1299346 九、發明說明： 本發明主張於2003年11月19日向韓國專利局提出 申请之韓國專利申請第2003-82342號以及於2004年8月 27日提出申請之韓國專利申請第2〇〇冬68〇1〇號，其内容 完全併入本案參考之。 【發明所屬之技術領域】 3本發明是有關於—種雷射標示用之樹脂組成物，且特 別是有關於一種具有高對比、抗化學性絕佳且可以以雷射 光束輕易婦其形成在物品上之白色文字或標記的透明度 的雷射標示用之樹脂組成物。 【先前技術】 曰检筛印刷(tampon print)或絲網印刷(silk screen print) 是一種廣泛使用在塑膠製品表面上標示文字或符號的技 ，。然而，此種印刷技術十分複雜，且需要專業技術人士 ，執仃並且非常耗時。此外，這一種技術很難在不規則的 ^面上標核字或記號。為了避免原來塗佈社字或記號 ^刮傷或_ ’通常，在形成透明的塗佈層後，必須再進 :丁後處理’例如是以紫外光照射固化。然而，以紫外光固 、、ΐί行Ϊ處理的實例中，材料無法回收再利用。再者，以 ^進行後處理時，工件的污染物或是有毒物質的揮發可 ^ ^造成嚴重的環境污染問題。 縮斤另、種在塑膠製品上標示文字或記號的方法稱之為壓 "示去(compressed labeling method)。然而，這種方法的 缺點是其所紅蚊钱魏科永久性。 1299346 ^ 近年來，為解決上述問題，有一種利用雷射光束在塑 膠製品的表面上標示文字或記號的方法被廣為使用，此種 方法稱為雷射標示法。雖然，此方法在初期所投入的成本 ，，於傳統的標示方法高出許多，但由於雷射標示法具有 許夕的優點，因而被廣泛使用。亦即，此方法可以以電腦 來设计文字或圖案，而且，如有需要，也可以很容易且很 决又有效率地改變文字或記號的設計，以製造精巧且均勻 =標記物品。而且，即使是不是熟悉此項技藝的人亦可以 70美無缺地進行標示的工作。此外，由於這種雷射標示的 方去在執行時並不需要接觸，因此，即使在不規則的表面 亦可輕易地標示文字或記號。由於並不需要使用到溶劑， 口此，不會有環境污染或有毒物質的問題。另一個優點是 材料可回收。因此，此種雷射標示技術的應用發展得相當 快速。 ^在μ射標示的技術中，樹脂製的物品在吸收雷射光能 =後，其表面在低於熔點的溫度會起泡，待雕刻的區域在 ^射雷射光後會被蒸發，同時在所標示的表面會產生化學 =化’而使其顏色改變、漂自。然而，以雷射照射的方式 在黑色的背景上標示白色的文字或記號的實例中，所標示 1文字或記號的自色並不_，這是因為在進行雷射^示 時’產生過量的雷射光束能量而使得殘留的碳沉積或是材 ^發生氧化所致。在使科，紋雷射標示的物品接觸各 種化學物質，則物品的表面易產生化學裂解。例如，物品 的冷藏劑成分在起泡的過程中與起泡劑接觸，或是射出成 1299346 形的物品被污染，而以有機溶劑清洗物品時，物品的抗化 學性則變成一項非常重要的課題。 曰本專利早期公開第2001-302922號揭露一種用於雷 射標示之樹脂組成物，其包括ABS樹脂，馬來硫亞氨-基共 聚合物、氰化的乙烯基化合物、氧化鐵黑色顏料以及其他 的著色劑。然而，其所揭露的樹脂組成物用於雷射標示時， 所標示之物品的白色並不明顯，這是因為殘留的碳沉積在 所標示之物品的表面上，導致其帶有不期望的黃色。 日本專利早期公開第2002-212451號揭露一種在黑色 背景上標不白色文字或記號的方法。此方法係將pMMA樹 脂和ABS樹脂以一定的比例混合來製備一種組成物，並在 其中加入硬酯酸金屬鹽、碳黑以及氧化鈦。然而，所標示 之物品的白度(whiteness)無法令人滿意。 曰本專利早期公開第2001-139758號揭露一種在橡膠 聚合物存在下雷射標示的方法，此方法係至少使用一種選 自於丙，酸g旨、芳香族乙烯化合物、氰化的乙烯基化合物 f及^來硫亞氨、乙烯(甲基)丙烯酸酯酯類一氧化碳基 一/、水CT物樹知、碳黑、氧化鐵、三氧化四鐵或鈦黑所組 成之化口物知群做為黑色顏料。然而，依據使用的經驗， 此組成並不能調整翻度。若是所使用的麟過量，所使 用之材料=射輯能會非常高，㈣的作用會勝過雕 f且所心不的物品的表面會被破壞，導致碳殘留沉積在 义面上1¾無法得到明亮的白色文字或 化學性並不像專利中所揭露的一樣。 躲J几 1299346 【發明内容】 一本發明提供一種雷射標示用之樹脂組成物，當以雷射 光束標示白色文字或記號時可調整透明的程度，並且其所 標示的文字或記號的白度佳且抗化學性非常好。 依據本發明之目的，提供一種雷射標示用樹脂組成物，其 在100重置份的透明樹脂組成物中包括〇·⑻仍至〇·5重量 伤的黑色顏料、黑色染料或其混合物；以及〇•⑻〇丨至〇.5 重畺份的籃色染料、藍色顏料或其混合物。透明樹脂組成 物包括80至99wt%的透明橡膠四元共聚合物組成物，其 含有與芳香乙烯基化合物、（甲基）丙烯酸烧酯以及乙烯基 氰基化合物接枝的橡膠高分子混合物或僅由大粒徑聚丁二 沐橡膠乳膠構成的橡膠高分子，此橡膠高分子混合物包括 一種小粒徑的聚丁二烯橡膠乳膠以及一種大粒徑的聚丁二 _橡膠乳膠；以及1至20 wt%的熱塑性胺基曱酸酯彈性體 或熱塑性醯胺彈性體，其中小粒徑的聚丁二烯橡膠乳膠的 粒徑為600至1500埃，而大粒徑的聚丁二浠橡膠乳膠的粒 徑為2600至5000埃。 依照本發明實施例所述，在橡膠高分子混合物包括小 粒徑的聚丁二烯橡膠乳膠及大粒徑的聚丁二烯橡膠乳膠的 情況下，上述透明橡膠四元共聚合物組成物包括3至15 重量份的小粒徑聚丁二烯橡膠乳膠；5至25重量份的大粒 徑聚丁二烯橡膠乳膠；5至30重量份的芳香基乙烯基化合 物；40至70重量份的（曱基)丙烯酸烷酯化合物；以及1 至20重量份的乙烯基氰基化合物。 1299346 當本發明之組成物應用於半透明物品時，上述黑 料或黑色染料的含量為0.0005至〇 〇3重量份。、 依照本發明另依實施例所述，上述小粒徑的聚丁二烯 橡膠乳膠及大粒徑的聚丁二烯橡膠乳膠的膠體含量為％ 至95%，且膨潤係數為12至3〇。 … 依照本發明另依實施例所述，上述透明橡膠四元共聚 合物組成物包括折射率為15〇8至1 528的橡膠，且其較 佳的含量為5至25重量份。 ’'乂 當本發明之組成物用於半透明物品時，上述熱塑性彈 性體和上述透明橡膠四元共聚合物之間的折射率的差以不 超過0.01較佳。 上述黑色顏料的粒徑以17至4〇nm較佳。 此外，上述藍色染料以蒽醌基染料較佳，上述藍色顏 料了以疋選自於青鈦基顏料（沖也也巧紐⑹basecj。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 〇1〇, its content is fully incorporated into this case. [Technical field to which the invention pertains] 3 The present invention relates to a resin composition for laser marking, and particularly relates to a high contrast, chemical resistance, and can be easily formed by a laser beam. The resin composition used for the laser marking of the white text on the item or the transparency of the mark. [Prior Art] Tampon print or silk screen print is a technique widely used to mark characters or symbols on the surface of plastic products. However, such printing techniques are complex and require skilled personnel, are stubborn and time consuming. In addition, this technique is difficult to mark words or symbols on irregular surfaces. In order to avoid the original application of the word or mark ^scratch or _ ', usually, after the transparent coating layer is formed, it is necessary to carry out the post-treatment, for example, by ultraviolet light irradiation. However, in the case of ultraviolet light curing, the material cannot be recycled and reused. Furthermore, when post-treatment with ^, the volatilization of the workpiece or the volatilization of toxic substances can cause serious environmental pollution problems. The method of marking a character or a mark on a plastic product is called a compressed labeling method. However, the disadvantage of this method is that it is permanent for the red mosquitoes. 1299346 ^ In recent years, in order to solve the above problems, there is a method of using a laser beam to mark characters or marks on the surface of a plastic article, which is called a laser marking method. Although the cost of this method in the initial stage is much higher than the conventional labeling method, it is widely used because of its advantages. That is, this method can design text or graphics with a computer, and, if necessary, can easily and resolutely and efficiently change the design of the text or mark to create a compact and uniform = marked item. Moreover, even those who are not familiar with the art can perform the marking work without any problems. In addition, since the laser markings do not need to be touched during execution, the characters or symbols can be easily marked even on irregular surfaces. Since there is no need to use solvents, there is no problem of environmental pollution or toxic substances. Another advantage is that the material is recyclable. Therefore, the application of such laser marking technology has developed quite rapidly. ^ In the technique of μ-marking, after the resin-made article absorbs the laser light energy, its surface will foam at a temperature lower than the melting point, and the area to be engraved will be evaporated after the laser beam is emitted, and at the same time The marked surface will produce a chemical change that will change its color and float. However, in the case of marking a white text or a mark on a black background in the form of laser irradiation, the self-color of the marked 1 character or symbol is not _, because an excessive amount is generated when the laser is performed. The energy of the laser beam causes residual carbon deposition or oxidation of the material. When the articles marked with the ray and the laser are exposed to various chemicals, the surface of the article is susceptible to chemical cracking. For example, the cold component of the article is in contact with the foaming agent during foaming, or the article that is shot into the shape of 1299346 is contaminated, and when the article is cleaned with an organic solvent, the chemical resistance of the article becomes a very important one. Question. A resin composition for laser marking, which comprises an ABS resin, a maleic sulfoximine-based copolymer, a cyanated vinyl compound, an iron oxide black pigment, and the like, is disclosed in Japanese Laid-Open Patent Publication No. 2001-302922. Other coloring agents. However, when the resin composition disclosed is used for laser marking, the white color of the marked article is not obvious because residual carbon is deposited on the surface of the marked article, resulting in an undesired yellow color. . Japanese Patent Laid-Open Publication No. 2002-212451 discloses a method of marking a white text or a mark on a black background. This method prepares a composition by mixing pMMA resin and ABS resin in a certain ratio, and adding a metal stearate, carbon black, and titanium oxide thereto. However, the whiteness of the marked item is unsatisfactory. A method for laser labeling in the presence of a rubber polymer is disclosed in the method of at least one of the vinyl compounds selected from the group consisting of C, C, aromatic vinyl compounds, and cyanidation. f and ^ to thiocarbamate, ethylene (meth) acrylate esters such as carbon monoxide - /, water CT tree knowledge, carbon black, iron oxide, ferric oxide or titanium black It is a black pigment. However, depending on the experience used, this composition does not adjust the turning. If the used lining is excessive, the material used will have a very high level of energy, and the effect of (4) will be better than that of the embossed and the surface of the object will be destroyed, resulting in the deposition of carbon residue on the surface. Bright white text or chemistry is not as disclosed in the patent.隐JJ1299346 [Invention] The present invention provides a resin composition for laser marking, which can adjust the degree of transparency when a white letter or mark is marked by a laser beam, and the whiteness of the marked character or mark Good and chemically resistant. According to an object of the present invention, there is provided a resin composition for laser marking comprising a black pigment, a black dye or a mixture thereof which is 〇·(8) still up to 重量·5 weight damage in a 100-replacement portion of the transparent resin composition; 〇•(8)〇丨至〇.5 Heavy-duty basket dyes, blue pigments or mixtures thereof. The transparent resin composition includes 80 to 99% by weight of a transparent rubber quaternary copolymer composition containing a rubber polymer mixture grafted with an aromatic vinyl compound, a (meth)acrylic acid ester, and a vinyl cyano compound or only a rubber polymer composed of a large particle size polybutadiene rubber latex, the rubber polymer mixture comprising a small particle size polybutadiene rubber latex and a large particle size polybutadiene rubber latex; and 1 to 20 a wt% thermoplastic amine phthalate elastomer or a thermoplastic guanamine elastomer, wherein the small particle size polybutadiene rubber latex has a particle size of 600 to 1500 angstroms, and the large particle size polybutadiene rubber latex The particle size is from 2,600 to 5,000 angstroms. According to the embodiment of the present invention, in the case where the rubber polymer mixture includes a small particle size polybutadiene rubber latex and a large particle size polybutadiene rubber latex, the above transparent rubber quaternary copolymer composition includes 3 to 15 parts by weight of a small particle size polybutadiene rubber latex; 5 to 25 parts by weight of a large particle size polybutadiene rubber latex; 5 to 30 parts by weight of an aromatic vinyl compound; 40 to 70 parts by weight (fluorenyl) alkyl acrylate compound; and 1 to 20 parts by weight of a vinyl cyano compound. 1299346 When the composition of the present invention is applied to a translucent article, the content of the above black or black dye is from 0.0005 to 重量3 parts by weight. According to another embodiment of the present invention, the small particle size polybutadiene rubber latex and the large particle size polybutadiene rubber latex have a colloid content of from % to 95% and a swelling coefficient of 12 to 3 〇. . According to another embodiment of the invention, the above transparent rubber quaternary copolymer composition comprises a rubber having a refractive index of from 15 to 8 528, and a preferred content thereof is from 5 to 25 parts by weight. When the composition of the present invention is used for a translucent article, the difference in refractive index between the above thermoplastic elastomer and the above transparent rubber quaternary copolymer is preferably not more than 0.01. The above black pigment preferably has a particle diameter of 17 to 4 Å. Further, the above blue dye is preferably a fluorenyl dye, and the above blue pigment is selected from the group consisting of a cerium-based pigment (Chong also 巧巧纽(6) basecj
Pigment)、銘藍基顏料、深藍基顏料(phthalocyan based pigment)所組成之族群其中之一。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，作詳細說明如下。 【實施方式】 本發明將詳述如下。 本發明之雷射標示樹脂組成物包括100重量份的透明 樹脂組成物[(A)+(B)]中含有⑹0 0005至〇·5重量份的黑色 顏料、黑色染料或其混合物以吸收雷射光，以及(D)〇 〇〇〇1 1299346 至〇·5重量份用以增加所標示之文字或記號白度的藍色顏 料、藍色染料或其混合物，其中透明樹脂組成物[(Α)+(Β)] 包括(Α)80至99wt%的透明橡膠四元共聚合物組成物，組成 物含有與芳香乙烯基化合物、（曱基）丙烯酸烧酯以及乙烯 基氰基化合物接枝的橡膠高分子混合物，橡膠高分子混合 物係由小粒徑的聚丁二烯橡膠乳膠及大粒徑的聚丁二烯橡 膠乳膠所組成；或僅由大粒徑聚丁二烯橡膠乳膠以構成透 明橡膠四元共聚合物，此共聚合物具有絕佳的耐衝擊性、 耐化學性及加工性；以及(B)1至2〇 wt%的熱塑性胺基甲酸 酯彈性體或熱塑性醯胺彈性體，其折射率與用來增加耐化 學性的透明橡膠聚合物的折射率大致相同。 (A)透明橡膠四元共聚合物 /一透明橡膠四元共聚合物的製備方法包括⑻製備小游 f聚丁二烯橡輒膠’其平均粒徑為獅至15⑻埃膠體令 量為70至95%，以聚合起始劑和二丁烯在如反 反應膨濁係數㈣ling index)為12至3 = :二浠橡膠乳膠，其平均粒徑為26〇〇 =二 470.950,，index)^ 乳膠之粒徑以及⑷連續或= :、重量份的芳香基;稀基化 基化合物，並在65至8。。。進行接枝共聚的乙《氮 1299346 人—由於使用於本發明的聚丁二烯橡膠乳膠的粒徑及膠體 :量有报大的影響，這一些影響包括物品的透明 二取㈣度’因此在以透明的橡膠四元乳膠取代大粒捏 二二丁，烯橡膠乳膠時，選擇適當混合比例的小粒徑聚; 一$橡膠乳膠及大粒徑聚丁二烯橡膠乳膠是十分重要的。 換吕之，當橡膠乳膠的粒徑小時，可增加物品的透明度 =衝擊性並且其流動性會減少。當粒徑增加時，耐衝擊性 變，，但透明度降低。因此，為增加透明度和耐衝擊強度， ^疋】粒瓜橡添乳膠和大粒徑橡膠乳膠之適當混合比是非 ^重要的。若是橡膠乳膠之膠體含量低，在接枝&合^橡 膠乳膠中的單體會過度膨潤，亦即，外觀粒徑增加，透明 f降^耐衝擊強度增加。然、而，奸橡膠乳膠的膠體含 里過咼，膨潤的範圍變小，可增加透明度，但，外衝擊吸 收力（external impact absorbing capability)降低，亦即，耐衝 擊性下降。 ^用於本發明的單體混合物的折射率對透明度有極大的 影響，並且可藉由單體的含量錢混合_來調整之。接 枝組份的總折射率與聚丁二稀的折射率實質相同可確保皇 透明度，即大社518。在接枝組份中，苯乙烯的折射物 為159，甲基丙烯酸甲醋的折射率約為149，丙烯猜的折 射率約為1.518。 在透明橡膠四το共聚合物的組份中，聚丁二稀橡膠成 分主要是用來增加物品的衝擊強度，其較佳 橡膠四元共聚合物總含量的5至25重量份。若是聚 12 1299346 橡膠成分的含量少於5重量份，則非常難以具有足夠的耐衝 擊強度。若是聚丁二烯橡膠成分的含量大於25重量份，則 會因為過量而使機械強度下降。 、 芳香乙烯基化合物主要是用來提升加工性，並且推測 其。卩分可提供一些能量給即將藉由吸收雷射光能而熔融 膨潤的照射部以及可被雷射光束熔化的染料和顏料。芳香 乙烯基化合物的含量是透明橡膠四元共聚合物總重量的15 至30重量份，以使透明橡膠四元共聚合物的折射率 1.518 〇 再者，（曱基）丙烯酸烷酯化合物可吸收較少量的雷射 光，且可能起泡而不會被雕刻（engraved)，藉此可增加光擴 散的效率，增加所標示的文字或記號的白度。而且，（甲基) 丙烯酸烷酯化合物在進行雷射照射時其材料比較不會被破 壞，因此可增加最終物品對於氣候變化的耐候性 (weatherability)。 乙烯基氰基化合物可增加抗化學性，其使用的較佳量 為透明橡膠四元共聚合物總重量的丨至如重量份。若是乙烯 基氰基化合物的使用量低於1重量份，本發明之樹脂組成物 所形成的最終物品的抗化學性將會降低。若是乙烯基氰基 化合物的使用量超過20重量份，則所製備的聚合物將帶有 車父強的頁色調，而影響雷射標示後所標示之文字或記號的 可見度。 在進行接枝聚合反應時，化合物可以以整份(lump)的 方式、多步驟加入的方式、連續加入的方式加入於反應室 13 1299346 本發明中’可結合整份加人的方式以及連續加入的 方式來調整應用。 後：本發明之翻橡膠四元絲合物的製備方法將詳述如 (1)製備聚丁二烯橡膠乳膠 (a)製備小粒徑橡膠乳膠 至重里&的l3’二丁埽、1至4重量份的乳化劑、0.1 份的聚合起始劑、G G重量份的電解液、〇」 1份的分子量控糊以及9G至13G重量份的蒸顧水 正77的方式加人於反應室巾，並於5岐65 t進行反應約 至12小¥。接著’另外將G.G5y .2重量份的分子量控制 別以整份砂式加从應冑巾，於55錢。c反應約5至15 小時，以形成小粒徑的聚丁二烯橡膠乳膠，其平均粒徑為 600埃至·埃，膠體含量為7〇%至95%，膨潤係數為似 30 〇 本發明所使用的乳化劑之實例包括烷芳基磺酸鹽、鹼 金屬甲基烧基硫酸鹽、石黃化燒基醋、脂肪酸急(fatty acid soap)、松香酸的鹼金屬鹽等，其可單獨使用或將至少兩種 化合物合併使用。聚合起始劑可以是水溶性的過硫酸鹽化 合物或過氧化物，亦可使用氧化還原起始劑系統作為起始 劑。水溶性的過硫酸鹽可溶化合物的較佳例包括過硫酸^ 化合物、過硫酸钟化合物等。過氧化物起始劑之實例包括 氫過氧化異丙苯(cumene hydroperoxide)、氫過氧化二異丙 基苯(diisopropyl benzenehydroperoxide)、第三丁基過氧化 14 1299346 氫（tertiary butyl hydroperoxide)、對 _ 甲燒過氧化氫 (p-methane hydroperoxide)-過氧化苯（benzoylperoxide) 等’其可單獨使用或將至少兩種化合物合併使用。亦可使 用偶氮二異丁腈(Azobisisobutyronitrile，AIBN)。 本發明所使用的電解液之實例包括KC1、NaC卜 KHC03、NaHC03、K2C03、Na2C03、KHS03、NaHS03、 K4P207、K3P〇4、Na3P04、K2HP04、Na2HP04等等。這一 些化合物可單獨使用或將至少兩種化合物合併使用。較佳 的分子量控制劑包括硫醇(mercaptans)等。 (b)製備大粒徑橡膠乳膠(熔化小粒徑橡膠乳膠） 將3至4重量份的水溶性醋酸溶液緩慢加入於1〇〇重量 份粒徑為600埃至1500埃的小粒徑橡膠乳膠，其粒徑為6〇〇 埃至1500埃，膠體的含量為70%至95%，膨潤係數為12至 3〇，以攪拌製造顆粒體，接著，停止攪拌以製備大粒徑橡 膠乳膠，其粒徑為2600埃至5000埃，膠體的含量為7〇%至 95%，膨潤係數為12至3〇。用來增加耐衝擊性的大粒徑 膠乳膠的製備可採用直接聚合之方式。然而，採用聚合方 法必須耗費相當長的時間且限於形成含有高膠體含量^大 粒徑橡膠乳膠。因此，為能在短時間之内製造具有高膠體 含量的大粒徑橡膠乳膠，較佳的方法是先製備高膠體^量 的小粒徑橡膠乳膠，再將酸性物質加入於小橡职 中以製備大粒魏膠。 料⑽ (2)製備接枝共聚合物 以上述方法製備含有3至15重量份的小粒徑聚二丁烯 1299346 橡膠乳膠和5至25重量份的大粒徑聚丁二烯橡膠乳膠的混 合物，並將此混合物加入15至3〇重量份的芳香乙烯基化合 物、40至70重量份的（甲基)丙浠酸烧酯化合物以及丨至2〇重 量伤的乙烯基氰基化合物，與〇·2至〇·6重量份的乳化劑、 0.2至0.6重量份的分子量控制劑以及〇〇5至〇3重量份的聚 合起始劑進行接枝共聚合反應。較佳的接枝共聚合反應係 於65 C至80 °C進行大約4至7小時。在聚合反應中，（甲基) 丙烯酸烷酯化合物的實用例包括曱基丙烯酸甲酯、丙烯酸 甲酯等。芳香乙烯基化合物的實用例包括苯乙烯、α•甲基 苯乙烯、鄰·乙基苯乙烯、對-乙基苯乙烯、乙烯基甲苯等。 乙烯基氰基化合物的實用例包括丙烯腈、甲基丙烯腈、α_ 乙基丙烯腈等。聚合反應中所使用之乳化劑的實例包括烷 芳基磺酸鹽、鹼金屬硫酸鹽、磺化烷基酯、脂肪酸皂、松 香酸的鹼金屬鹽等，其可單獨使用或將至少兩種化合物合 併使用。分子量控制劑的典型例包括叔-十二烷硫醇。聚合 起始劑包括過氧化物以及還原劑構成的氧化還原觸媒系統 化合物，其中過氧化物例如是氫過氧化異丙苯、氫過氧化 二異丙基苯或過硫化物，還原劑例如是甲醛次硫酸氫鈉 (sodium formaldehyde sulfoxylate)、乙二胺四乙酸鈉、硫酸 亞鐵、葡萄糖、吡咯鈉(sodium pyrrolinate)、硫酸鈉。在進 行聚合反應後，乳膠的聚合轉換率不少於98%。以氯化鈣 水溶液使乳膠凝結，再除水乾燥，以獲得透明橡膠四元共 聚合物粉末。 (B)熱塑性彈性體 16 1299346 、熱塑性彈性體是用以在中間製程中，如起泡過程中用 來增加對溶劑的抗化學性。清洗試劑是用來移除射出成带 後的π染物或是最終物品在實際使用的過程巾可能接觸^ -種溶劑。在詩標科，為助於起泡，會添加各種 添加劑，而此熱塑轉性體有助於分散這—些無機^加 劑並可避免錢添加㈣響雷射標示狀樹脂組成物之 耐，擊強度。若是雷射標示用之樹脂僅使用透明橡踢四元 共聚合物’其祕標示的能力佳，減鮮性差，因此可 能會在中間製程或實際使㈣接觸各種化學品而產生 it f塑性彈性體可用來增加透明橡膠四元共聚合_ 抗化學性而不影響其透明度。 明龍熱麵縣彈㈣或熱塑㈣轉性體的透 日橡，?7〇共聚合物具有良好的相容性(⑺寧咖㈣，這 用，例如熱塑性胺基甲酸輯性體或熱塑性 笑之的醯胺基和透明橡膠四元共聚合物中的羧酸 偶極鍵所造成的結果。此外，絲和苯 是埶ί性=交互作用可改善彈性體的相容性。因此，若 與透日^^ 酯彈性體或熱塑性醯胺彈性體的折射率 可維持Ji^70共聚合物相似，職彼此之_交互作用 、、、寺/、所形成之混合組成物的總透明度。 熱塑月雷射標示物品的例子中，並不需要考慮 子中，射率。在形成半透财射標示物品的例 明橡膠四酸醋彈性體或熱繼胺彈性體和透 來口物之間的折射率的差以不超過〇 〇1為較 17 1299346 佳。若是熱塑性胺基甲酸酯彈性體或熱塑性醯胺彈性體和 透明橡膠四元共聚合物之間的折射率的差大於〇〇1，則隨 著所使用的熱塑性彈性體含量的增加，樹脂組成物所形^ 的最終物品的透明度將變差。 乂 由於熱塑性胺基甲酸酯彈性體或熱塑性醯胺彈性體具 有高親水性，因此，所形成的最終產品在實際使用時不^ 吸附灰塵，並可增進其低溫的耐衝擊性以及伸長度。θ (c)黑色顏料、黑色染料或其混合物 黑色顏料、黑色染料或其混合物可提供聚合分子鏈吸 收雷射光束能量後膨潤所需要的能量，且可被氧化除色 (discolored)，以使白色文字或標記可被肉眼所見。因此， 所使用的材料的特性以及用量對於文字或標記的白度及/ 或可見度(visibility)有非常大的影響。 又 曰若是黑色顏料使用過量，雖然可以雷射光束能量的雷 射量進行雷射標示，但卻會產生負面影響。亦即，會造: 2度的氧化殘留，且有一些未氧化的黑色顏料會殘留在背 厅、顏色上並且會因為提供了過量的能量，雕刻會勝過起 泡，^所標示之物品的表面將因為樹脂組成物全部易於氧 ^和奴化而變得混亂(messy)。相反地，若是黑色顏料的用 量^少，提供給標示表面的能量不足，難以使聚合物分子 鏈膨潤，f射標示所需的雷射絲能量增加，將使得所印 記的表面帶黃色調，或導致雷射標示的效能變差。在形成 明雷射標示物品的例子中，標示時所需的雷射光束的 能1增加，黑色顏料或黑色染料的使用量必須有所限制以 18 1299346 維持透明度。 (c-1)黑色顏料 佳的=?碳黑時，其較佳的粒徑為17至—，且較 口11111，^:5至().5重1份。若是黑色顏料的粒徑小於 量係盘i進度和耐衝擊強度。黑色顏料的使用 ^制、射標不的物品為不透明或透明有關。 色句ir=的物品時，黑色練的侧量與背景的 (Λ；Β^ =:r將重變二；==低 :，，。當背景的顏色充么二 需:黑。當在灰色背景上標示白色標記時， 而要大里的…色顏料，則可以使用氧化欽。 在製造透明的物品的例子中 所使用的碳黑的量以〇._5至〇〇 :度，:,， 調整透明度，則可將碳黑與里 。如有需要 =因IS透:的物品時，由於碳黑所能吸收的能量 有限，因此在進仃雷射標示工作時 ^ 是碳黑的含量低於0.0005重量份， S田射此里。右 能量不足，無法在透明或是;收的雷射光束的 缺。相县，甚h 丰透的物品上標示文字或記 唬仁疋右疋進行印記時的雷射能量過高， -些組份㈣為照射高能的雷射光束而發生不期望的石= 19 1299346 現象。若是碳黑的含量超過0.03重量份，透明 難以製造透明或是半透明的物品。 (C-2)黑色染料 在調整透明或是半透明物品的背景顏色時，通常 =黑色染料。在一實例中，係單獨使用碳黑來調整透明曰产， =而其所能調整的空間有限。因此，爲能適當地調整透明 =可採用分散性良好的黑色染料結合碳黑。黑色染料的 =使用量為G_1至G.1重量份。若要將背景改變成其他 顾色，則可將各種顏色的染料結合黑色染料一起使用。 (D)監色染料、藍色顏料及其混合物 =用藍色染料、藍色顏料及其混合物可改善所要標示 之2字或記號的白度和可見度。在進行雷射標示時，雷射 =軚不之物品的表面會因為吸收能量氧化而使其表面帶有 汽色，而k色染料或藍色顏料可消除這一種現象，以進一 二曰加所‘示之文字或記號的白度和可見度。尤其是當材 料，能讀的雷射光束能錄少時，像是透贼是半透明 ，口口，則必須增加雷射光束照射的強度，如此，將導致物 。口^於氧化。在此例中，可依據氧化的程度調整藍色染料 或監色顏料的使用量，以使得所標示的白色文字或記號清 晰可見。 本發明所使用的藍色染料的實例包括蒽醌基染料。藍 色顏料的貫例包括菁鈦基顏料(phthalocyanine based P gment)、銘藍基顏料、深藍基顏料(ultramarine based pigment)等等。 20 1299346 士通常’以藍色染料或藍色顏料做為增加白度的添加劑 Ν' ’其車父佳的使用量為0 00010 5重量份。 同時，本發明之雷射標示用樹脂組成物更包括氧化 鈦，其可在雷射光束照射時助於樹脂的起泡。此外，氧化 鈦可用來赃紐的穿透度歧在進行雷射標科改盖所 ^不之區域的白度。^是氧化鈦的顆粒變大，氧化鈦將使 $田射文字或標記帶有黃色調，顯現良好的光遮蔽 能力。若是氧化鈦的顆粒變小，將使得雷射標示的文字或 —己稍微帶有藍色調，而增加所標示之文字或標記的可見 度。此外’為了幫助樹脂起泡，可以添加各種無機添加劑 如滑石以及氧化鈦。在此财，若是無機添加劑分散不當， 所標示之物品的表©將變得不平整。因此，較佳的是採用 母料批次(master bateh)的方式。使用無機添加劑會破壞物 品的耐衝擊誠。然而，由於本發明之組成包括熱塑性胺 基甲酸輯性體或熱塑性_彈性體，因此，可減緩财衝 擊強度減損的情形’並且其可有效地分散錢添加劑。 將以上所述的所有成分，包括透明橡膠四元共聚合物 ，末、熱雜彈性體、黑.色鋪、黑色純、藍色染料、 監士顏料料混合，並在約為朦^關為挪⑶溫度下 私C藉以依知、本發明以母料粒料(master 方式 製備樹脂組成物。以母料粒料(pellet)或片料(chip)製備時， 如有需要可添加抗氧化劑、熱穩定劑、潤賴、耐候性增 進劑（weatherability enhancer)、抗靜電劑、抗直菌劑 (antlfungalagent)等等。此外’可選擇性添加用來調整顏色 21 1299346 的他種著色劑。 本發明將以以下的實例更進一步詳述於後，然其並非 用以限制本發明之範圍。 預備例1 1-(1):製備聚二丁烯橡膠乳膠 (a) 製備小粒徑橡膠乳膠 將110重量份的蒸餾水、100重量份的1，3_丁二烯單 體、1.2重量份的松香钾(potassium rosinate)乳化劑、1·5重 量份的油酸卸(potassium oleate)、0.15重量份Na2C〇3電解 液、〇·5重量份的KHC03以及0·3重量份叔十二硫醇 (tert-dodecyl mercaptan) (TDDM)分子量控制劑以整份 (lump)的方式置於充氮的聚合反應器（壓力鍋）中。將反應的 溫度升溫至55°C，然後，在反應的初期將0.3重量份整份的 亞硫酸鉀起始劑加入於反應器中進行反應1〇小時。之後， 再於反應器中加入〇·〇5重量份的TDDM於65 °C下進行反應 8小時，以完成反應，形成粒徑為1000埃、膠體含量為9〇〇/0 且膨潤係數為18的橡膠乳膠。 (b) 製備大粒徑的橡膠乳膠(熔化小粒徑橡膠乳膠） 將所製備的小粒徑橡膠乳膠1〇〇重量份加入於反應器 中，並將攪拌速度控制於lOOrpm，溫度控制於30°C，接著， 將3.5重量份的7wt%的醋酸水溶液緩慢加入於反應器中反 應1小時。之後，停止攪拌，將小粒徑的橡膠乳膠熔化以製 備大粒也的橡膠乳膠，大粒徑的橡膠乳膠的粒徑為3000 埃’膠體含量為9G%，膨潤係數為17。 22 1299346 1-(2):製備接枝共聚合物 將100重量份的蒸餾水、〇·2重量份的油酸鈉乳化劑、 18.72重量份的甲基丙烯酸甲酯、7·28重量份的苯乙烯、3·33 重量份的丙烯腈、〇·2重量份的TDDM、0.048重量份的焦磷 酸納、0.012重量份的葡萄糖(dextrose)、〇 〇〇1重量份硫酸 鐵以及0·04重篁份的氫過氧化異丙苯（cumene hydroperoxide)以整份的方式加入於5〇。〇充氮的反應器 中’該反應器中已置入12重量份以上述方法製備的大粒徑 橡膠乳膠。然後，將反應的溫度升溫至73它反應2小時。然 後’將的乳化混合溶液連續加入於反應器中反應4小時，此 乳化混合溶液包含60重量份的蒸餾水、〇·4重量份的油酸 納、37·44重量份的甲基丙烯酸曱醋、ΐ4·56重量份的苯乙 烯、6.67重量份的丙烯腈、〇·25重量份的TDDM、〇·〇48重 量份的焦磷酸鈉、0.012重量份的葡萄糖、〇.001重量份的 硫酸鐵以及0.10重量份的氫過氧化異丙苯。接著，升溫至 76 °C，再反應1小時，以完成反應。聚合反應的轉換率約 為99.5%,固態凝結含量為〇.1%。之後，以氯化鈣水溶液 使乳膠固化，再清洗之，以形成粉末，此粉末稱之為透明 橡膠四元共聚合物Al〇 預備例2 :製備接枝共聚合物 將100重量份的蒸餾水、〇·2重量份的油酸鈉乳化劑、 11.98重量份的甲基丙烯酸甲酯、4.52重量份的笨乙稀4 重量份的丙烯腈、0.2重量份的叔十二硫醇、〇 Q48重量份 的焦填酸納、0.012重量份的葡萄糖、〇·〇〇ΐ重量份硫酸鐵 23 1299346 以及0.04重量份的氫過氧化異丙苯以整份的方式加入於50 它充氮的反應器中，該反應器中已置入8重量份以上述方法 製備的小粒徑橡膠乳膠以及10重量份以上述方法製備的大 粒徑橡膠乳膠。然後，將反應的溫度升溫至73°C反應2小 時。然後，將乳化混合溶液連續加入於反應器中反應4小 時，此乳化混合溶液包含70重量份的蒸餾水、0.4重量份的 油酸鈉、35.92重量份的曱基丙烯酸甲酯、13.58重量份的 苯乙烯、12重量份的丙烯腈、〇·25重量份的叔十二硫醇、 0.048重量份的焦磷酸鈉、0 012重量份的葡萄糖、〇 〇〇1重 量份的硫酸鐵以及〇·1〇重量份的氫過氧化異丙苯。接著， 升溫至76 °C，再反應1小時，以完成反應。聚合反應的轉 換率約為99.8%，固態凝結含量為ο」]%。之後，以氯化|弓 水溶液使乳膠固化，再清洗之，以形成粉末，此粉末稱之 為透明橡膠四元共聚合物A2。 預備例3 將150重量份的蒸餾水、〇·5重量份的油酸鈉乳化劑、 49·74重量份的曱基丙烯酸曱酯、17.26重量份的苯乙烯、8 重置份的内烯腈、〇·5重量份的叔十二硫醇、0.096重量份 的焦填酸納、〇·024重量份的葡萄糖、〇 〇〇2重量份硫酸鐵 以及108重量份的氫過氧化異丙苯以整份的方式連續加入 充滿氮氣且已置入25重量份以上述方法製備的大粒 徑橡膠乳膠的反應器中反應5小時，然後升溫至80。(3再反應 1小時。聚合反應的轉換率約為99.2%，固態凝固含量為 〇·3%。之後，以氯化鈣水溶液使乳膠固化，再清洗之，以 24 1299346 形成粉末，此粉末稱之為透明橡膠四元共聚合物A3。 例1 將97重量份由預備例1所製備的透明橡膠四元共聚合 物A1以及做為樹脂組成物基本成分的3重量份折射率為 1.518的熱塑性胺基甲酸酯彈性體$〇1〇11化學股份有限公 司製造的K470A)以及做為著色劑的〇 〇5重量份的碳黑和 0.03重罝份的藍色染料（Bayer股份有限公司製造的 Macrolex Blue 05)置於混合器中並混合之。接著，以雙鏍 桿擠壓機擠壓造粒，擠壓柱係調整在約為]^^。之後，將 所製得的顆粒射出成形，以製備3毫米厚的碟狀樣品 (plate-shaped sample)。其後，以Nd : YAG 雷射標示機⑽ 組名稱·· SY-2000)將所製備的碟狀樣品雷射標*，此機a 是由ΕΟ·股份有限公司製造，雷射波長為職nm = 動頻率為5kHz，雷射能量為3瓦特。 、 例2〜6 以相同於例m方式對幻所示組成的樣品 示’並評估各個樣品的物性。其評估之結果 射軚 例7〜立 衣i所不。 以相同於例1的方式，但雷射能量改變為3〜 表2所示之組成的樣品進行雷射標示，並評估各 品的物性。其評估之結果如下表2所示。 估各個樣 比較例1 ^及增加白度的著色助齊 二相同於例！的方式對表3所示組成的樣 示，其除了熱塑性彈性體以^^。 $仃雷射標 之外 25 1299346 僅使用透明的橡膠四元取 物性，其評估騎果如^。評估各個樣品的 ib較例2〜R 不 性。其評估之絲射標示，麟估各個樣品的物 二==;備二已標示之物品的物性係 Izod衝墼強磨 在1/8英对的樣品中形成—個缺口，使強 測試機ASTMD2S6測量衝擊強度。文用福衝擎強度 透明廑 又 以ASTMD 1003测量透明度。 折射率 以ASTMD 542測量折射率。 標示度 以肉眼觀測評估標示度。 抗化學性-1 將1/8对抗張強度之樣品置於〇 7%將被固定的應變爽 具(strainzig)上’並將其浸於環戊烷中1分鐘，之後取出， 再置於室溫4小時。轉細—般的賴機即論如公司 型號：42〇2]評估樣品浸於環戊烷前、後的拉伸量 (d〇ngati〇n)，並以下式1估算拉伸維持率（elongation maintenance rate): 26 1299346 [式i] 曰拉伸維持率(〇/〇),浸泡後之拉伸量)/(浸泡前之拉伸 量)]xlOO。 抗化皋性-2 將!/8"t抗張強度之樣品置於〇·7%將被固定的應變夹 具上^並覆蓋薄紗紙(tissuepaper)，再以滴管加入5次己烧。 此處係以一般的測試機台[Instr〇n公司型號·· 評估 逐滴加入己烷前、後樣品的拉伸量並以下式1估算拉伸維持 率： [式2] 拉伸維持率(％) = [(逐滴加入後的拉伸量)/(逐低加入Pigment), Minglan based pigment, one of the ethnic groups consisting of phthalocyan based pigment. The above and other objects, features and advantages of the present invention will become more apparent from the <RTIgt [Embodiment] The present invention will be described in detail below. The laser marking resin composition of the present invention comprises 100 parts by weight of the transparent resin composition [(A) + (B)] containing (6) 0 0005 to 5 parts by weight of a black pigment, a black dye or a mixture thereof to absorb the laser light. And (D) 〇〇〇〇1 1299346 to 〇·5 parts by weight of blue pigment, blue dye or a mixture thereof for increasing the whiteness of the marked character or mark, wherein the transparent resin composition [(Α)+ (Β)] comprises (Α) 80 to 99% by weight of a transparent rubber quaternary copolymer composition containing a rubber grafted with an aromatic vinyl compound, a (meth) acrylate and a vinyl cyano compound. Molecular mixture, rubber polymer mixture is composed of small particle size polybutadiene rubber latex and large particle size polybutadiene rubber latex; or only large particle size polybutadiene rubber latex to form transparent rubber a meta-copolymer having excellent impact resistance, chemical resistance and processability; and (B) 1 to 2% by weight of a thermoplastic urethane elastomer or a thermoplastic phthalamide elastomer, Its refractive index and transparent rubber used to increase chemical resistance Substantially the same as the refractive index of the polymer. (A) Preparation method of transparent rubber quaternary copolymer/transparent rubber quaternary copolymer comprises (8) preparing a small-f-butadiene rubber ruthenium whose average particle size is lion to 15 (8) angstrom colloidal volume is 70 To 95%, the polymerization initiator and dibutene in the reaction index (four) ling index is 12 to 3 =: diterpene rubber latex, the average particle size is 26 〇〇 = two 470.950, index) ^ The particle size of the latex and (4) continuous or =:, parts by weight of the aromatic group; the dilute base compound, and is between 65 and 8. . . B. Copolymerization of B. Nitrogen 1,299,346 people - due to the large particle size and colloid: the amount of polybutadiene rubber latex used in the present invention, these effects include the transparency of the article (four degrees). When a transparent rubber quaternary latex is used to replace the large-size kneaded di-n-butyl rubber, a small particle size of a suitable mixing ratio is selected; a rubber latex and a large-diameter polybutadiene rubber latex are very important. For Lu, when the rubber latex has a small particle size, it can increase the transparency of the article = impact and its fluidity will decrease. When the particle size is increased, the impact resistance is changed, but the transparency is lowered. Therefore, in order to increase the transparency and impact strength, the proper mixing ratio of the granule rubber latex and the large particle rubber latex is not important. If the colloidal content of the rubber latex is low, the monomer in the graft & rubber latex will be excessively swollen, that is, the appearance particle size is increased, and the transparent f lowering resistance is increased. However, the colloidal rubber latex has a colloidal inclusion, and the swelling range is small, which increases the transparency, but the external impact absorbing capability is lowered, that is, the impact resistance is lowered. The refractive index of the monomer mixture used in the present invention has a great influence on the transparency, and can be adjusted by the monomer content. The total refractive index of the graft component is substantially the same as the refractive index of the polybutadiene dilute to ensure transparency. In the graft component, the refractory of styrene was 159, the refractive index of methyl methacrylate was about 149, and the refractive index of propylene was about 1.518. In the component of the transparent rubber tetra-co-copolymer, the polybutadiene rubber component is mainly used to increase the impact strength of the article, which is preferably 5 to 25 parts by weight based on the total content of the rubber quaternary copolymer. If the content of the rubber component of the poly 12 1299346 is less than 5 parts by weight, it is very difficult to have sufficient impact strength. If the content of the polybutadiene rubber component is more than 25 parts by weight, the mechanical strength may be lowered due to the excess. The aromatic vinyl compound is mainly used to improve the processability and is presumed to be. The enthalpy provides some energy to the illuminating portion that will be melted by absorbing the laser light energy and the dye and pigment that can be melted by the laser beam. The content of the aromatic vinyl compound is 15 to 30 parts by weight based on the total weight of the transparent rubber quaternary copolymer, so that the refractive index of the transparent rubber quaternary copolymer is 1.518 〇, and the (alkyl) acrylate compound can be absorbed. A smaller amount of laser light, and possibly blistering, is not engraved, thereby increasing the efficiency of light diffusion and increasing the whiteness of the marked text or mark. Moreover, the (meth)acrylic acid alkyl ester compound is relatively uncorrupted when subjected to laser irradiation, thereby increasing the weatherability of the final article for climate change. The vinyl cyano compound can increase the chemical resistance, and the preferred amount thereof is from 丨 to parts by weight based on the total weight of the transparent rubber quaternary copolymer. If the amount of the vinyl cyano compound used is less than 1 part by weight, the chemical resistance of the final article formed by the resin composition of the present invention will be lowered. If the vinyl cyano compound is used in an amount exceeding 20 parts by weight, the prepared polymer will have a strong page color tone and affect the visibility of the characters or marks indicated by the laser mark. In the graft polymerization, the compound can be added to the reaction chamber in a lump manner, in a multi-step manner, and continuously added. 13 1299346 In the present invention, the method can be combined with the entire addition and continuous addition. The way to adjust the app. After: the preparation method of the retort rubber quaternary compound of the present invention will be described in detail as (1) preparing a polybutadiene rubber latex (a) to prepare a small particle size rubber latex to the heavy & l3' dibutyl hydrazine, 1 To 4 parts by weight of the emulsifier, 0.1 part of the polymerization initiator, GG parts by weight of the electrolyte, 1 part of the molecular weight controlled paste, and 9G to 13G parts by weight of the water is positively added to the reaction chamber. Towels, and reacted at about 5 岐 65 t to about 12 small ¥. Then, the molecular weight of G.G5y.2 parts by weight was additionally controlled by adding a whole amount of sand to the towel, at 55 money. c reacting for about 5 to 15 hours to form a small particle size polybutadiene rubber latex having an average particle diameter of 600 angstroms to angstroms, a colloidal content of 7 to 95%, and a swelling coefficient of 30 〇. Examples of the emulsifier to be used include an alkylarylsulfonate, an alkali metal methylsulfonate sulfate, a pyruvate vinegar, a fatty acid soap, an alkali metal salt of rosin acid, and the like, which may be used alone. Use or combine at least two compounds. The polymerization initiator may be a water-soluble persulfate compound or a peroxide, and a redox initiator system may also be used as a starter. Preferable examples of the water-soluble persulfate-soluble compound include a persulfate compound, a persulfate compound, and the like. Examples of peroxide initiators include cumene hydroperoxide, diisopropyl benzene hydroperoxide, tert-butyl peroxidate 14 1299346 hydrogen (tertiary butyl hydroperoxide), _ P-methane hydroperoxide-benzoylperoxide or the like can be used alone or in combination of at least two compounds. Azobisisobutyronitrile (AIBN) can also be used. Examples of the electrolytic solution used in the present invention include KC1, NaC, KHC03, NaHC03, K2C03, Na2C03, KHS03, NaHS03, K4P207, K3P〇4, Na3P04, K2HP04, Na2HP04 and the like. These compounds may be used singly or in combination of at least two compounds. Preferred molecular weight controlling agents include mercaptans and the like. (b) Preparation of a large particle size rubber latex (melted small particle size rubber latex) 3 to 4 parts by weight of a water-soluble acetic acid solution is slowly added to 1 part by weight of a small particle size rubber latex having a particle diameter of 600 angstroms to 1500 angstroms , having a particle size of 6 〇〇 to 1500 Å, a colloid content of 70% to 95%, a swelling coefficient of 12 to 3 Torr, and agitating the granules, and then stopping the stirring to prepare a large-diameter rubber latex. The particle size is from 2,600 angstroms to 5,000 angstroms, the colloid content is from 7 to 95%, and the swelling coefficient is from 12 to 3 angstroms. The large particle size latex used to increase the impact resistance can be prepared by direct polymerization. However, the polymerization method has to take a considerable amount of time and is limited to the formation of a rubber latex containing a high colloid content. Therefore, in order to be able to produce a large-diameter rubber latex having a high colloid content in a short period of time, a preferred method is to prepare a high-molecular-weight small-sized rubber latex, and then add the acidic substance to the small rubber. Preparation of large size Wei gum. (10) (2) Preparation of Graft Copolymer A mixture of 3 to 15 parts by weight of a small particle size polydibutene 1299346 rubber latex and 5 to 25 parts by weight of a large particle size polybutadiene rubber latex is prepared by the above method. And adding 15 to 3 parts by weight of an aromatic vinyl compound, 40 to 70 parts by weight of a (meth)propionic acid ester compound, and a vinyl cyano compound having a weight of 2 to 〇, and 〇 2 to 6 parts by weight of an emulsifier, 0.2 to 0.6 parts by weight of a molecular weight controlling agent, and 5 to 3 parts by weight of a polymerization initiator are subjected to graft copolymerization. The preferred graft copolymerization is carried out at 65 C to 80 ° C for about 4 to 7 hours. In the polymerization reaction, practical examples of the (meth)acrylic acid alkyl ester compound include methyl methacrylate, methyl acrylate, and the like. Practical examples of the aromatic vinyl compound include styrene, ?-methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyltoluene, and the like. Practical examples of the vinyl cyano compound include acrylonitrile, methacrylonitrile, α-ethyl acrylonitrile, and the like. Examples of the emulsifier used in the polymerization reaction include an alkylarylsulfonate, an alkali metal sulfate, a sulfonated alkyl ester, a fatty acid soap, an alkali metal salt of abietic acid, and the like, which may be used alone or at least two compounds. Combined use. Typical examples of the molecular weight controlling agent include t-dodecyl mercaptan. The polymerization initiator includes a peroxide and a redox catalyst system compound composed of a reducing agent, wherein the peroxide is, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide or persulfide, and the reducing agent is, for example, Sodium formaldehyde sulfoxylate, sodium edetate, ferrous sulfate, glucose, sodium pyrrolinate, sodium sulfate. After the polymerization, the polymerization conversion ratio of the latex is not less than 98%. The latex was coagulated with an aqueous solution of calcium chloride and dried by water to obtain a transparent rubber quaternary copolymer powder. (B) Thermoplastic elastomers 16 1299346. Thermoplastic elastomers are used to increase the chemical resistance to solvents in intermediate processes such as foaming. The cleaning reagent is used to remove the π dye that is ejected into the tape or the final article may be exposed to the solvent in the actual process. In the poetry standard, in order to help foaming, various additives are added, and the thermoplastic transducing body helps to disperse these inorganic additives and can avoid the addition of (4) the resistance of the laser-labeled resin composition. Strike strength. If the resin used for laser marking only uses the transparent rubber-kick quaternary copolymer, its ability to mark the secret is good, and the fresh-keeping property is poor. Therefore, it may be in the intermediate process or actually make (4) contact with various chemicals to produce it f plastic elastomer. Can be used to increase the transparent rubber quaternary copolymerization _ chemical resistance without affecting its transparency. Minglong hot noodles bombs (four) or thermoplastic (four) transgenic body of the Japanese rubber, ? 7 〇 copolymer has good compatibility ((7) Ning coffee (four), which uses, for example, thermoplastic amine formic acid or thermoplastic The result of laughing the carboxylic acid dipole bond in the amide-based and transparent rubber quaternary copolymers. In addition, silk and benzene are 埶 性 = interaction can improve the compatibility of the elastomer. The refractive index of the fusible elastomer or thermoplastic amide elastomer can be maintained similar to that of the Ji^70 copolymer, the interaction between the interaction, the temple, and the total transparency of the mixed composition formed. In the example of a plastic laser marking article, it is not necessary to consider the rate of the shot. Between the example rubber tetraacetate elastomer or the hot-step amine elastomer and the perforated material forming the semi-permeable indexing article The difference in refractive index is not more than 〇〇1, which is better than 17 1299346. If the difference in refractive index between the thermoplastic urethane elastomer or the thermoplastic phthalamide elastomer and the transparent rubber quaternary copolymer is greater than 〇〇 1, with the increase in the content of thermoplastic elastomer used, resin The transparency of the final article of the shape of the object will be deteriorated. 乂Because the thermoplastic urethane elastomer or the thermoplastic phthalamide elastomer has high hydrophilicity, the final product formed does not absorb dust in actual use. And can improve its low temperature impact resistance and elongation. θ (c) black pigment, black dye or a mixture of black pigment, black dye or a mixture thereof can provide the energy required for the polymeric molecular chain to absorb the energy of the laser beam and swell. And can be oxidized and discolored so that the white text or mark can be seen by the naked eye. Therefore, the characteristics and amount of the material used are very large for the whiteness and/or visibility of the text or mark. In addition, if the black pigment is used excessively, although it can be laser marked with the laser energy of the laser beam energy, it will have a negative effect. That is, it will produce: 2 degree oxidation residue, and some unoxidized Black pigments will remain in the back hall, color, and because of the excess energy provided, the engraving will outperform the blistering, and the surface of the marked item will In the case where the resin composition is easily oxidized and enslaved, it becomes messy. Conversely, if the amount of the black pigment is small, the energy supplied to the surface of the label is insufficient, and it is difficult to swell the polymer molecular chain. The increase in the energy of the laser will cause the imprinted surface to be yellowish or cause the performance of the laser marking to deteriorate. In the example of forming a bright laser marking article, the energy of the laser beam required for marking is increased by 1. The amount of black pigment or black dye used must be limited to maintain transparency with 18 1299346. (c-1) Black pigment is good = carbon black, its preferred particle size is 17 to -, and the mouth is 11111, ^: 5 to (). 5 weights 1 part. If the particle size of the black pigment is less than the amount of the tray i progress and impact strength. The use of black pigments, the target is not opaque or transparent. When the color sentence ir= the item, the black side and the background (Λ; Β^ =:r will change to two; == low:,,. When the background color is filled with two: black. When in gray When the white mark is marked on the background, and the color pigment of the big one is used, the oxidation can be used. The amount of carbon black used in the example of manufacturing a transparent article is adjusted by 〇._5 to 〇〇: degrees, :,, Transparency can be used to turn carbon black into the inside. If there is a need for the product due to IS: because the energy absorbed by the carbon black is limited, the carbon black content is less than 0.0005 when the laser marking operation is performed. Weight, S field shot here. Right energy is insufficient, can not be transparent or; the lack of laser beam received. Xiang County, even h abundant items marked on the text or recorded on the right side of the mark The laser energy is too high, and some components (4) cause undesired stone = 19 1299346 phenomenon when irradiating a high-energy laser beam. If the carbon black content exceeds 0.03 parts by weight, it is difficult to manufacture transparent or translucent articles. (C-2) Black dye is usually used when adjusting the background color of transparent or translucent items. In one example, carbon black is used alone to adjust the transparency, and there is limited space for adjustment. Therefore, in order to properly adjust the transparency, a black dye having good dispersibility can be used in combination with carbon black. The amount of black dye used is G_1 to G.1 parts by weight. To change the background to other colors, dyes of various colors can be used in combination with black dyes. (D) Color-control dyes, blue pigments and their Mixture = use blue dye, blue pigment and their mixture to improve the whiteness and visibility of the 2 words or symbols to be marked. When performing laser marking, the surface of the laser = 軚 之 会 会 会 会The surface is provided with a vapor color, and the k-color dye or the blue pigment can eliminate this phenomenon, in order to add the whiteness and visibility of the words or symbols shown, especially when the material can read the thunder. When the beam of light can be recorded, if the thief is translucent, the mouth must increase the intensity of the laser beam, so that the object will be oxidized. In this case, it can be adjusted according to the degree of oxidation. Blue dye or The amount of the color pigment used is such that the marked white characters or marks are clearly visible. Examples of the blue dye used in the present invention include a mercapto dye. Examples of the blue pigment include a phthalocyanine based P gment ), Ming blue-based pigments, ultramarine based pigments, etc. 20 1299346 Usually 'blue dye or blue pigment as an additive to increase whiteness ' ' 'The use of its car is 0 00010 parts by weight. Meanwhile, the resin composition for laser marking of the present invention further comprises titanium oxide, which can assist the foaming of the resin when irradiated by the laser beam. In addition, titanium oxide can be used for the permeability of the neon. The whiteness of the area where the laser standard is changed. ^ is that the particles of titanium oxide become larger, and the titanium oxide will make the text or mark with a yellow tone, showing good light shielding ability. If the particles of titanium oxide become smaller, the text marked by the laser or the blue mark will be slightly increased, and the visibility of the marked text or mark will be increased. Further, in order to help the resin to foam, various inorganic additives such as talc and titanium oxide may be added. In this case, if the inorganic additives are improperly dispersed, the table © of the marked items will become uneven. Therefore, it is preferred to use a master batch (master bateh). The use of inorganic additives can destroy the impact resistance of the product. However, since the composition of the present invention includes a thermoplastic urethane composition or a thermoplastic elastomer, the situation in which the damage of the impact strength is reduced can be alleviated' and it can effectively disperse the money additive. Mix all the ingredients described above, including transparent rubber quaternary copolymer, end, thermal hybrid, black, color, black pure, blue dye, and sergeant pigment materials, and At the temperature of the (3) temperature, it is known that the resin composition is prepared by masterbatch in the master method. When preparing as a masterbatch pellet or chip, an antioxidant may be added if necessary. A heat stabilizer, a moisturizing agent, a weatherability enhancer, an antistatic agent, an antifungal agent, etc. Further, a coloring agent for adjusting the color 21 1299346 can be selectively added. The following examples will be further described in detail below, but are not intended to limit the scope of the present invention. Preparation Example 1 1-(1): Preparation of polydibutene rubber latex (a) Preparation of small particle size rubber latex 110 Parts by weight of distilled water, 100 parts by weight of 1,3-butadiene monomer, 1.2 parts by weight of rosin potassium emulsifier, 1.5 parts by weight of oleic acid oleate, 0.15 parts by weight of Na2C 〇3 electrolyte, 〇·5 parts by weight of KHC03 and 0·3 The amount of tert-dodecyl mercaptan (TDDM) molecular weight control agent is placed in a nitrogen-filled polymerization reactor (pressure cooker) in a lump manner. The temperature of the reaction is raised to 55 ° C. Then, 0.3 parts by weight of the potassium sulfite initiator in the initial stage of the reaction was added to the reactor for 1 hour, after which 5 parts by weight of TDDM was added to the reactor at 65 ° C. The reaction was carried out for 8 hours to complete the reaction to form a rubber latex having a particle diameter of 1000 angstroms, a colloidal content of 9 Å/0 and a swelling coefficient of 18. (b) Preparation of a rubber latex of a large particle size (melted small particle size rubber) Latex) The prepared small particle size rubber latex was added to the reactor in an amount of 1 part by weight, and the stirring speed was controlled at 100 rpm, the temperature was controlled at 30 ° C, and then 3.5 parts by weight of a 7 wt% aqueous acetic acid solution was slowly added. The reaction was added to the reactor for 1 hour. Thereafter, the stirring was stopped, and the rubber latex of a small particle size was melted to prepare a rubber latex of a large particle size. The rubber latex of a large particle size had a particle size of 3000 angstroms and a colloid content of 9 G%, swelling. The coefficient is 17. 22 1299346 1-(2) : Preparation of graft copolymer 100 parts by weight of distilled water, 2 parts by weight of sodium oleate emulsifier, 18.72 parts by weight of methyl methacrylate, 7.28 parts by weight of styrene, 3.33 parts by weight Acrylonitrile, ruthenium 2 parts by weight of TDDM, 0.048 parts by weight of sodium pyrophosphate, 0.012 parts by weight of dextrose, 1 part by weight of iron sulfate, and 0. 04 parts by weight of isopropyl peroxide Benzene hydroperoxide was added in 5 parts in a portion. In the nitrogen-filled reactor, 12 parts by weight of the large-diameter rubber latex prepared by the above method was placed in the reactor. Then, the temperature of the reaction was raised to 73 and it was reacted for 2 hours. Then, the emulsified mixed solution was continuously added to the reactor for 4 hours, and the emulsified mixed solution contained 60 parts by weight of distilled water, 4 parts by weight of sodium oleate, 37.44 parts by weight of methacrylate vinegar, Ϊ́4·56 parts by weight of styrene, 6.67 parts by weight of acrylonitrile, 〇·25 parts by weight of TDDM, 〇·〇 48 parts by weight of sodium pyrophosphate, 0.012 parts by weight of glucose, 〇.001 parts by weight of iron sulfate, and 0.10 parts by weight of cumene hydroperoxide. Subsequently, the temperature was raised to 76 ° C and further reacted for 1 hour to complete the reaction. The conversion rate of the polymerization reaction was about 99.5%, and the solid condensation content was 〇.1%. Thereafter, the latex is solidified with an aqueous solution of calcium chloride, and washed to form a powder. This powder is referred to as a transparent rubber quaternary copolymer Al 〇 Preparation Example 2: Preparation of a graft copolymer 100 parts by weight of distilled water, 2 parts by weight of sodium oleate emulsifier, 11.98 parts by weight of methyl methacrylate, 4.52 parts by weight of stupid ethylene 4 parts by weight of acrylonitrile, 0.2 parts by weight of t-dodecyl mercaptan, 〇Q 48 parts by weight The sodium pyroate, 0.012 parts by weight of glucose, ruthenium and osmium weight of iron sulfate 23 1299346 and 0.04 parts by weight of cumene hydroperoxide are added in part to 50 of its nitrogen-filled reactor. In the reactor, 8 parts by weight of the small particle size rubber latex prepared by the above method and 10 parts by weight of the large particle size rubber latex prepared by the above method were placed. Then, the temperature of the reaction was raised to 73 ° C for 2 hours. Then, the emulsified mixed solution was continuously added to the reactor for 4 hours, and the emulsified mixed solution contained 70 parts by weight of distilled water, 0.4 parts by weight of sodium oleate, 35.92 parts by weight of methyl methacrylate, and 13.58 parts by weight of benzene. Ethylene, 12 parts by weight of acrylonitrile, 25 parts by weight of tert-dodecyl mercaptan, 0.048 parts by weight of sodium pyrophosphate, 0,012 parts by weight of glucose, 1 part by weight of iron sulfate, and 〇·1〇 Parts by weight of cumene hydroperoxide. Then, the temperature was raised to 76 ° C, and further reacted for 1 hour to complete the reaction. The conversion rate of the polymerization reaction was about 99.8%, and the solid condensation content was ο"]%. Thereafter, the latex is solidified with a chlorinated aqueous solution of the bow and then washed to form a powder which is referred to as a transparent rubber quaternary copolymer A2. Preparation Example 3 150 parts by weight of distilled water, 5 parts by weight of sodium oleate emulsifier, 49.74 parts by weight of decyl decyl acrylate, 17.26 parts by weight of styrene, 8 parts by weight of internal acrylonitrile, 5 parts by weight of tert-dodecyl mercaptan, 0.096 parts by weight of sodium pyrophosphate, 024 parts by weight of glucose, 2 parts by weight of iron sulfate, and 108 parts by weight of cumene hydroperoxide The reaction was carried out continuously for 5 hours in a reactor filled with nitrogen and placed in 25 parts by weight of the large-diameter rubber latex prepared by the above method, and then heated to 80. (3 further reaction for 1 hour. The conversion rate of the polymerization reaction is about 99.2%, and the solidification content is 〇·3%. Thereafter, the latex is solidified with an aqueous solution of calcium chloride, and then washed to form a powder of 24 1299346, which is called powder. It is a transparent rubber quaternary copolymer A3. Example 1 97 parts by weight of the transparent rubber quaternary copolymer A1 prepared in Preparation Example 1 and 3 parts by weight of a thermoplastic resin having a refractive index of 1.518 as a basic component of the resin composition K470A) manufactured by urethane elastomer, 〇1〇11 Chemical Co., Ltd., and 5 parts by weight of carbon black and 0.03 parts by weight of blue dye as a coloring agent (manufactured by Bayer Co., Ltd.) Macrolex Blue 05) is placed in the mixer and mixed. Next, the granulation was carried out by a double boring extruder, and the extrusion column was adjusted to be about φ. Thereafter, the obtained pellets were injection molded to prepare a plate-shaped sample having a thickness of 3 mm. Thereafter, the prepared dish sample laser mark* was prepared by Nd:YAG laser marking machine (10) group name·· SY-2000). This machine a was manufactured by ΕΟ·股份有限公司, and the laser wavelength was for the job nm. = The dynamic frequency is 5 kHz and the laser energy is 3 watts. Examples 2 to 6 show the samples of the phantom composition in the same manner as in the example m and evaluate the physical properties of the respective samples. The results of the evaluation are shots. Example 7~ Liyi i does not. The samples in the same manner as in Example 1 except that the laser energy was changed to 3 to the composition shown in Table 2 were subjected to laser marking, and the physical properties of the respective articles were evaluated. The results of the evaluation are shown in Table 2 below. Estimate the various comparisons 1 ^ and increase the whiteness of the color of the two help the same! The manner of the composition shown in Table 3 is in addition to the thermoplastic elastomer. $仃雷射标 Outside 25 1299346 Use only transparent rubber quaternary property, which evaluates riding fruit as ^. The ib of each sample was evaluated to be inferior to Example 2 to R. The silk mark of the evaluation, Lin estimated the sample of each sample ===; the physical properties of the marked article Izod rushed to form a gap in the 1/8 inch pair of samples, making the strong test machine ASTMd2S6 The impact strength was measured. Wenfu rushing strength, transparent 廑 and measuring transparency with ASTMD 1003. Refractive Index The refractive index was measured in ASTM D 542. Marking degree The degree of labeling is evaluated by visual observation. Chemical Resistance-1 Place 1/8 of the tensile strength sample on 〇7% of the strain strain that will be fixed and immerse it in cyclopentane for 1 minute, then remove and place in the chamber. Warm for 4 hours. The fine-grained machine is as follows: company model: 42〇2] evaluate the amount of stretching before and after immersion in cyclopentane (d〇ngati〇n), and estimate the tensile maintenance rate (elongation) Maintenance rate): 26 1299346 [Formula i] 曰 stretch retention (〇 / 〇), the amount of stretching after soaking) / (stretching amount before immersion)] x lOO. Anti-Chemistry-2 Place the sample of !/8"t tensile strength on a strain clamp that will be fixed on 〇·7% and cover the tissue paper, then add 5 times to the simmered tube. Here, the tensile test rate is estimated by the general test machine [Instr〇n model evaluation of the amount of stretching of the sample before and after the dropwise addition of hexane and the following formula 1: [Formula 2] Tensile maintenance ratio ( %) = [(stretching amount after drop addition) / (adding low
ί例 " 1 2 3 4 5 6 边明的四元 橡膠共聚合物 Α1 97 97 97 98 Α2 95 A3 97 熱塑性彈性體 Β1 3 5 3 2 Β2 3 Β3 3 - ； 黑色顏料和 黑色染料 碳黑 0.05 0.05 0.05 0.05 0.05 0.05 黑色染料 ----- 增加白度之 著色助劑 藍色染料 0.03 0.03 0.03 0.03 0.03 藍色顏料 0.02 ---- 評估項 耐衝擊強度 10 15 25 10 11 -------- J1_ 透明度 不透明 不透明 不透明 不透明 不透明 不透明 抗化學性-1 93% 97% 100% 96% 100% 90%__ 抗化學性-2 67% 75% 96% 72% 100% 65% 背景顏色 黑 黑 黑 黑 黑 J：_ 標示的顏色 白 白 白 白 白 白 標示度 佳 佳 佳 佳 佳 一—-—* 隹 一能量（瓦特） 3 —Τ 3 3 3 ------ 3 —--J 前的拉伸量)]xlOO。 ___ 表 1 Ν·Β·) A1 :為橡膠含量的12 wt% ’折射率為1·517 ; 27 1299346 A2 :為橡膠含量的18 wt%，折射率為1518 ; A3 :為橡膠含量的25 wt%，折射率為丨518 ; B1 :熱塑性胺基甲酸酯彈性體的折射率為1518 (Kolon化學股份有限公司製造的K470A); B2 :熱塑性胺基甲酸酯彈性體的折射率為1525 (Kolon化學股份有限公司製造的K285PCAT); B3 ··熱塑性醯胺彈性體的折射率為151 (Sany〇化學公 司製造的PelestatNC6321); 碳黑·韓國Nippi製造的黑色顏料〇7 ; 黑色染料· Mitsubishi公司製造的Diaresin Black B ; 藍色染料：Bayer公司製造的透明藍3R (Macr〇lex Blue 3R);以及 藍色顏料· Holiday公司製造的群青〇5(Ultramarine Blue 05) ° 表2例例" 1 2 3 4 5 6 Quaternary rubber conjugated polymer Α1 97 97 97 98 Α2 95 A3 97 Thermoplastic elastomer Β1 3 5 3 2 Β2 3 Β3 3 - ; Black pigment and black dye carbon black 0.05 0.05 0.05 0.05 0.05 0.05 Black dye----- Adding whiteness to the coloring aid Blue dye 0.03 0.03 0.03 0.03 0.03 Blue pigment 0.02 ---- Evaluation of impact strength 10 15 25 10 11 ----- --- J1_ Transparency Opaque Opaque Opaque Opaque Opaque Opaque Opaque Chemical Resistance -1 93% 97% 100% 96% 100% 90%__ Chemical Resistance - 2 67% 75% 96% 72% 100% 65% Background Color Black Black, black and black J: _ The color of the mark is white, white and white, and the degree is good. Jia Jia Jia——* 隹一 energy (Watt) 3 —Τ 3 3 3 ------ 3 —--J Stretch))xlOO. ___ Table 1 Ν·Β·) A1: 12 wt% of rubber content 'refractive index is 1.517; 27 1299346 A2: 18 wt% of rubber content, refractive index is 1518; A3: 25 wt% of rubber content %, refractive index is 丨518; B1: thermoplastic urethane elastomer has a refractive index of 1518 (K470A manufactured by Kolon Chemical Co., Ltd.); B2: thermoplastic urethane elastomer has a refractive index of 1525 ( K285PCAT manufactured by Kolon Chemical Co., Ltd.; B3 · Thermoplastic polyamide elastomer has a refractive index of 151 (Pelestat NC6321 manufactured by Sany Chemical Co., Ltd.); Carbon black · Black pigment 〇7 manufactured by Nippi, Korea; Black dye · Mitsubishi Made by Diaresin Black B; Blue Dye: Transparent Blue 3R (Macr〇lex Blue 3R) manufactured by Bayer; and Ultramarine Blue 05 by Blue Pigment· Holiday Company Table 2
28 1299346 評估項 背景顏色 黑色 黑色 墨藍色 (blackish blue) 灰青色 (grayish blue) 灰青色 深灰色 (dark gray) 標示的顏色 白色 白色 白色 白色 白色 白色 標不度 佳 佳 佳 佳 佳 佳 雷射能量（瓦特） 25 25 20 7 3 7 29 1299346 表3 比較例 1 2 3 4 5 6 7 — ___— 聚合物 Α1 100 70 30 ABS 25 25 30 30 SAN 25 30 70 70 ΡΜΜΑ 50 75 70 10 一^^ 黑色顏料或 黑色染料 碳黑 0.05 0.15 0.5 0.5 0.5 0.5— 三氧化四鐵 0.3 增加白度 之著色助劑 氧化鈦 0.3 0.2 評估項 耐衝擊強度 10 14 7 3 12 17 19^ 透明度 不透明 不透明 不透明 不透明 不透明 不透明 不透明 抗化學性_1 23% 75% 23% 16% 65% 84% 75% 25% 抗化學性-2 59% 77% 22% 18% 53% 82% 80% 25% 背景顏色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 標示的顏色 白色 白色 白色 白色 白色 白色 白色 白色 標不度 佳 差 差 差 差 差 差 差 一 诲射能重（瓦特） 3 25 3 7 3 3 3 1 Ν·Β·) ABS : 丁二烯/苯乙烯/丙稀腈(wt%)=5〇/36/15， SAN :苯乙烯/丙烯腈(wt%)=75/25， PMMA : LG化學股份有限公司製造的正_850。 如表1所示，例1〜6之方法所製備的樣品在浸入環戊烷 或己烧後的拉伸雜率佳。觀察例卜6所製備的樣品被桿 示的狀態。觀測的結果顯示所標示的樣品在不透明黑 景上的（白度)佳。 例7〜9所製備的樣品全部是半透明。使 =時，=維持率佳，所標示之樣品在半透日収色j上 的（白度)隹。 例1〇〜12所製備的不透明樣品的背景顏色改變，立上 具有良好的(白度)。各個樣品在浸入 %戍炫或己燒後的拉伸維持率佳。 30 1299346 t匕較例1的成品的背景色為不透明的黑色且所標示的 文子f己號全部為狀況良好的白色Μ旦，在浸入環姐或 己烷後的拉伸維持因子顯著下降。 3例2:8的成品的背景色為不透明的黑色且所標示 部分的樣品在浸人環戊烧或己烧 後的拉伸維持率下降。 制&、如2述’本發明之祕雷射標*狀齡組成物所 „組成物可形成高可見度的白色記號而不會帶有普色 砸且可㈣地聰所標*之物品的透明度。，、 服—f'、、:本發明已以較佳實施例揭露如上，然其並非用以 =發明’,任何熱習此技藝者，在不脫離本發明之精神 範圍内田可作些許之更動與潤飾，因此本發明之伴護 範圍當視_之巾請糊範_界定者為準。u之㈣ 【圖式簡單說明】 益 一”、 【主要元件符號說明】 盔 3128 1299346 Approved background color black black blue (grayish blue) gray cyan dark gray (dark gray) color white white white white white white label (Watt) 25 25 20 7 3 7 29 1299346 Table 3 Comparative Example 1 2 3 4 5 6 7 — ___— Polymer Α 1 100 70 30 ABS 25 25 30 30 SAN 25 30 70 70 ΡΜΜΑ 50 75 70 10 One ^^ Black Pigment or black dye carbon black 0.05 0.15 0.5 0.5 0.5 0.5 - Fe3O3 0.3 Increase the whiteness of the coloring agent titanium oxide 0.3 0.2 Evaluation of the impact strength 10 14 7 3 12 17 19^ Transparency opaque opaque opaque opaque opaque opaque Chemical resistance _1 23% 75% 23% 16% 65% 84% 75% 25% Chemical resistance - 2 59% 77% 22% 18% 53% 82% 80% 25% Background color black black black black black black Black black marked color white white white white white white white white label good difference difference difference difference difference shot energy ( Special) 3 25 3 7 3 3 3 1 Ν·Β·) ABS : Butadiene/styrene/acrylonitrile (wt%)=5〇/36/15, SAN: styrene/acrylonitrile (wt%) =75/25, PMMA: _850 manufactured by LG Chem. As shown in Table 1, the samples prepared by the methods of Examples 1 to 6 had a good stretching ratio after immersing in cyclopentane or hexane. The state in which the sample prepared in Example 6 was shown was observed. The results of the observations show that the indicated samples are better (whiteness) on the opaque black background. The samples prepared in Examples 7 to 9 were all translucent. When =, the ratio is good, and the indicated sample is (whiteness) 半 on the semi-transparent day color. The background color of the opaque sample prepared in Examples 1 to 12 was changed to have a good (whiteness). The tensile retention of each sample after immersion in % 戍 or hexane was good. 30 1299346 t The background color of the finished product of Comparative Example 1 was opaque black and the marked texts were all in good condition, and the tensile maintenance factor after immersion in Ring Sister or hexane was significantly reduced. The background color of the 3:8 finished product was opaque black and the tensile strength of the sample of the indicated portion was reduced after immersion in cyclopentane or after burning. The composition of the present invention can form a high-visibility white mark without a plain color and can be (4) Transparency., 服-f',: The present invention has been disclosed in the preferred embodiment as above, but it is not intended to be used in the invention, and any person skilled in the art can make a few changes without departing from the spirit of the invention. The change and the retouching of the present invention, therefore, the scope of the invention is determined by the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _