the petroleum resin is twisted: ...the knife amount adjuster is second, and the hot melt of the present invention is reduced. Then use the Fang Xiange petroleum resin group. Page 12 7042-6319-PF (N2); Tcshiau.ptd 1313704 V. Invention description (7) ------- The product is described in detail. The aromatic petroleum resin composition for a heat-sensitive adhesive of the present invention is preferably a hindered amine compound 〇〇. 〇 3 to 2 parts by weight, preferably 0 parts by weight of the aromatic petroleum resin for the hot-melt adhesive. 〇3~. 5 parts by weight = matcher. When the amount of the hindered amine compound is less than 〇3 parts by weight, the heating stability of the obtained aromatic petroleum resin composition deteriorates, which is not preferable. On the other hand, when the amount of the hindered amine compound is more than 2 parts by weight, the heating stability 77 of the obtained aromatic petroleum resin composition is not improved, which is not preferable. The hindered amine compound used in the present invention, if it is a compound called a restricted amine compound, can be used without limitation, and in particular, a fragrance for a hot-melt adhesive which is excellent in heat stability can be obtained. The petroleum resin composition is preferably a compound having a 2,2,6,6-tetraalkyl-4-piperidinyl group of the following general formula. 【化1】

R5 此處’一般式中的R1~R4係碳數為卜4的烷基，R5係氫 或可具有取代基之碳數為卜8的烷基或烷氧基。R1〜R4可相 互為相同或不同’作為其具體實例，可舉出曱基、乙基 等，而以曱基較佳。作為的具體實例，可舉出氫、甲R5 Here, R1 to R4 in the general formula are an alkyl group having a carbon number of 4, and R5 is a hydrogen or an alkyl group or alkoxy group having a carbon number of a substituent. R1 to R4 may be the same or different from each other. As a specific example thereof, a mercapto group, an ethyl group or the like may be mentioned, and a mercapto group is preferred. As a specific example, hydrogen, A

五、發明說明（8) 基、及辛基等，而以氫及甲基較佳。 以一般式所不的受阻胺化合物之分子量4〇〇~4〇〇〇為習 ，而作為受阻胺系光穩定劑（HALS)在市面上有販售。 =為具體的市售品，可舉出：Ciba .Speciaity . ^6°11^=5(股份）或旭電化工業（股份）所製造的雙（2,2,6, 哌ί 哌啶基）癸二酸酯、雙（1，2,2,6’6一五甲基-1 质啶基）力二酸酯、四（2,2,6,6_四甲 旨、四(1，2,2,6,6-五甲基-二咬 $1違2其3 4 丁烧四叛酸醋、聚[{6_(11，33_四甲基丁 ^〕）^基}六甲#{(2’2,6,6_四甲基_4_脈唆基）亞氨 方法i發：用芳香族石油樹脂組成物之製造 份，ί可：Ϊ 者劑用芳香族石油樹脂1〇〇重量 伤右可调配受阻胺化合物0.03~2重量份， 的方法。通常，关岙旄rt 則可使用任何 氧化而形成過氧化物，若對县：$在5溫下也容易受到 熱熔融，則引起& % & & ”子的芳香族石油樹脂加 加熱著色、f ::過；容易產生結皮或 更為優異的熱熔接著劑用芳香族；I油樹;:性、加熱穩ί性 用芳香族石油樹脂的聚合反 ‘去：j :: 低分子化合物之饴尤々+ _ 爾去共存的溶劑或 族石油樹脂中謂配说㈣纟融狀態的熱炼接著劑用芳香 且，於】物之方法為較佳。* 吟的調配15内的氧濃度係1 000PPm以下較 1313704 五、發明說明（9) 佳、lOOppm以下更佳、 、 :”己：的溶融狀態的熱熔接ΐ 7用下芳二^ 化、特別是基於氧的氧化，故較=了香族石油樹脂的氧 再者，本發明的熱熔接著劑用 係，只要不超脫本發明的目的，、 矣石油樹脂組成物 成物的添加劑，例如可調配•、―、常作為調配至樹脂組 化劑、硫系抗氧化劑、内㈣^系抗氧化劑、填系抗氧 顏料、碳酸約、破璃珠粒料^乳化劑、紫外線吸收劑、 其次’就本發明的熱熔接 在本發明的熱炼接著劑加以詳細說明。 和醋共聚物雖未特別加以限定成的乙烯·不飽 可舉出：乙酸乙婦酯(VAc)、一元仁幾作:二飽和醋’例如， 等。特別是由接著劑的柔軟性之7^酸看乙來歸醋、丙稀酸醋 XT#AEVA)^^ 點看來，含有VAC2〇〜in番番。/ 由黏者性的觀 .2〇〇〇_分指數j以下稱為md係 ASTM D— 1 238 — 89，以 處;係意指依據 鐘的條件加以測定時的每單位時C門所負=16()g、時間10分 分鐘）。 』疋吋町母早位時間所流出的公克數（g/10 使用的熱熔接著劑組成物中作為具黏著性樹脂所 芳香族者劑用芳香族石油樹脂及/或熱溶接著劑用 :香族石油樹脂組成物，可單獨使用，也可併用2種以 前述的乙烯.不飽和酯共聚物、與熱熔接著劑用芳香 第15頁 7042-6319-PF(N2);Tcshiau.ptd 13137045. Description of the invention (8) Base, octyl and the like, and hydrogen and methyl are preferred. The molecular weight of the hindered amine compound which is not in the general formula is 4〇〇~4〇〇〇, and the hindered amine light stabilizer (HALS) is commercially available. = For specific commercial products, Ciba.Speciaity. ^6°11^=5 (shares) or bismuth (2,2,6,piperazinyl) manufactured by Asahi Kasei Co., Ltd. Sebacate, bis(1,2,2,6'6-pentamethyl-1 -pyridyl) diacid ester, tetra (2,2,6,6_tetrazide, four (1,2) , 2,6,6-pentamethyl-two bite $1 violates 2 of its 3 4 diced four rebel vinegar, poly[{6_(11,33_tetramethylbutyl^)))} hexa#{(2 '2,6,6_Tetramethyl_4_ 唆 唆 ) ) ) 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚The right side can be adjusted with a hindered amine compound in a ratio of 0.03 to 2 parts by weight. Generally, rt can be used to form a peroxide by any oxidation, and if it is susceptible to heat fusion at a temperature of 5 at a temperature of 5, it causes &; % && "Aromatic petroleum resin with heat coloring, f:: over; easy to produce skinning or more excellent aromatics for hot melt adhesive; I oil tree;: sex, heat stability The polymerization of aromatic petroleum resin is reversed: j:: low molecular compound, 饴 々 _ 尔Or a petroleum resin, it is said that (4) the hot-melting adhesive in the molten state is aromatic, and the method is better. * The oxygen concentration in the blending 15 is less than 1 000 ppm and compared with 1313704. 9) Better, less than lOOppm, and: ": The hot-melt joint in the molten state of 己 7 is treated with argon, especially oxygen-based oxidation, so the oxygen of the aromatic petroleum resin is further reduced. The hot-melt adhesive for use in the invention, as long as the object of the present invention is not deviated, the additive of the ruthenium petroleum resin composition, for example, can be formulated, and is often formulated into a resin grouping agent, a sulfur-based antioxidant, and the like. (4) ^ is an antioxidant, filled with an antioxidant pigment, carbonic acid, glass beads, emulsifier, ultraviolet absorber, and then 'the heat fusion of the present invention is described in detail in the hot-melt adhesive of the present invention. Although ethylene is not particularly limited, it may be exemplified by ethyl acetate (VAc) and monobasic: di-saturated vinegar, for example, etc., especially from the softness of the adhesive. B to vinegar, acrylic acid vinegar XT #AEVA) ^^ point Contains VAC2〇~in Fanfan./ From the view of stickiness. 2〇〇〇_分指数j is hereinafter referred to as md system ASTM D-1 238-89, where it is used; C gate per unit time = 16 () g, time 10 minutes).克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克The aromatic petroleum resin composition may be used singly or in combination with two kinds of the above-mentioned ethylene. Unsaturated ester copolymer, and a hot melt adhesive for aroma on page 15 7042-6319-PF (N2); Tcshiau.ptd 1313704

族石油樹脂及/或熱熔接著劑用芳香族石油樹脂組成物之 ，配比率m滿足作為熱溶接著劑所要求的特性則 未特別加以限制，冑圍可變得較為寬廣，但適當的調配比 率，，相，於乙烯.不飽和酯共聚物100重量份，則熱熔 接著劑用芳香族石油樹脂及/或熱炫接著劑用芳香族石油 樹脂組成物係以5 〇〜1 5 0重量份較佳，6 〇〜丨2 〇重量份更佳。 ，調配比率若超脫上述範圍（5〇〜15〇重量份）時，則熱熔接 著劑組成物的黏著性會減低而不符實用性。 作為本發明的熱熔接著劑組成物所使用的蠟，可舉 出·.石躐、微晶蠟等的石油蠟類；聚乙烯蠟、費歇爾—托 倫式蠘、聚丙烯蠟、無規聚丙烯蠟等的合成蠟；木蠟、加 洛巴蠛、蜂蠟等的天然蠟等，可作為單獨或混合物來加以 使用。 對於本發明的熱熔接著劑組成物，蠟的調配比率係， 相對於乙烯.不飽和酯共聚物1 〇 〇重量份，則以丨〇〜丨〇 〇重 量份較適合、而10〜50重量份更佳。蠟的調配量若超過前 述範圍（10〜100重量份），則由於會導致熱熔接著劑組成物 的黏合強度減低，故不佳。 熱熔接著劑組成物的黏度雖基於使用目的而有所不 同’但其黏度調整受到調配物，亦即乙烯.不飽和酯共聚 物的分子量、具黏著性樹脂的黏度、蠟的黏度所左右，而 且即使這些調配物的調配比率有所改變。因而，依目的之 不同，需將調配比率予以最適化。通常，在180 °C的熔融 黏度以100〜lOOOOmPa.s為較佳。The aromatic petroleum resin composition of the petroleum resin and/or the hot-melt adhesive is not particularly limited as long as the ratio m satisfies the characteristics required as the hot-melt adhesive, and the circumference can be broadened, but appropriate blending The ratio of the phase, in the case of 100 parts by weight of the ethylene-unsaturated ester copolymer, the aromatic petroleum resin for the hot-melt adhesive and/or the aromatic petroleum resin composition for the heat-thinking agent is 5 〇 to 150 weight. Preferably, the amount of 6 〇 ~ 丨 2 更 is better. When the blending ratio exceeds the above range (5 Torr to 15 Torr by weight), the adhesion of the heat-fusible composition is lowered, which is not practical. Examples of the wax used in the composition of the hot-melt adhesive of the present invention include petroleum waxes such as sarcophagus and microcrystalline wax; polyethylene wax, Fischer-Toron type enamel, polypropylene wax, and no A synthetic wax such as a polypropylene wax; a natural wax such as wood wax, carbofuran or beeswax may be used alone or as a mixture. For the hot-melt adhesive composition of the present invention, the blending ratio of the wax is preferably 1 to 50 parts by weight based on 1 part by weight of the ethylene-unsaturated ester copolymer. Better. When the amount of the wax is more than the above range (10 to 100 parts by weight), the bonding strength of the hot-melt adhesive composition is lowered, which is not preferable. The viscosity of the composition of the hot-melt adhesive is different depending on the purpose of use, but the viscosity adjustment is affected by the formulation, that is, the molecular weight of the ethylene-unsaturated ester copolymer, the viscosity of the adhesive resin, and the viscosity of the wax. And even if the formulation ratio of these formulations changes. Therefore, depending on the purpose, the blending ratio needs to be optimized. Generally, the melt viscosity at 180 ° C is preferably 100 to 100 mPa·s.

1313704 五、發明說明（11) 本發明的 料、以抗氧化 機填充材料等 的方法，亦即 造方法的炼融 難的極低之溫 特別問題。另 物的分解、或 若考量這些情 合係可使用習 混煉機、捏和 本發明的 途，亦即紙、 性樹脂、熱塑 黏合方法 用的熱溶接著 機、喷霧型熱 塗布機、擠壓 發明效果： 要可調配 油、增塑 組成物能 成分而製 若不是熔 或流動的 乙烯•不 生著色者 180-200 放式煉膠 混合槽等 用於以往 等的木材 合0 出：喷嘴 熱炫塗布 熱熔接著劑組成物依需 劑為主的各種穩定劑、 。本發明的熱熔接著劑 在熔融下混合各種調配 溫度雖無特別限制，但 度、或是調配物不熔融 一方面，對於高溫，則 基於具黏著性樹脂而產 形，則160〜230 °c較佳， 知的方法之擠壓機、開 機、捏和鏤銑機、熔融 熱溶接著劑組成物可使 聚酯薄膜、金屬、合妬 性彈性體、橡膠等的黏 雖未特別加以限制，但 劑用的設備，例如可舉 熔塗布機、扁平噴嘴型 型塗布機等。 顏料、染 劑、以及無 夠藉由習知 得。於本製 融攪摔有困 低溫，則無 飽和酯共聚 ’故不佳。 °C更佳。混 機、班伯里 來實施β 習知的用 、布、熱塑 可利用一直以來所使 型熱熔塗布 機、輥筒型1313704 V. INSTRUCTION DESCRIPTION OF THE INVENTION (11) The method of the present invention, the method of filling the material with an antioxidant, etc., is also a problem of extremely low temperature which is difficult to refine in the manufacturing method. Decomposition of another substance, or a combination of the above, may be carried out using a conventional kneader, kneading the present invention, that is, a hot melt machine for paper, resin, thermoplastic bonding method, spray type hot coater Extrusion effect: It is necessary to adjust the oil and plasticizer composition to make it if it is not melted or flowing. • No coloring. 180-200. : Nozzle hot coating hot melt adhesive composition based on various stabilizers. The hot-melt adhesive of the present invention is not particularly limited in mixing under various conditions of melting, but the degree or the formulation is not melted. On the one hand, for high temperature, it is formed based on an adhesive resin, and 160 to 230 ° C. Preferably, the known method of the extruder, the starter, the kneading and milling machine, and the molten hot-melt adhesive composition can make the adhesion of the polyester film, the metal, the conjugated elastomer, the rubber, etc., not particularly limited. However, the apparatus for the agent may be, for example, a melt coater or a flat nozzle type coater. Pigments, dyes, and not enough are known. In the case of this system, if there is a low temperature, then the unsaturated ester copolymerization is not good. °C is better. Mixing machine, Banbury, etc., the use of cloth, thermoplastics, and thermoplastics can be used to make hot melt coaters and rolls.

如以上所示，本發明的熱熔接著劑用芳香族石油樹脂 了 .’、、炫接著劑用芳香族石油樹脂組成物、以及使用此石油 樹脂或石油樹脂組成物的熱熔接著劑組成&，係加熱穩定 性與耐熱黏著性相當優異者。As described above, the hot-melt adhesive of the present invention is composed of an aromatic petroleum resin, an aromatic petroleum resin composition for a blistering agent, and a hot-melt adhesive composition using the petroleum resin or petroleum resin composition. ;, is the heating stability and heat resistance is quite excellent.

1313704 五、發明說明（12) 【實施方式】 實施例： 以下，藉由實施例對本發明加以說明，但本發明毫不 受到這些實施例限制。再者，於實施例、比較例中所使用 的原料樹脂、調配物、組成物的調製、分析、試驗法係如 下述。1313704 V. DESCRIPTION OF THE INVENTION (12) [Embodiment] The present invention is described below by way of examples, but the invention is not limited by the examples. Further, the preparation, analysis, and test methods of the raw material resins, formulations, and compositions used in the examples and comparative examples are as follows.

1. 原料 (l)EVA 東曹股份公司製，Nipo flex 0B 53 C(乙酸乙烯酯含量 =28 重量％、MI = 400g/10 分鐘） 東曹股份公司製，Nipof lex 0B54A — 3(乙酸乙烯酯含 量=33 重量％、MI = 400g/10 分鐘） (2 )熱熔接著劑用芳香族石油樹脂：基於實施例卜3、 比較例1〜3所述的條件來製造。 (3) 熱熔接著劑用芳香族石油樹脂組成物：基於實施 例4〜7、比較例4 ~ 5所述的條件來製造。 (4) 躐.石蠛（日本精蠛公司製，paraffinwaxi55F)、 費歇爾-托侖式蠟（Sasol Ltd製，PARAFLINT HI) (5) 抗氧化劑：苯酚系抗氧化劑（Ciba .Spacialty · Chemicals 製 ’ irganoxl010) (6) 受阻胺化合物：adKSTAB光穩定劑LA—77〔旭電化 工業製’雙（2，2，6，6 -四甲基-4 -脈咬基）癸二酸醋〕 2. 熱熔接著劑組成物之調製方法 如實施例所記述。1. Raw material (l) EVA made by Tosoh Corporation, Nipo flex 0B 53 C (vinyl acetate content = 28% by weight, MI = 400g/10 minutes) manufactured by Tosoh Corporation, Nipof lex 0B54A - 3 (vinyl acetate) Content = 33% by weight, MI = 400 g/10 minutes) (2) Aromatic petroleum resin for hot melt adhesive: It was produced based on the conditions described in Example 3 and Comparative Examples 1 to 3. (3) Aromatic petroleum resin composition for hot melt adhesive: It was produced under the conditions described in Examples 4 to 7 and Comparative Examples 4 to 5. (4) 蠛. sarcophagus (made by Nippon Seiki Co., Ltd., paraffinwaxi 55F), Fischer-toronian wax (PARAFLINT HI, manufactured by Sasol Ltd) (5) Antioxidant: phenolic antioxidant (Ciba.Spacialty · Chemicals ' irganoxl010) (6) Hindered amine compound: adKSTAB light stabilizer LA-77 [Shuang (2,2,6,6-tetramethyl-4 - nucleus) azelaic acid vinegar]. The method of preparing the hot melt adhesive composition is as described in the examples.

7042-6319-PF(N2);Tcshiau.ptd 第18頁 1313704 五、發明說明（13) 3.分析方法 (1) 原料油的各成分之含量：利用菊β 來加以分析。 和用各知的氣相層析法 (2) 重均分子量：以聚苯乙烯為標準物質，利用 滲透層析法來加以測定。 & —(3)質子核磁共振（核磁共振光譜）：使熱熔接著劑 芳香族石油樹脂溶解於氣仿-d〔和光純藥工業（股份） 中，以一般的核磁共振測定法加以測定。對於所得 譜’基於下述計算式來求得面積比率。 们九 X 100 面積比率U)=(各尖峰面積）/(全部尖峰面積的人 σ 口丁） 再者，各尖峰如下： 芳香族性氫尖峰：7. 0~8. 0ppm 烯烴性雙鍵氫尖峰：5. 0~6. Ορριη 來自羥基的氫尖峰：3. 5〜5. 0ppm (4) 羥值：依據Jis K-0070 C 1 9 66 )的方法來測定。 (5) 軟化溫度：依據jis κ-253 1 ( 1 960)(環球法）的方 法來測定 4.試驗方法 (1)耐熱黏著性的試驗方法：耐熱蠕變試驗 依據JAI-7(日本黏合工業會規格），以裁剪成5〇_\ 1 5 0mm的厚紙板2片（K Liner)作為受黏合體，使用熱熔間 隔時間試驗器，以塗布溫度18〇艽、塗布速度7. 5m/分鐘、 塗布面積（黏合面積）5〇min X 1 〇〇mm、塗布量〇. 〇3g/cm2的條7042-6319-PF(N2); Tcshiau.ptd Page 18 1313704 V. INSTRUCTIONS (13) 3. Analytical methods (1) Content of each component of raw material oil: Analysis was carried out using chrysanthemum β. And known gas chromatography (2) Weight average molecular weight: using polystyrene as a standard substance, and measuring by permeation chromatography. & (3) Proton nuclear magnetic resonance (NMR): The hot-melt adhesive aromatic petroleum resin was dissolved in a gas-d-[Wo Pure Chemical Industry Co., Ltd., and measured by a general nuclear magnetic resonance measurement method. The area ratio was determined for the obtained spectrum 'based on the following calculation formula. 9 N 100 area ratio U) = (each peak area) / (all peak area of the person σ mouth Ding) Again, the peaks are as follows: Aromatic hydrogen peak: 7. 0~8. 0ppm olefinic double bond hydrogen Spike: 5. 0~6. Ορριη Hydrogen peak from hydroxyl group: 3. 5~5. 0ppm (4) Hydroxyl value: determined according to the method of Jis K-0070 C 1 9 66 ). (5) Softening temperature: Measured according to the method of jis κ-253 1 (1 960) (ring and ball method) 4. Test method (1) Test method for heat-resistant adhesion: Heat-resistant creep test according to JAI-7 (Japan bonding industry) 5米/分钟, The coating temperature is 18 〇艽, the coating speed is 7.5 m / min, and the coating temperature is 18 〇艽, the coating speed is 7.5 m / min. , coating area (adhesive area) 5〇min X 1 〇〇mm, coating amount 〇. 〇3g/cm2 strip

7042-6319-PF(N2);Tcshiau.ptd7042-6319-PF(N2); Tcshiau.ptd

1313704 五、發明說明（14) 件，在一片受黏合體的單面塗布熱熔接著劑組成物， 隔時間2秒鐘後黏貼至另一片受黏合體，施予2kg ^二 荷，放開冷卻，作成黏合試驗片。其次，將上述 片裁剪成25 mm X 150 mm後，藉由τ型剝離的方式，於=山 吊掛著30 0g/25mm的負荷之狀態，於55。〇的烘箱中< ^一端 置著，測定負荷至落下為止的時間（分鐘）。上述& 則表示耐熱黏著性越是優異。 越長 (2)加熱穩定性的試驗方法：加熱變質試驗 將利用則述的2 ·熱熔接著劑組成物之調製方法 的熱熔接著劑50g置入18(TC的吉爾老化恒溫箱中，1 1 時觀察試樣表面。以凝膠、碳化物等的熱變質物1313704 V. Inventive Note (14), apply a hot-melt adhesive composition on one side of a bonded body, stick to another bonded body after 2 seconds, apply 2kg ^ two charge, release the cooling , made a bonded test piece. Next, after the above-mentioned sheet was cut into 25 mm X 150 mm, the load of 30 0 g/25 mm was hung on the mountain by the τ-type peeling method, and it was 55. In the oven of the crucible, the end of the ^^ was placed, and the time (minutes) until the load was dropped was measured. The above & means that the heat-resistant adhesiveness is more excellent. The longer the (2) test method for the heating stability: the heating and deterioration test is carried out by using the hot-melt adhesive 50 g of the method of preparing the hot-melt adhesive composition described above into the 18 (TC Gil aging incubator, 1 1) Observe the surface of the sample. Thermally altered substances such as gels, carbides, etc.

現的時間當作冑質時間。上述時間越長則表 J 越是優異。 .，、、德疋r生 「熱熔接著劑用芳香族石油樹脂之製造」 實施例1 : 」 。於藉由石油類的熱分解所得到的沸點範圍為14〇〜28〇 5的範圍之館分（可聚合成分：乙稀基甲細、茚4〇%、 2稀m、雙環戍二烯1%)100重量份中，添加三氣化硼 本龄錯合物〔STELLA CHEMIFA 化硼苯 重量%作為弗里德爾-克拉夫茨型催化劑，於75。。 f仃2小時聚合之後，以苛性鈉水溶液去除催化劑，装餾 =相的未反應油而得到熱熔接著劑用芳香族石油樹脂’、、The current time is taken as the enamel time. The longer the above time, the better the table J is. .,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The range of the boiling point range obtained by thermal decomposition of petroleum is in the range of 14 〇 to 28 〇 5 (polymerizable component: ethylene fine, 茚 4 〇%, 2 dilute m, dicyclodecadiene 1 %) In 100 parts by weight, a boron trioxide-based compound (STELLA CHEMIFA) was added as a Friedel-Crafts type catalyst at 75. . After the polymerization for 2 hours, the catalyst was removed with an aqueous solution of caustic soda, and the unreacted oil of the phase was charged to obtain an aromatic petroleum resin for hot-melt adhesives.

(A)。此樹脂（A)的物性（軟化溫度、分子量分布、質子核 磁共振測定結果、以及羥值）如第1表所示。 X(A). The physical properties (softening temperature, molecular weight distribution, proton nuclear magnetic resonance measurement results, and hydroxyl value) of the resin (A) are shown in Table 1. X

7042-6319-PF(N2);Tcshiau.ptd 第20頁 i 1313704 五、發明說明（15) 實施例2 : 將藉由石油類的熱分解所得到的沸點範圍為丨4 〇〜2 8 0 °c的範圍之餾分作成可聚合成分：乙烯基曱苯29%、節 41%、苯乙烯27%、雙環戊二烯4%，除了將聚合溫度設為90 C之外，利用與實施例1同樣條件來調製熱熔接著劑用芳 香族石油樹脂（B)。此樹脂（B)的物性（軟化溫度' 分子量 为布、質子核磁共振測定結果、以及經值）如第1表所示。 實施例3 : 將藉由石油類的熱分解所得到的沸點範圍為丨4 〇〜2 8 0 °〇的範圍之餾分作成可聚合成分：乙烯基甲苯42%、節 46%、苯乙烯12%、雙環戊二烯1%，除了將聚合溫度設為6〇 C之外，利用與實施例1同樣條件來調製熱熔接著劑用芳 香族石油樹脂（C)。此樹脂（C )的物性（軟化溫度、分子量 -分布、質子核磁共振測定結果、以及羥值）如第1表所示。 比較例1 : 將藉由石油類的熱分解所得到的沸點範圍為丨4 〇〜2 8 0 °(：的範圍之餾分作成可聚合成分：乙烯基甲苯5 3%、節 38%、苯乙烯4%、雙環戊二烯5%，添加三氟化硼醚錯合物 〔STELLA CHEMIFA CORPORATION 三氟化硼乙謎〕1. 〇 重量 % ’除了將聚合溫度設為6 0 °C之外’利用與實施例1同樣條 件來調製熱熔接著劑用芳香族石油樹脂（D)。此樹脂（D)的 物性（軟化溫度、分子量分布、質子核磁共振測定結果' 以及羥值）如第1表所示。 比較例2 :7042-6319-PF(N2); Tcshiau.ptd Page 20 i 1313704 V. Description of Invention (15) Example 2: The boiling point range obtained by thermal decomposition of petroleum is 丨4 〇~2 8 0 ° The fraction in the range of c was made into a polymerizable component: vinyl benzene 29%, ganglion 41%, styrene 27%, and dicyclopentadiene 4%, and the same as in Example 1 except that the polymerization temperature was 90 C. The condition is to modulate the aromatic petroleum resin (B) for the hot melt adhesive. The physical properties (softening temperature 'molecular weight of the cloth, proton nuclear magnetic resonance measurement result, and menstrual value) of the resin (B) are shown in Table 1. Example 3: A fraction having a boiling point range of 丨4 〇~2 80 °〇 obtained by thermal decomposition of petroleum was used as a polymerizable component: vinyl toluene 42%, section 46%, styrene 12% In the same manner as in Example 1, except that the polymerization temperature was set to 6 〇C, the aromatic petroleum resin (C) for hot-melt adhesive was prepared. The physical properties (softening temperature, molecular weight distribution, proton nuclear magnetic resonance measurement results, and hydroxyl value) of the resin (C) are shown in Table 1. Comparative Example 1: A fraction having a boiling point range of 丨4 〇~2 800 ° (by a thermal decomposition of petroleum) was used as a polymerizable component: vinyl toluene of 5 3%, a section of 38%, and styrene. 4%, 5% of dicyclopentadiene, addition of boron trifluoride etherate complex [STELLA CHEMIFA CORPORATION boron trifluoride puzzle] 1. 〇% by weight 'except that the polymerization temperature is set to 60 °C' The aromatic petroleum resin (D) for a hot-melt adhesive was prepared under the same conditions as in Example 1. The physical properties (softening temperature, molecular weight distribution, proton nuclear magnetic resonance measurement result, and hydroxyl value) of the resin (D) were as shown in Table 1. Shown Example 2:

7042-6319-PF(N2);Tcshiau.ptd 第21頁 1313704 五、發明說明（16) 。於冑由石油類的熱分解所得到的彿點範圍為14()~28() C的範圍之館分（可聚合成分··乙締基甲苯39%、⑽％、 苯乙烯m、雙環戊二烯8%)100重量份中，添加苯紛2重量 份之後’調製可聚合成分使成為5n ’除了將聚合溫度設 為4(TC之外’利用與實施例3同樣條件來調製熱溶接著劑 用芳香族石油樹脂（E) ^此樹脂（E)的物性（軟化溫度、分 子量分布、質子核磁共振測定結果、以及經值）如^i表所 示0 比較例3 : 依照專利文獻4的特開昭55_ 65248號公報，於藉由石 油類的熱分解所得到的沸點範圍為14〇〜28〇 t的範圍之餾 分（可聚合成分：乙烯基甲苯41%、茚4〇%、苯乙烯17%、 環；^二烯i%)ioo重量份中，添加二烯值為7(cg/g)的市售 松節油〔和光純藥工業（股份）製〕23重量份、苯酚5重量 份之後，調製可聚合成分使成為5〇%，添加三氟化硼苯酚7042-6319-PF(N2); Tcshiau.ptd Page 21 1313704 V. Description of invention (16). In the range of 14 () ~ 28 () C obtained from the thermal decomposition of petroleum, the concentration of the point of the Buddha is 39%, (10)%, styrene m, dicyclopentan In 8% of 100 parts by weight of the diene, after adding 2 parts by weight of benzene, 'modulating the polymerizable component to be 5n', except that the polymerization temperature was set to 4 (other than TC), the same conditions as in Example 3 were used to prepare hot solution. Aromatic petroleum resin (E) for the agent ^ Physical properties (softening temperature, molecular weight distribution, proton nuclear magnetic resonance measurement results, and menstrual value) of the resin (E) as shown in Table 1. Comparative Example 3: According to Patent Document 4 JP-A-55-65248, a fraction having a boiling point range of 14 〇 to 28 〇t obtained by thermal decomposition of petroleum (polymerizable component: vinyl toluene 41%, 茚4% by weight, styrene) 17 parts by weight of a commercially available turpentine (manufactured by Wako Pure Chemical Industries, Ltd.) having a diene value of 7 (cg/g) and 5 parts by weight of phenol after adding a diene value of 7 (cg/g) , modulating the polymerizable component to be 5 % by weight, adding boron trifluoride phenol

錯合物〔STELLA CHEMIFA CORPORATION三氟化硼苯酚〕J 0重量％ ’於20 C進行3小時聚合之後，以苛性鈉水溶液去 除催化劑’並蒸餾油相的未反應油而得到熱熔接著劑用芳 香族石油樹脂（F)。樹脂（F)的物性（軟化溫度、分子量分 布、質子核磁共振測定結果、以及羥值）如第丨表所示。 第22頁 7042-6319-PF(N2);Tcshiau.ptd 1313704 五、發明說明（17) [第1表】 實施例1 寶施例2 實施例3 比較例1 比較例2 比較例3 樹脂A 樹脂B 樹脂C 榭脂D 樹脂E 樹脂F 軟化®STc) 120 116 119 120 120 123 分子重耐 830 770 850 770 840 730 分子s_ 1350 1240 1480 1580 1500 1250 Mw/Mn 1.63 1.61 1.74 2.05 1.79 1.71 裡値 (mg-KOH/g) 4 0 0 0 10 15 質子核磁共振光譜0¾面清 芳細4氫 41.08 42.12 39.44 37.18 38.89 36.3 應性®«氫 0.02 0.64 0.18 0.77 1.15 1.47 來自^的氫 0.45 0.27 0 0 0.87 0.76The complex compound [STELLA CHEMIFA CORPORATION boron trifluoride phenol] J 0% by weight 'after 3 hours of polymerization at 20 C, the catalyst was removed with an aqueous solution of caustic soda and the unreacted oil of the oil phase was distilled to obtain a hot-melt adhesive fragrance. Group petroleum resin (F). The physical properties (softening temperature, molecular weight distribution, proton nuclear magnetic resonance measurement results, and hydroxyl value) of the resin (F) are shown in the table. Page 22 7042-6319-PF(N2); Tcshiau.ptd 1313704 V. Inventive Note (17) [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Resin A Resin B Resin C Resin D Resin E Resin F Softening® STc) 120 116 119 120 120 123 Molecular weight resistance 830 770 850 770 840 730 Molecular s_ 1350 1240 1480 1580 1500 1250 Mw/Mn 1.63 1.61 1.74 2.05 1.79 1.71 値 (mg -KOH/g) 4 0 0 0 10 15 Proton nuclear magnetic resonance spectrum 03⁄4 face clear aromatic 4 hydrogen 41.08 42.12 39.44 37.18 38.89 36.3 Qualitative® «hydrogen 0.02 0.64 0.18 0.77 1.15 1.47 Hydrogen from ^0.45 0.27 0 0 0.87 0.76

再者，於比較例卜3所得到的熱熔接著劑用芳香族石 >由樹脂（D、E、F )係未滿足芳香族性氫面積比率為 39〜43%、烯烴性雙鍵氫面積比率為〇· 7%以下、來自羥基的 氫面積比率為0.5%以下、分子量分布（Mw/MrOai.H以 下、羥值為5mg -KOH/g以下的各項目之全部或者任一項。 「熱熔接著劑用芳香族石油樹脂組成物之製造」 實施例4 : 於氧濃度2ppm的氮氣流下，相對於剛製造後的樹脂 (^)100重量份’在1〇〇 °c、攪拌轉速3〇〇rpm的條件下調配 受阻胺化合物〔旭電化工業製、商品名ADKSTAB光穩定劑 L A — 7 7〕0 · 1重量份’得到熱熔接著劑用芳香族石油樹脂Further, the aromatic stone for hot-melt adhesive obtained in Comparative Example 3 was not satisfied with the aromatic hydrogen area ratio of 39 to 43% by the resin (D, E, F), and the olefinic double bond hydrogen The area ratio is 〇·7% or less, the hydrogen area ratio from the hydroxyl group is 0.5% or less, and all or any one of the items having a molecular weight distribution (Mw/MrOai.H or less and a hydroxyl value of 5 mg-KOH/g or less). Production of a composition of an aromatic petroleum resin for a hot-melt adhesive agent" Example 4: Under a nitrogen gas flow having an oxygen concentration of 2 ppm, 100 parts by weight of the resin (^) immediately after manufacture was at 1 ° C, stirring speed 3 Under the condition of 〇〇 rpm, a hindered amine compound was prepared (manufactured by Asahi Kasei Co., Ltd., trade name ADKSTAB light stabilizer LA-7 7) 0 · 1 part by weight 'to obtain an aromatic petroleum resin for hot melt adhesive

組成物（G)。樹脂組成物（G )的調配比如第2表所示。 實施例5 : 利用和實施例4同樣的方法，在樹脂（b )中調配受阻胺 4匕合物而得到熱炼接著劑用芳香族石油樹脂組成物（H)。 樹脂組成物（H)的調配比如第2表所示。Composition (G). The formulation of the resin composition (G) is shown in Table 2. Example 5: A hindered amine 4 composition was blended in a resin (b) in the same manner as in Example 4 to obtain an aromatic petroleum resin composition (H) for a hot-melt adhesive. The formulation of the resin composition (H) is shown in Table 2.

1313704 五、發明說明（18) 實施例6 : 利用和實施例4同樣的方法，在樹脂（C )中調配受阻胺 化合物而得到熱熔接著劑用芳香族石油樹脂組成物（I )。 樹脂組成物（I)的調配比如第2表所示。 實施例7 : 於氧濃度2ppm的氮氣流下，相對於剛製造後的樹脂 (A)100重量份’在l〇〇°c、攪拌轉速3〇〇rpm的條件下調配 受阻胺化合物〔旭電化工業製、商品名ADKSTAB光穩定劑 LA — 77〕0. 02重量份，得到熱熔接著劑用芳香族石油樹脂 組成物（J )。樹脂組成物（J )的調配比如第2表所示。 比較例4 : 利用和實施例4同樣的方法，在樹脂（D )中調配受阻胺 化合物而得到熱熔接著劑用芳香族石油樹脂組成物（K)。 樹脂組成物（K)的調配比如第2表所示。 比較例5 : 利用和實施例4同樣的方法，在樹脂（E )中調配受阻胺 化合物而得到熱熔接著劑用芳香族石油樹脂組成物（L)。 樹脂組成物（L)的調配比如第2表所示。 【第2表】 罝施例4實施例5音施例6 實施例7 比較例4比較例5 組成物ΰ驵成物Η绀成物1 誠物J 组成物κ組成物L 凳阻胺化合物屋量份） 〇.1 U.1 〇1 0.02 0.1 0.1 芳香族石油樹脂 酿分） ABC 100 100 100 A 100 D E 100 100 「熱熔接著劑組成物之製造」 實施例8 :1313704 V. Inventive Note (18) Example 6: A hindered amine compound was blended in a resin (C) in the same manner as in Example 4 to obtain an aromatic petroleum resin composition (I) for a hot-melt adhesive. The formulation of the resin composition (I) is shown in Table 2. Example 7: Under a nitrogen gas stream having an oxygen concentration of 2 ppm, a hindered amine compound was formulated with respect to 100 parts by weight of the resin (A) immediately after manufacture, at a stirring speed of 3 rpm. The product, product name ADKSTAB Light Stabilizer LA - 77] 0. 02 parts by weight, to obtain an aromatic petroleum resin composition (J) for hot melt adhesive. The formulation of the resin composition (J) is shown in Table 2. Comparative Example 4: A hindered amine compound was blended in a resin (D) in the same manner as in Example 4 to obtain an aromatic petroleum resin composition (K) for a hot-melt adhesive. The formulation of the resin composition (K) is shown in Table 2. Comparative Example 5: A hindered amine compound was blended in a resin (E) in the same manner as in Example 4 to obtain an aromatic petroleum resin composition (L) for a hot-melt adhesive. The formulation of the resin composition (L) is shown in Table 2. [Table 2] Example 4 Example 5 Sound Example 6 Example 7 Comparative Example 4 Comparative Example 5 Composition ΰ驵 Composition 1 诚JJ Composition κ Composition L Stool amine amide compound house Quantities) 〇.1 U.1 〇1 0.02 0.1 0.1 Aromatic petroleum resin brewing) ABC 100 100 100 A 100 DE 100 100 "Manufacture of hot melt adhesive composition" Example 8:

1313704 五、發明說明（19) 將 EVA〔東曹（股份）、Nip0fiex 0B53C〕100 重量份、 在製造例1所調製的熱熔接著劑用芳香族石油樹脂（A)1 〇〇 重量份、Paraffinwax 155F 25 重量份、PARAFLINT HI 25 重量份、抗氧化劑0.8重量份置入500ml的特氟隆（註冊商 才示）燒杯中’於1 8 0 C保溫的烘箱中使内容物完全溶融之 後，充分地進行攪拌•混合’冷卻，調製熱熔接著劑組成 物。該熱炼接著劑組成物的耐熱蠕變試驗及加熱變質試驗 的結果如第3表所示。 實施例9〜1 0、比較例6〜8 : 除了將熱熔接著劑組成物的原料之EVA、石油樹脂、 蠟、以及抗氧化劑的調配組成如第3表所述加以改變之 外’與實施例8同樣地調製熱熔接著劑組成物。其耐熱蠕 變試驗及加熱變質試驗的結果如第3表所示。 【第3表】1313704 V. Inventive Note (19) 100 parts by weight of EVA (Tosoh Co., Ltd., Nip0fiex 0B53C), 1 part by weight of aromatic petroleum resin (A) for hot-melt adhesive prepared in Production Example 1, and Paraffinwax 155F 25 parts by weight, PARAFLINT HI 25 parts by weight, 0.8 parts by weight of antioxidant, placed in a 500ml Teflon (registered by the registrar) beaker, after fully immersing the contents in an oven insulated at 180 ° C, fully Stirring, mixing, and cooling are performed to prepare a hot melt adhesive composition. The results of the heat-resistant creep test and the heat-deformation test of the hot-melt adhesive composition are shown in Table 3. Examples 9 to 10, Comparative Examples 6 to 8: Except that the composition of the EVA, petroleum resin, wax, and antioxidant of the raw material of the hot-melt adhesive composition was changed as described in Table 3 Example 8 The composition of the hot melt adhesive was similarly modulated. The results of the heat-resistant creep test and the heat deterioration test are shown in Table 3. [Table 3]

SjffiftiMn 比較例6比較例7比較例8 EVA OB54A 3 OB53C 100 100 1nn 100 100 100 Β C D E F Too 100 100 100 100 100 嫌 155F Paraffinwax PARAFLINT H1 25 25 25 ~ —25 25 25 25 25 25 25 25 抗氧化翔(Irganoxl 010) 01 ηΞ— 0 8 0 8 0.8 加熱變質時間(小時） 耐熱蟠變時間(分錠） m T2〇~~ 98 g〇 24 24 96 20 74 96 再者’實施例8〜10的熱熔接著劑組成物係，加熱變質 時間、对熱螺變時間皆很長，在加熱穩定性、耐熱黏著性 方面相當優異。然而，於比較例6 ~ 8，加熱變質時間、耐 7042-6319-PF(N2);Tcshiau.ptd 第25頁 1313704 五、發明說明（20) 熱蠕變時間皆很短，在加熱穩定性、耐熱黏著性方面很 差。 實施例11〜1 4、比較例9〜1 2 : 除了將熱熔接著劑組成物的原料之EVA、石油樹脂、 蠟、以及抗氧化劑的調配組成如第4表所述加以改變之 外，與實施例8同樣地調製熱熔接著劑組成物。其耐熱蠕 變試驗及加熱變質試驗的結果如第4表所示。 【第4表】 加熱變 .耐熱 再者，實施例11〜1 4的熱熔接著劑組成物係 質時間、耐熱蠕變時間的平衡良好，在加熱穩定性 黏著性方面相當優異。然而，於比較例9 ~12厂加熱變質f 間、耐熱蠕變時間的平衡不佳，在加熱穩定性、耐熱黏著 性方面很差。 " 實施例1 5 ~ 1 8 '比較例1 3〜1 4 : /外π π坏竹IL· V Λ、；&冲… 物、蠟、以及抗氧化劑的調配組成如第5表所述加以 成 除了將熱溶接著劑組成物的原料之EVa、石油樹細祖 改 7042-6319-PF(N2);Tcshiau.ptd 第26頁 1313704 五、發明說明（21) 變之外，與實施例8同樣地調製熱熔接著劑組成物。其耐 熱蠕變試驗及加熱變質試驗的結果如第5表所示。 【第5表】 ΪΙΕ例15寅施例16貴胞例17竇施例18 tE蚁例13比較例14 EVA OB54A 3 OB53C 100 100 100 1〇〇 100 1〇〇 伯油UJe C? 組成物 Η 1 J Κ L 100 一 100 100 100 100 100 ® 155F Paraffinwax PARAFLINTH1 ~25 25 25 25~ 25 25 25 25 25 25 25 抗氧化劑(Irganoxl 010) 0.8 U.8 0.8 η η 0.8 0.8 加熱留質Βί®(小時） 耐熱蛹變雕份鐘） 可44以上144以上144以上~~Ϊ44~ .11〇 103 115 1〇〇 48 48 25 67SjffiftiMn Comparative Example 6 Comparative Example 7 Comparative Example 8 EVA OB54A 3 OB53C 100 100 1nn 100 100 100 Β CDEF Too 100 100 100 100 100 155F Paraffinwax PARAFLINT H1 25 25 25 ~ 25 25 25 25 25 25 25 25 Antioxidant Xiang ( Irganoxl 010) 01 ηΞ— 0 8 0 8 0.8 Heating deterioration time (hours) Heat decay time (minutes) m T2〇~~ 98 g〇24 24 96 20 74 96 Furthermore, the heat fusion of Examples 8 to 10 The composition of the coating agent has a long heating and deterioration time and a long time for thermal screwing, and is excellent in heat stability and heat-resistant adhesion. However, in Comparative Examples 6-8, heating deterioration time, resistance to 7042-6319-PF (N2); Tcshiau.ptd page 25 1313704 5. Invention description (20) Hot creep time is very short, in heating stability, The heat resistance is very poor. Examples 11 to 14 and Comparative Examples 9 to 1 2: In addition to the composition of the EVA, petroleum resin, wax, and antioxidant of the raw material of the hot-melt adhesive composition, as described in Table 4, In Example 8, the hot-melt adhesive composition was prepared in the same manner. The results of the heat-resistant creep test and the heat deterioration test are shown in Table 4. [Table 4] Heating change. Heat resistance Further, the hot-melt adhesive compositions of Examples 11 to 14 have a good balance between the system time and the heat-resistant creep time, and are excellent in heat stability and adhesion. However, in the comparative examples 9 to 12, the deterioration of the heat-resistant creep time and the heat-resistant creep time were poor, and the heat stability and heat-resistant adhesiveness were poor. " Example 1 5 ~ 1 8 'Comparative Example 1 3~1 4 : /External π πDirty Bamboo IL·V Λ,; & rush... The composition of the substance, wax, and antioxidant is as described in Table 5. In addition to the EVa of the raw material of the hot-melt adhesive composition, the petroleum tree fine ancestor 7042-6319-PF (N2); Tcshiau.ptd page 26 1313704 5. The invention description (21) is changed, and the embodiment 8 The hot melt adhesive composition was prepared in the same manner. The results of the heat creep resistance test and the heat deterioration test are shown in Table 5. [Table 5] Example 15 寅 Example 16 Your cells Example 17 Sinusion Example 18 tE ant Example 13 Comparative Example 14 EVA OB54A 3 OB53C 100 100 100 1〇〇100 1 〇〇Boiler UJe C? Composition Η 1 J Κ L 100 a 100 100 100 100 100 ® 155F Paraffinwax PARAFLINTH1 ~25 25 25 25~ 25 25 25 25 25 25 25 Antioxidant (Irganoxl 010) 0.8 U.8 0.8 η η 0.8 0.8 Heat retention Βί® (hours) Heat-resistant metamorphosis engraved clock) 44 or more 144 or more 144 or more ~~Ϊ44~.11〇103 115 1〇〇48 48 25 67

再者’實施例1 5〜1 8的熱熔接著劑組成物係，加熱變 質時間、财熱蠕變時間皆很長，在加熱穩定性、财熱黏著 性方面相當優異。然而’於比較例丨3 ~丨4，加熱變質時 間、对熱樓變時間皆很短’在加熱穩定性、财熱黏著性方 面很差。甚且，使用調配受阻胺化合物〇ΰ3重量份以上的 樹脂組成物（G、Η、I)之實施例1 5〜1 7的加熱變質時間、耐 熱蠕變時間，比起使用未調配受阻胺化合物的樹脂組成物 (A、Β、C)之實施例8~10的加熱變質時間、耐熱蠕變時間 都還長’故受阻胺化合物的調配效果相當顯著。Further, the hot-melt adhesive composition of Examples 1 to 5 has a long heating and deterioration time and a creepage time, and is excellent in heat stability and heat retention. However, in the comparative example 丨3 to 丨4, the heating deterioration time and the heat building change time are very short, and the heating stability and the heat and fat adhesion are very poor. Further, the heating deterioration time and the heat-resistant creeping time of Examples 15 to 17 in which the resin composition (G, Η, I) of the hindered amine compound is blended in an amount of 3 parts by weight or more are used, compared to the use of the unadapted hindered amine compound. In the resin compositions (A, Β, C), the heating deterioration time and the heat-resistant creep time of Examples 8 to 10 were both long, so that the compounding effect of the hindered amine compound was remarkable.

1313704圖式簡單說明 7042-6319-PF(N2);Tcshiau.ptd 第28頁Brief description of 1313704 pattern 7042-6319-PF(N2);Tcshiau.ptd第28页

Claims (1)

1313704 六、申請專利範園 利用1質；用芳香族石油樹脂，其特徵在於: 39 4 =)稀 =雙 β I从与 雙虱面積比率為0. 以下、（3)來自 1:7:以；面積比率為〇.5%以下’且分子量分布(Mw/Mn)為 石油2樹Ϊ申：ίϋ f圍第1項所述的熱熔接著劑用芳香族 石油樹月曰，其中如申請專利範園 用芳香族石油樹脂的經值係5mg—_g以下的』接者劑 族石3丄t請I:範圍第1或2項所述的熱嫁接著劑用芳香 族石油樹知，其中係將藉由石 θ ^ ^ II® 1 40^280 ^ ^ ^ " 克拉夫次型催化劑以聚合溫度5"。。。施行 4 —種㈣接著劑用芳香族石油樹脂組成物，其特徵 ，於.相對於如申請專利範圍第丨、2或3項所述的執熔 者劑用芳香族石油樹脂100重量份，則調配受阻胺化合物 0.03〜2重量份而構成。 5. —種製造方法，係如申請專利範圍第4項所述的埶 熔接著劑用芳香族石油樹脂組成物之製造方法，其特徵在 於：將調配受阻胺化合物時之調配器内的氧濃度控制‘ 1 00Oppm 以下。 ' 6. —種熱熔接著劑組成物，其特徵在於：相對於乙 烯.不飽和酯共聚物1〇〇重量份，則調配如申請專利範圍 7042-6319-PF(N2);Tcshiau.ptd 第29頁 1313704 六、申請專利範圍 ------ - 第1、2或3項所述的熱熔接著劑用 中請專利範圍第4項所述的熱溶接著劑用' ^ G j /樹或脂如 組成物50〜15〇重量份、蠟1(M00重量份而構成。 7.如申請專利範圍第6項所述著劑組成物’ f明寻π犯固步 乙酸乙烯酯共聚物。 其中乙烯·不飽和酯共聚物係匕％1313704 VI. Application for patent gardens using 1 quality; using aromatic petroleum resin, characterized by: 39 4 =) dilute = double β I and the area ratio of double bismuth is 0. Below, (3) from 1:7: The area ratio is 〇.5% or less' and the molecular weight distribution (Mw/Mn) is petroleum 2 tree Ϊ :: ϋ ϋ 围 围 围 围 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族 芳香族Fan Park uses aromatic petroleum resin with a value of 5mg-_g or less. 接接剂族石3丄t Please I: The thermal grafting agent described in the first or second item is known as aromatic petroleum tree. The polymerization temperature is 5" by the θ ^ ^ II® 1 40^280 ^ ^ ^ " Kraft subtype catalyst. . . An aromatic petroleum resin composition for a fourth (4) adhesive, which is characterized in that, in comparison with 100 parts by weight of an aromatic petroleum resin for a fluxer as described in claim 2, 2 or 3 of the patent application, The hindered amine compound is formulated in an amount of 0.03 to 2 parts by weight. 5. A method of producing an aromatic petroleum resin composition for a tantalum melt adhesive according to claim 4, characterized in that the oxygen concentration in the dispenser when the hindered amine compound is formulated Control '1 00Oppm or less. 6. A hot-melt adhesive composition characterized by being formulated in an amount of 1 part by weight relative to the ethylene-unsaturated ester copolymer, as in the patent application range 7042-6319-PF (N2); Tcshiau.ptd Page 29, 1313704 VI. Scope of application for patents ------ - For hot melt adhesives as described in items 1, 2 or 3, use ' ^ G j / for hot melt adhesives as described in item 4 of the patent scope The tree or fat is composed of 50 to 15 parts by weight of the composition and wax 1 (M00 parts by weight. 7. The composition of the agent as described in claim 6 of the patent application' f Among them, ethylene·unsaturated ester copolymer system% 7042-63]9-PF(N2);Tcshiau.ptd 第30寅7042-63]9-PF(N2);Tcshiau.ptd第30寅
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