TW200422343A - Polyoxymethylene resin composition for laser marking - Google Patents

Abstract

Disclosed is a polyoxymethylene resin composition for laser marking, including 100 parts by weight of polyoxymethylene, 0.01-3.0 parts by weight of carbon black, and 0.01-5.0 parts by weight of dihydrazide, characterized in that the use of the dihydrazide as a thermal stabilizer results in enhanced thermal stability of molded articles and decreased emission of formaldehyde. Thus, the polyoxymethylene composition can function to exhibit superior laser marking results, and to improve abrasion resistance, durability, chemical resistance and fatigue resistance. Further, the molded articles from the polyoxymethylene composition are subjected to laser marking with an Nd:YAG laser, whereby white or multi-colored shapes can be displayed on multi-colored articles and also designs can be freely modified through connection with auto cads, thus realizing desired quality of the articles.

Description

200422343 玖、發明說明 [發明所屬之技術領域] 一般而言，本發明係有關於一種雷射標記之聚縮醛樹 月曰組成物，具體而言，係有關於一種用於雷射標記之聚縮 駿樹脂組成物；其中，係使用二醯肼化合物作為熱安定劑 以A進运射;f示5己之模製品的熱安定性，並減少製造過程中 的曱酿釋放（emission)。 [先前技術] 一般而言，為了在樹脂模製品或塗覆有樹脂之模製品 上標記所需的標識、符號、以及圖樣，通常係使用熱強化 油墨（heat-reinforced)進行印刷法。然而，當縮醛係結晶樹 脂時，在印刷過程會導致油墨黏著性不佳的結果。因此， 進行該印刷程序時必需進行預處理俾獲得較高的黏著性。 再者，根據一般習用的情況，油墨印刷部分對於低溫、磨 耗、及化學腐蝕性的抗性並不充分。 因此，為了解決使用熱強化油墨之印刷法所衍生的問 題，而提出藉由雷射照射標記熱塑性塑膠之方法。 雷射標記法的優點係在於在需要經常變換之小量操作 上的快速標記，不需要預處理以及後處理，以及製程簡單 不而頜外的材料與加工步驟。再者，藉由與電腦輔助繪圖 幸人體之連線，可以不受限地修改標記圖樣；因此，所需成 本較低。然而，相較於印刷製程，雷射標記製程較不適合 廣泛地用於彩色製品。 雷射標記技術中所使用的雷射包括Nd: YAG(鈥：釔 92491 射按…人進仃橾記之材料，使用Md : YAG 运射可以在金屬、塑膠、矽、太 ,^ ^ 木材、紙、皮革、以及玻璃 上形成雷射標記0再者，Nd : yag +似女兩七人丄 ACj雷射亦用於切割材料或 甘 標記。此外，上述可用以進行雷射標記之表面， 亦可根據表面標記的方法進行 丁于雕凸錦或雕刻。亦即，該 加工表面經挖刻而形成經雕 ,_ 4Φ λα ^ ° 經褪色進行…J表面’或该標的物表面係 記的效果。 表面經汙雕凸飾而產生標 就標記的類型而言，i方 钟映播— ”万法包括用於夜視電器開關與 k膠4示5己之雕刻’盆係葬由带 八η 9由^射^射部分之蒸發而完全移 除毛邊，用於塑膠標記以200422343 发明. Description of the invention [Technical field to which the invention belongs] In general, the present invention relates to a laser-marked polyacetal tree composition, specifically, to a laser-marked polymer Resin resin composition; wherein, the dihydrazine compound is used as the thermal stabilizer to be injected with A; f shows the thermal stability of the molded product and reduces the emission during the manufacturing process. [Prior art] In general, in order to mark required marks, symbols, and patterns on a resin molded article or a resin-coated molded article, a heat-reinforced printing method is generally used. However, when the acetal-based crystalline resin is used, the result is poor ink adhesion during printing. Therefore, it is necessary to perform a pretreatment when performing this printing process to obtain high adhesion. Furthermore, according to the general practice, the resistance of the printed portion of the ink to low temperature, abrasion, and chemical corrosion is insufficient. Therefore, in order to solve the problems arising from the printing method using thermally strengthened ink, a method of marking thermoplastics by laser irradiation has been proposed. The laser marking method has the advantages of fast marking on small operations that require frequent changes, no pre-processing and post-processing, and simple process, but also extra-jaw materials and processing steps. Furthermore, by connecting to a computer-assisted drawing fortunately, the mark pattern can be modified without restriction; therefore, the required cost is low. However, compared to the printing process, the laser marking process is less suitable for being widely used in color products. Lasers used in laser marking technology include Nd: YAG (—: Yttrium 92491, which is a material that people can remember. Using Md: YAG can be used for metal, plastic, silicon, silicon, wood, Laser marks are formed on paper, leather, and glass. Furthermore, Nd: yag + two or seven female ACJ lasers are also used to cut materials or marks. In addition, the above surfaces can be used for laser marking. Ding Yu carving or engraving can be carried out according to the method of surface marking. That is, the processed surface is carved to form warped carving, _ 4Φ λα ^ ° faded ... J surface 'or the effect of the surface of the object . The surface is stained with convex carving to produce the label. As far as the type of marking is concerned, “Fang Zhongying—“ Wan Fa includes a carving for night vision electrical switches and K glue. ^ 射 ^ The evaporation of the shot part completely removes the burrs, and is used for plastic marking to

刻與褪色，其係同時地對,二:外之大部分金W 與褪色，該經照射之表面係 订㈣ 鍵盤之塑膠標記，或使用古似°刀毛邊，以及用於例如 袍色與漂白，其传率之金屬表面之褪色標記之 變化，而非在標記表面進行雕刻。 顏色 就此項而言，曰+車 ..,,,.^ 專利特開昭58^7496號揭示一種較 間早的標記製程，A私过丄 裡孕乂 知糟由雷射加工表面物 成所期望之標記，亦gp ^ I物理又化而形 ，…、加工法。再者，日本專 昭63A6790號、61_4 本專利特開 306285號揭示_種_ 犰以及曰本專利特開平1- 射標記製程。糟由添加能夠祕色及脫色之填料的雷 上述使用此種填料+ 基材係經顏料染色，^ 的特徵係在於，該 用不同於基材之顏色進行標記製 9249] 6 南對比之白色標記之 t 4寸別是，針對在黑色基材上形成 田射襟記組成物的研究。 如’曰本專利特開平11-i 40271號係揭干播勹社 聚縮醛遍石卢g夕干， 現係揭不一種包括 為〗7… 运射標記樹脂組成物，該碳黑之顆粒尺寸 油吸收至/〇nm，且每100毫克之DBP(鄰苯二甲酸二丁醋） 上述之 200 €升。在此實例中，在黑色基材上使用 標記。樹脂組成物可以形成高對比性與高亮度之白色 成物/而’由上述組成物所形成之模製品中，由於該組 機找转具有碳黑及顏料，故熱安定性較低，而造成褪色及 械械特性降低的結果。 成铷在美國弟5,218,041號專利中，係揭示-種聚縮醛組 忒、、且成物包含聚縮醛、環内橋接之共聚物、酚型抗 氧化劑、以月π爾 Λ ^ ^ 古1 反"、、，以解決上述問題，並減少該組成物在 程下之甲㈣放。上料利之優點係在於減少 酸1的釋放，但使用了 #故 、橋接之共聚物而降低了聚縮醛樹 月曰之機械特性。 [發明内容] θ本卷明之達成係發明人為克服習知技術中的既存問 題點，針對雷射標記之聚縮醛樹脂組成物進行深入且完整 :研九1現將一酉&肼化合物添加至雷射標記用之聚縮駿 t月曰、且成物中用作為熱安定劑，卩以增進雷射標記之模製 。口的煞安定性並減少製造過程中的曱醛釋放。 口此本發明之一目的即係在於提供一種具有優豈的 熱安定性的雷射標記用之聚縮酸樹脂組成物。 ” 92491 7 200422343 本發明之另一目的係提供一種在製造過程中能減少 曱酸釋放的雷射標記用之聚祕樹脂組成物。 本發明之又一目的係提供一種能展現出較佳的上色 效果以及較南亮度的雷射標記用之聚縮醛樹脂組成物。 ^為達成本發明上述目的，係提供一種雷射標記用之聚 縮駿樹脂組成物，該組成物係包含1〇〇重量份之聚縮駿、 〇·01至3·0重量份之碳黑、以及0.01至5.0重量份之二醯 ••肼化合物。 ~ [實施方式] ^本發明所揭示雷射標記用之聚縮醛樹脂組成物的特 徵係在於使用二醯肼化合物作為熱安定劑，而增進雷射標 屺之模製品的熱安定性，並在製造的過程中降低了曱醛二 釋放。 ^The engraving and fading are at the same time, two: most of the outer gold W and fading, the irradiated surface is customized with the plastic markings of the keyboard, or use the ancient ° knife edge, and used for example robe color and bleach The change of the faded mark on the metal surface of the transmission rate, instead of engraving on the mark surface. In this regard, the color + car .. ,,,. ^ Patent Publication No. 58 ^ 7496 discloses an earlier marking process, and the processing of the surface is made by laser processing. The desired mark is also physically shaped, gp ^ I, ..., processing method. Furthermore, Japanese Patent No. 63A6790 and 61_4 Japanese Patent Laid-Open No. 306285 disclose _species_ arm and Japanese Patent Laid-open No. Hei 1-shot marking process. Adding filler capable of secreting and decoloring. The use of such filler + base material is dyed with pigment. ^ Is characterized in that it is marked with a color different from the base material. 9249] 6 South contrast white mark In particular, the 4-inch t-inch is a study on the formation of a field shot on a black substrate. For example, Japanese Patent Laid-Open No. 11-i No. 40271 discloses the polyacetal of Shijiazhuang Co., Ltd., which is located in Shilug, Xixian. It is now disclosed that the type of resin composition includes: 7 ... transport mark resin composition, the carbon black particles The size oil absorbs to / 0 nm, and the above 200 € liter per 100 mg of DBP (dibutyl phthalate). In this example, a mark is used on a black substrate. The resin composition can form a high-contrast and high-brightness white product / and in the moldings formed from the above-mentioned composition, the carbon black and pigment are used in this group of machines, so the thermal stability is low, resulting in The result of fading and reduced mechanical properties. Cheng Zhi in U.S. Patent No. 5,218,041 discloses a kind of polyacetal group, and the product contains polyacetal, an intra-ring bridged copolymer, a phenolic antioxidant, and ^^^^ 1 In order to solve the above problems and reduce the release of the composition under the process. The advantage of feeding is that the release of acid 1 is reduced, but the use of ### bridging copolymer reduces the mechanical properties of polyacetal. [Summary of the Invention] θ The achievement of this book is to overcome the existing problems in the conventional technology. The inventors have conducted in-depth and complete research on laser-labeled polyacetal resin compositions. The shrinkage for laser marking is described as follows, and the product is used as a thermal stabilizer to enhance the molding of the laser marking. The stability of the mouth and reduce the formaldehyde release during the manufacturing process. One of the objects of the present invention is to provide a polyacetal resin composition for laser marking having excellent thermal stability. 92491 7 200422343 Another object of the present invention is to provide a polymer resin composition for laser marking which can reduce the release of osmic acid during the manufacturing process. Another object of the present invention is to provide a resin composition which can show better performance. The polyacetal resin composition for laser marking with color effect and lighter brightness. ^ In order to achieve the above object of the present invention, a polyacetal resin composition for laser marking is provided, and the composition contains 100%. Parts by weight of polycondensate, 0.01 to 3.0 parts by weight of carbon black, and 0.01 to 5.0 parts by weight of hydrazine compound. ~ [Embodiment] ^ Polymer for laser marking disclosed in the present invention The acetal resin composition is characterized by the use of a dihydrazine compound as a thermal stabilizer, which enhances the thermal stability of the molded product of the laser target, and reduces the release of the secondary aldehyde during the manufacturing process. ^

本發明之雷射標記用組成物 趁、0.01至3.0重量份之碳黑、 二醯肼。 包含100重量份之聚縮 以及0·01至5·0重量份 之 +發明所使用的聚縮駿樹脂係由曱醛基團所組成之 :聚物，其係以下…示之單元作為主要的基本單元， 或係由下式1之曱醛基團與下式2所示 棬砧如入 < 早肢基團進行隨 域的聚合反應所獲得者： 式1 +ch2〇+ 式2 -[-(CX】X2)、〇-]一 92491 200422343 2 T相同或不同，分別為氫、烷基基 或芳基基團’以及 Α 士乐 夂χ為2至6之整數，其條件為X】與 不可同日守為氫。含取 Μ ♦、伯酪樹脂具有1 05000至200,000之平 均分子量。 卞 該曱Sir均參^ κ物係由甲醛或其環狀募聚物（亦即，三卩萼烷） 之聚合反應所升> 士、 , ) ^成。此外，該曱醛共聚物包括式1之甲醛 基團 2之單體基團，該共聚物係由Μ或其環狀募 水物 式3所不之環狀醚化合物，或下式4所示之環 狀縮曱私化合物邊4千# 刃進订丨現機的共聚合反應所形成者： 式3 X3The composition for laser marking of the present invention uses 0.01 to 3.0 parts by weight of carbon black and dihydrazine. Contains 100 parts by weight of polycondensation and 0.001 to 5.0 parts by weight of the polycondensation resin used in the invention is a polymer consisting of an aldehyde group: a polymer, which is shown in the following as the main unit The basic unit, or the one obtained from the aldehyde group of the following formula 1 and the anvil represented by the following formula such as < the early limb group is subjected to a domain-dependent polymerization reaction: Formula 1 + ch2〇 + Formula 2-[ -(CX) X2), 〇-]-92491 200422343 2 T is the same or different, respectively hydrogen, alkyl or aryl group 'and A Shile Α χ is an integer of 2 to 6, and its condition is X] And the same day keep for hydrogen. Containing M ♦, primary casein resin has an average molecular weight of 15,000 to 200,000.卞 This 曱 Sir is a compound of κ, which is formed by the polymerization reaction of formaldehyde or its cyclic polymer (ie, trioxane). In addition, the acetaldehyde copolymer includes a monomer group of the formaldehyde group 2 of Formula 1, and the copolymer is a cyclic ether compound different from Formula 3 or a cyclic water-collecting compound thereof, or as shown in Formula 4 below. Cyclic deflation private compound 边 4 千 # Into the order 丨 formed by the copolymerization reaction of the machine: Formula 3 X3

式4 X5 〇W〇 其中，χ3、X4、X5、及x6可相同或不同，分別為氫、 或烧基基團，邡町連接至相同碳原子或連接至不同碳原 子，以及η及πι分別為2至6之整數。 就該隨機的麸聚合反應所使用之共聚單體而言，該環 狀醚化合物的系範性實例為環氧乙烷、環氧丙烷、環氧丁 92491 9 200422343 烷、及苯醚；以及該環狀縮曱醛化合物的實例包含丨，3-二 卩亏戊、二乙二醇縮甲醛、1，3-丙二醇縮曱醛、15心丁二醇縮 甲醛、込3·二氧環庚烷縮曱醛（di〇xepaneformai)、以及n心 三氧咁（l，3,6-tri0X0cane)。較佳者係使用選自環氧乙烷、 1，3-二卩亏戊、1，肛丁二醇縮曱醛、及其混合物之共聚單體。 f述共聚單體係在路易士酸催化劑存在的條件下添加至三 §烧或甲駿以進行隨機的共聚合反應’俾獲得主鏈具有兩 鱗個或多個連接碳原子且㈣A 15(rc或更高之甲縮駿共聚 物。 在該曱醛共聚物中，曱醛聚合物對甲醛重複單體之莫 耳比‘在0. 〇 5至5 0之範圍内，較佳為〇 ·丨至2 〇之範圍内 形成該曱醛聚合物之聚合反應中所用之催化劑的具 體貫例包括 BFS · 〇H2、BFS · OEh、BF3 · 〇Bu2、BFs · CH3C〇2H、bf3 · pf5hf、bf3-i〇-羥基乙醯苯等；其中，Et 係表不乙基，Bu係表示丁基。較佳者，係使用Β]ρ3 · ο%、 _ BF3 · 〇Bu2。該催化劑之添加量，卩）莫耳三嗜燒計，較 佳係在2χ ΙΟ·6至2x 1〇-2莫耳之範圍内。 泫聚合反應的示例包括整體聚合反應、懸浮聚合反 • 應、或溶液聚合反應，該反應係在0至1 〇〇°C的條件下進 行’較佳係在2 0至8 0 °C的條件下進行。 然而，該聚合反應之後，會留下使催化劑去活性之去 /舌丨生；=1彳，例如二乙〗女之二級胺類、例如嚷吩之環狀辟化入 物、例如三苯基膦之磷化合物、以及經烷基取代之二聚氰 胺化合物。此種去活性劑係具有未共用電子對之路易士 92491 10 200422343 鹼，可與催化劑形成錯合物。 t甲酸之聚合反應後’使用鏈轉移試劑⑽ain transfer agent)，例如經烧基取代之賴或鍵類。特別是，較 使用包含二曱氧基曱烷之烷基醚。 ’、 :所製備之聚_脂而言’較佳者係具有約_ —…谷點、結晶度為65至85%、且平均分子量為 1〇,〇〇〇至20Μ00之聚縮醛均聚物或共聚物。 =者’在本發明中，係使用碳黑作為吸收雷射光之材 二能階雷射時能獲得較佳的標記結果。在使 ±人^搭樹脂所形成之基材進行上色，特別是笔色 二:？於結合有碳黑之樹脂的雷射標記與黑度主要係取決 心::：：均顆粒尺寸以…之吸收，亦即個別碳 μ Λ 木之顆粒釔構，以及碳黑之添加量。 ，特別是黑色，以及雷射標記對於碳黑添加量的效果 果不=同。因此’為了同時獲得較佳的上色與雷 = 擇適當的碳黑是相當重要的。在本發明中，較佳係 ^粒尺寸為10至5〇譲，以及每100毫克之贿油 40至1 〇〇 cc之碳黑。若碳黑的顆粒尺寸小於w 咖’會減弱樹赌中的分散性。同時，若顆粒尺寸大於50 :，則會降低該聚祕樹脂的上色。此外，#該碳黑每⑽ , 油吸收小於40 cc時，會降低該聚縮醛樹脂的 士反之’虽该碳黑每】〇〇毫克之油吸收大於】⑽ ’則會減弱樹脂中的分散性。特別是，經·〇h覆以增 4散性之免#、’由於與聚祕樹脂末端基®之相容性， ΠFormula 4 X5 〇W〇 Wherein, χ3, X4, X5, and x6 may be the same or different, respectively, hydrogen, or a alkynyl group, 邡 machi is connected to the same carbon atom or to different carbon atoms, and η and π are respectively Is an integer from 2 to 6. As far as the comonomers used in the random bran polymerization are concerned, typical examples of the cyclic ether compound are ethylene oxide, propylene oxide, butylene oxide 92491 9 200422343 alkane, and phenyl ether; and Examples of the cyclic formal compounds include 1,3-dipyrene, diethylene glycol formal, 1,3-propanediol formal, 15-butanediol formal, and 込 3 · dioxetane Dioxepaneformai and n-cardioxane (l, 3,6-tri0X0cane). It is preferred to use a comonomer selected from the group consisting of ethylene oxide, 1,3-dioxobutane, 1, butanediol acetal, and mixtures thereof. The co-monomer system described above is added to the three sintered or Jiajun in the presence of a Lewis acid catalyst to carry out a random copolymerization reaction. 'The main chain has two scales or more connected carbon atoms and ㈣A 15 (rc Or higher. In this formaldehyde copolymer, the molar ratio of the formaldehyde polymer to the repeating monomer of formaldehyde is in the range of 0.05 to 50, preferably 0.005. Specific examples of the catalyst used in the polymerization reaction forming the aldehyde polymer in the range of 2 to 0 include BFS · 〇H2, BFS · OEh, BF3 · 〇Bu2, BFs · CH3C〇2H, bf3 · pf5hf, bf3- i〇-hydroxyacetophenone, etc., wherein Et represents ethyl, Bu represents butyl. More preferably, B] ρ3 · ο%, _BF3 · 〇Bu2. The amount of the catalyst added, 卩) Mole triple burner, preferably in the range of 2 × 10 · 6 to 2 × 10-2 Moore.的 Examples of polymerization reactions include monolithic polymerization, suspension polymerization, or solution polymerization. The reaction is carried out at a temperature of 0 to 100 ° C. 'Preferably at 20 to 80 ° C Next. However, after the polymerization reaction, there will be a deactivation / tongue of the catalyst; = 1 彳, such as diethyl secondary amines, such as ring-shaped chemical compounds such as triphenyl, such as triphenyl Phosphine phosphorus compounds, and alkyl-substituted melamine compounds. This deactivator is a Lewis base with no shared electron pair 92491 10 200422343, which can form a complex with the catalyst. After the polymerization of formic acid, a chain transfer agent (such as ain transfer agent) is used, such as a substituted or bonded group. In particular, an alkyl ether containing a dimethoxyoxane is more preferably used. ',: For the prepared poly-lipid', the preferred one is a polyacetal homopolymer having a valley point, a crystallinity of 65 to 85%, and an average molecular weight of 10,000 to 20M00. Substance or copolymer. = 'In the present invention, the use of carbon black as a material for absorbing laser light can obtain better marking results when using a two-level laser. Color on the substrate made of ± human resin, especially pen color. The laser marking and blackness of resins combined with carbon black are mainly determined by the :::: absorption of the average particle size, that is, the yttrium structure of individual carbon μ Λ wood particles, and the amount of carbon black added. , Especially black, and the effects of laser marking on the amount of carbon black added are not the same. Therefore, in order to obtain better coloring and lightning at the same time, it is very important to choose an appropriate carbon black. In the present invention, carbon black having a particle size of 10 to 50 mm and 40 to 100 cc per 100 mg of bribe oil is preferred. If the particle size of carbon black is smaller than wca ', the dispersibility in the tree bet will be weakened. At the same time, if the particle size is larger than 50 :, the coloring of the polyresin will be reduced. In addition, # the carbon black per ⑽, when the oil absorption is less than 40 cc, the taxi of the polyacetal resin will be reduced; on the contrary, although the carbon black will have an oil absorption greater than ⑽ 毫克 per milligram of oil, the dispersion in the resin will be weakened Sex. In particular, after the 〇h coating with the increase of the dispersion of the exempt #, ’due to the compatibility with the polymer resin end group ®, Π

9249 J 200422343 □此’僅少置的碳黑即可達到所需的黑色程度。 、根據本發明，與標記組成物混合之碳黑，亦係用於黑 色或殊色基材進行白色標記的製程中。此外，灰色基材進 =上色時，亦可使用少量的碳黑，或將碳黑應用於與其他 稷雜：顏色混合。就其本身而言，以1〇〇重量份之聚縮醛 计’碳黑之用量係0·01至3 〇重量份。所使用的碳黑不足 0.0&1重量份時，會形成非期望之黑色程度；然而，所使用 的碳黑超過3.0重量份時，則會導致不良的標記結果。 再者，除了碳黑以外，亦可選用二氧化鈦（Ti〇2)、無 機顏料、以及有機顏料作為雷射吸收材料，以改善雷射標 記的效果。 而’使用包含碳黑以及其他顏料之聚縮㈣製材料 時’不利於主要形狀之沈激（depQSitic)n)或減低了成型之脫 杈性、去色與熱穩定性低所導致的機械特性下以 溫製程之曱醛釋放所產生的反感氣味。9249 J 200422343 □ This is only a small amount of carbon black to achieve the required level of blackness. According to the present invention, the carbon black mixed with the marking composition is also used in the process of performing white marking on black or special-colored substrates. In addition, a small amount of carbon black can be used when coloring the gray substrate, or carbon black can be used to mix with other: color. For its part, the amount of carbon black is from 0.01 to 300 parts by weight based on 100 parts by weight of the polyacetal. When the carbon black used is less than 0.0 < 1 part by weight, an undesired degree of blackness is formed; however, when the carbon black used exceeds 3.0 parts by weight, poor marking results may be caused. Furthermore, in addition to carbon black, titanium dioxide (Ti02), inorganic pigments, and organic pigments can also be used as laser absorbing materials to improve the effect of laser marking. And 'when using a polycondensation material containing carbon black and other pigments' is not conducive to depQSitic n) of the main shape or reduces the mechanical properties caused by de-branchability, decolorization and low thermal stability The offensive odor produced by the acetaldehyde released by the warm process.

在本發明中，由於使用二酿讲化合物作為熱安定劑， 該聚縮醛模製材料得以具有較佳的色彩均勻性 CO — )以及持久的亮度，同日寺，在高溫製造過程中展 現出優異的熱穩定性。 會與無機酸或有機酸 ’有機基團或自由基） 聚合物產物。因此， 、丙稀酸酯（aerylate 之改良劑、纖維處理 該二醯肼化合物具有反應性氫， 產生附加產物，或由反應性化合物（即 之反應所衍生之聚縮合反應期間產生 該二醯肼係用作為環氧樹脂之硬化劑 ester)之交聯劑、合成纖維或合成樹脂 92491 200422343 劑、或自由基清除物。 一特別是’由於添加了碳黑以及其他顏料，#由使用呈 有尚度誘發還原反應（reducti〇n-inducing)特性之—柄_ 一 免除了聚縮醛樹脂材料所引起之分解。因 。己用之聚縮醛樹脂組成物的熱安定性，同時降低了言⑼制 造過程中的甲醛釋放。較佳者’該二醯肼化合物係：：製 乙二酸二醯肼、丙二酸二醯肼、丁二酸二醯肼 '己二醆由 醯肼、癸二酸二醯肼 '十二烷酸二醯肼、異酞酸二醯二-= :，N，-_、間-苯_二_、以及對_苯_二_所構成 就其本身而言，以1〇〇重量份之聚縮醛計，該二醞 化，物之用量係〇.01至5.0重量份。若上述用量小於^1 重Ϊ份，將無法獲得所期望之熱安定性。同時，若用量^ 過5.0重量份，則該聚縮醛樹脂組成物具有較低的熱 性’且會由側反應導致性能的降低。 疋 為了使白色雷射標記具有高對比以及較佳的亮度，係 4擇性地使用二氧化鈦。在此實例中，該二氧化鈦之用量 以100重量份之雷射標記樹脂組成物計，係小於5 〇 f 份。 ·夏ΐ 然而，為了使黑色以外的其他預定顏色基材亦達到較 佳的白色雷射標記，係使用無機顏料顯現出預定顏色。= 佳者，該無機顏料係選自鈷綠、鈷藍、氧化鉻綠、鎘顏料、χ 鎳/鉻欽酸鹽、群青藍、或其混合物所構成之組群。就其本 身而言，該無機顏料之用4，以]00重量份之雷射標記用 9249] 200422343 之^纟彳§ 樹脂組成物計，係1 Q重量份以下 再者，為了能夠以白色以外的特定顏色標記預定 的基材，係選擇性地使用有機顏料顯、^色 . 寸疋顔色。較伴 者，機顏料係選自蒽醌，藍、酞青綠、鉻酞红 (Chr〇m〇phthal red)、或其混合物所構成之組群。:▲二， 況下，該有機顏料之用量，以i 〇 〇重| 清 似^ 4 I里知之雷射標記用之 ♦縮憋樹脂組成物計，係i 〇重量份以下。 、視需要’在不減損雷射照射標記特性的範圍内，可以 更進步使用已知的添加劑或填充劑。例如，爲 氣候的耐性，亦可進-步使用多種不同的安定劑、 劑、潤滑劑、塑化劑、晶核劑、脫模劑、抗： 界面活性劑。 以及 。同時，藉由以雷射光照射該樹脂組成物所形成之模製 :的預定部分’可輕易地進行雷射標記製程。就其本身而 S ’為了獲得所期望的標記，示例性方法係在標的物表面 的，當位置尺寸照射雷射，以及藉由遮蔽雷射的方式以所 期望之雷射形狀照射標的物的表面。 、邱適合的雷射實例包含碳酸氣體雷射、紅寶石雷射、半 導體雷射、氬氣雷射、準分子雷射、YAG雷射等。其中， "\Nd · YAG雷射較佳。就其本身而言，連續波或-般的 脈衝波均可使用；惟，較佳者係使用藉由連續波之 之掃描法中的高能脈衝雷射。 關 访如上所述，使用本發明之雷射標記樹脂組成物，能夠 進板衣。。的熱安定性。再者’纟製造的過程中，能夠減 92491 14 200422343 少甲酸的釋放，且亦可克服進行—般 磨耗所形成的耐久性問題。同樣地，亦可艇：該模製品之 溶劑浸漬後減損了抗化學腐钱性所導=油料浸漬或 外，本發明之樹脂組成物 、匕問題。此 力乂观具有優異的雷射 充分地維持纟㈣（aeetal)的基本特性，亦果’且能 學腐姓性、及耐疲勞性，因而可應 :寸性、抗化 件。 而要耐磨耗性的部 該雷射標記用樹脂組成物所製得之 YAG雷射進行雷射標記 、衣。。係以Nd: 行Μ進订快速印刷彦 預處理及後處理，且透盥 "，而不舄 < 电月匈緣圖辅助軟髁 不受限地修改圖樣，而獲得所具有所期望之Γ所复可以 品。再者，除了白色势σ / 口口貝的模製 巴氣口口以外的彩色製品亦 或彩色的電腦條碼、數字、標識、圖樣、以及”色 因此，太私日Η 不 及一維付號0 " 鵠射標記樹脂組成物可以声彡a r田 於多種油料或溶劑浸潰 了 ^廣泛地應用 腦條碼、數字、標識、圖樣、 =員不形色電 印刷製品印刷磨損的部# =^付5虎的部件；造成 示特性的部件。例如要一磨耗性與雷射標 鍵a的按鍵頂部部件 按鍵部件、汽車内部與外部^_ y件订動電話的 ^ # (h U1 、°卩件、Ά車的燃料部件、帶 扣口ίΜ牛（buckles)、拉#卹& 卞 綠。卩件、紀念品、玩具等。 在本發明的具體每 u 戶、例中’該聚縮醛樹脂.係細炫：％，並 利用雙螺桿押出機與碳聖刀_ ^ 知、，、二烙融，瓜In the present invention, the polyacetal molding material can have better color uniformity and long-lasting brightness due to the use of the second compound as a thermal stabilizer, and Tongri Temple has shown excellent performance during high-temperature manufacturing. Thermal stability. Will react with inorganic or organic acids ('organic groups or free radicals) polymer products. Therefore, the dihydrazine compound (aerylate modifier, fiber treatment of the dihydrazine compound has reactive hydrogen to produce additional products, or the dihydrazide is generated during the polycondensation reaction derived from the reactive compound (that is, the reaction) It is used as a cross-linking agent for epoxy resin hardener (ester), synthetic fiber or synthetic resin 92491 200422343 agent, or free radical scavenger. One particularly 'due to the addition of carbon black and other pigments, Reductioon-inducing characteristic of the degree-handle_ One eliminates the decomposition caused by the polyacetal resin material. Because. The thermal stability of the polyacetal resin composition has been used, while reducing the language Formaldehyde release during the manufacturing process. The preferred one is the dihydrazide compound system: making dihydrazine oxalate, dihydrazine malonate, and dihydrazine succinate. Adipazine is composed of hydrazine, sebac The acid dihydrazide 'dodecanoic acid dihydrazide, isophthalic acid dihydrazide- = :, N, -_, m-benzene_di_, and p-benzene_di_ constitute, Based on 100 parts by weight of polyacetal 0.01 to 5.0 parts by weight. If the above amount is less than ^ 1 part by weight, the desired thermal stability cannot be obtained. At the same time, if the amount is more than 5.0 parts by weight, the polyacetal resin composition has a lower It's thermal and will reduce performance due to side reactions. 疋 In order to make white laser markings have high contrast and better brightness, titanium dioxide is selectively used. In this example, the amount of titanium dioxide used is 100 parts by weight. Based on the laser marking resin composition, it is less than 50 f parts. · Xia Xun However, in order to achieve a better white laser marking for substrates of predetermined colors other than black, inorganic pigments are used to develop the predetermined color. = Preferably, the inorganic pigment is selected from the group consisting of cobalt green, cobalt blue, chrome oxide green, cadmium pigment, χ nickel / chromic acid salt, ultramarine blue, or a mixture thereof. For its part, the inorganic pigment Use of pigment 4 is based on [00249 parts by weight of laser marking 9249] 200422343 ^ 纟 彳 § Resin composition is 1 Q parts by weight or less, and in order to mark a predetermined substrate in a specific color other than white , Select The organic pigments are used to show the color and color. In contrast, the organic pigments are selected from the group consisting of anthraquinone, blue, phthalocyanine green, chrome phthalo red, or mixtures thereof. : ▲ Second, in this case, the amount of the organic pigment is based on i 〇〇 重 | Kiyoshi ^ 4 I know the shrinkage resin composition used for laser marking, it is i 〇 parts by weight or less, as required 'As long as the characteristics of laser irradiation markings are not degraded, the use of known additives or fillers can be further improved. For example, for weather resistance, a variety of different stabilizers, agents, lubricants, plastics can be further used. Chemical agent, crystal nucleating agent, release agent, anti: surfactant. as well as . At the same time, the laser marking process can be easily carried out by molding a predetermined portion of the molding formed by irradiating the resin composition with laser light. For its part, S ′ in order to obtain the desired mark, an exemplary method is to irradiate the laser at a position size on the surface of the target, and illuminate the surface of the target in a desired laser shape by shielding the laser. . Examples of suitable lasers include carbon dioxide gas lasers, ruby lasers, semiconductor lasers, argon lasers, excimer lasers, YAG lasers, and so on. Among them, " \ Nd · YAG laser is better. For its part, either a continuous wave or a pulse-like wave can be used; however, it is preferred to use a high-energy pulsed laser in the scanning method by a continuous wave. As mentioned above, the use of the laser-labeled resin composition of the present invention allows the board to be used. . Thermal stability. Furthermore, during the production of 纟, it can reduce the release of 92491 14 200422343 formic acid, and can also overcome the durability problem caused by ordinary wear. Similarly, it can also be used: the solvent impregnation of the molded product reduces the resistance to chemical corrosion = oil impregnation or in addition, the resin composition and the problem of the present invention. This force view has excellent laser light and fully maintains the basic characteristics of aeetal. It also learns the rotten name and fatigue resistance, so it can respond to size and resistance. The part that needs abrasion resistance is the YAG laser made of resin composition for laser marking. . It is based on the Nd: line M for rapid printing pre-processing and post-processing, and transparent ", and not < electric month Hungarian map assisted soft 髁 to modify the pattern without restriction, and get the desired Γ can be recovered. In addition, colored products other than the white potential σ / muzzle moulded Pakistani mouthpieces or colored computer barcodes, numbers, logos, patterns, and "colors. Therefore, it is too private and inferior to the one-dimensional pay number 0 & quot The radiolabeled resin composition can be immersed in a variety of oils or solvents. It is widely used in brain barcodes, numbers, logos, patterns, and printed parts. == 付 付 5 Tiger parts; parts that show characteristics. For example, abrasion and key top parts of the laser marking key a, key parts, car interior and exterior ^ _ y pieces of mobile phone ^ # (h U1, ° 卩, Fuel components of the car, buckles, buckles, pull-shirts & greens. Parts, souvenirs, toys, etc. In the specific example of the present invention, the polyacetal resin. Department Dazzling:%, and using a twin-screw extruder with a carbon holy knife

浴槽冷卻來自於押出機gp P ‘由々。P ,,柃眼杈之熔融物，以製備顆粒型式的 “““且成物。利用射 紙 1定田此衣仵之聚縮醛組 92491 15 200422343 成物經射出成型，而獲得射出成型材料。 精由後文所揭不之貫施例與比較例可更進一步瞭解 本發明，惟該等實施例與比較例僅係用以說明而非用以限 制本發明。 實施例與比較例中之組成物的物理特性，係根據下 列方法進行量測： 炼融流動指數（MI);流動性Bath cooling comes from the extruder gp P ‘Yu. P ,, the melt of the squinting branch, to prepare a granular type "" ". The product is made using injection paper 1 Dingtian polyacetal group 92491 15 200422343 into the injection molding to obtain the injection molding material The present invention can be further understood by the examples and comparative examples that will be disclosed later, but these examples and comparative examples are only for illustration and not for limiting the present invention. The physical properties of the composition are measured according to the following methods: Smelting flow index (MI); flowability

的條件下 根據ASTM D1238,在190°C負載2.16公斤 押出試品歷時10分鐘’量測由具有預定内徑之開孔所押出 的重量。所量測之重量數值越大’表示具有較佳的流動性； 反之，數值越小表示流動性越差。 抗拉強度以及拉伸伸長率 量測抗張強度以及伸長率。高數值 率高；反之，低數值表示抗張強度 根據 ASTM D63 8， 表不抗張強度以及伸長 以及伸長率低。Under the conditions of ASTM D1238, the test specimen was loaded at 190 ° C with a load of 2.16 kg for 10 minutes' to measure the weight extruded from an opening having a predetermined inner diameter. The larger the measured weight value is, the better the fluidity is; on the contrary, the smaller the value is, the worse the fluidity is. Tensile strength and tensile elongation Measure tensile strength and elongation. High values are high; conversely, low values indicate tensile strength. According to ASTM D63 8, tensile strength and elongation and elongation are low.

Izod衝擊強度 衝擊強度（有凹口的）。高 低數值表示衝擊強度低。 根據ASTM D256量測Iz〇d 數值表示衝擊強度南；相反地， 曱醛氣體釋放 將50毫升的蒸餾水注入！公升的聚乙烯瓶中，將測 試試月置人瓶中並使該測試試片維持未接觸^水的狀 態；接著’置於UL-Spec烘箱，在啊的條件下歷時^ 時。然後’將預定量的乙醯丙酮與醋酸銨添加至蒸餾水中， 形成發色團（chr刪phore)。藉由uv分光鏡量測該甲酸氣 9249] 16 200422343 體溶於蒸餾水之濃度。所量測的數值高，表示產生大量的 曱醛氣體；反之，數值低則表示僅形成少量曱醛氣體。 重量減損 在222 C之氮氣氣氛的熱重量分析（TGA)中，維持丄 小時，ΐ測試品減損的重量。高數值表示熱穩定性低；反 之，低數值表示熱穩定性高。 雷射標記（L-比例） 使用1064 nm之Nd : YAG雷射，在1〇χ 2〇 mm之方 形基材上標記“KEPITAL，，標識。使用購自X-Rite c〇·之 SP88分光光度計，在光源為D65的條件下，於ι〇。之角 度量測L比，即L-白/L-黑之比率。較高的比率則表示較 佳的結果。 實施例1 將1 00重篁分聚縮醛共聚合樹脂（商品名κεριτα[ F20-01，MI=9.5 克/10 分鐘，購自 K〇rea EngineeringIzod impact strength (notched). High and low values indicate low impact strength. The Iz〇d value measured according to ASTM D256 indicates the impact strength; conversely, the acetaldehyde gas is released. Inject 50 ml of distilled water! In a liter polyethylene bottle, place the test in a bottle and keep the test piece untouched by ^ water; then ‘place in a UL-Spec oven for ^ hours under ah ’s conditions. Then, a predetermined amount of acetoacetone and ammonium acetate are added to the distilled water to form a chrophore. The concentration of the formic acid gas in the distilled water was measured by a UV spectroscope 9249] 16 200422343. A high value indicates that a large amount of formaldehyde gas is generated; a low value indicates that only a small amount of formaldehyde gas is formed. Weight loss In thermogravimetric analysis (TGA) in a nitrogen atmosphere at 222 C, the weight of the test product was reduced for 丄 hours. High values indicate low thermal stability; conversely, low values indicate high thermal stability. Laser marking (L-scale) Nd: YAG laser at 1064 nm was used to mark "KEPITAL," on a square substrate of 10x20mm, using the SP88 spectrophotometer purchased from X-Rite c〇 · Under the condition that the light source is D65, the L ratio is measured at an angle of ι, that is, the ratio of L-white / L-black. A higher ratio indicates a better result. Centrifugal polyacetal copolymer resin (trade name κεριτα [F20-01, MI = 9.5 g / 10 minutes, purchased from Korea Engineering

Plastics Co. Ltd.，又稱‘P0M，）炫融，再使用雙螺桿押出機 使該樹脂與ι·ο重量份之乙二酸二醯肼（〇ADH)、〇 i5重量 份覆有OH基團之碳黑、以及0·05重量份之二氧化欽進行 捏合。藉由冷卻浴槽冷卻來自於押出機眼模之熔融物，以 製備顆粒式的聚縮I组成物’使射出成型機，由該顆 粒型式的聚縮醛組成物製備測試片。根據上述量測方法， 量測該測試片之物理特性。結果係示於下列表丨與表2中。 貫碎」列2 以實施例！之相同方法製備測試片，其差異係在於更 92491 …機顏料（群青藍）。根據上述量 <物理特性。結果係示於下列表2 進一步使用〇·5重量份 測方法，量測該測試片 中〇 實施例3 、# ffl η ^ ^ - 1用/只」織片，其差異係在於更 進一步使用〇 ·3 ΐ s:份之古换4 ^ | ^ . 機顏料（酞青藍）。根據上述量 測方法，量測該測試片之物 4里Plastics Co. Ltd., also known as 'P0M'), was melted, and then a twin screw extruder was used to make the resin and ι · ο parts by weight of hydrazine dioxazide (〇ADH) and 5 parts by weight of OH group Kneaded carbon black and 0.05 parts by weight of dioxin were kneaded. The molten material from the die of the extruder was cooled in a cooling bath to prepare a pellet-type polycondensation I composition. The injection molding machine was used to prepare a test piece from the pellet-type polyacetal composition. According to the above measurement method, the physical characteristics of the test piece are measured. The results are shown in the following table and Table 2. "Broken" column 2 Example! The same method was used to prepare the test piece, the difference was that it was more 92491… organic pigment (ultramarine blue). Based on the above amounts < physical properties. The results are shown in Table 2 below. Using 0.5 parts by weight of the test method, the test piece was measured. Example 3, # ffl η ^ ^-1 "Weaving piece, the difference lies in further use. · 3 ΐ s: Fenzhigu for 4 ^ | ^. Organic pigment (phthalocyanine blue). According to the above measurement method, measure the content of the test piece 4 miles

物理特性。結果係示於下列表2 中0 實施例4 ’其差異係在於並 量測該測試片之物 以實施例1之相同方法製備測試片 未使用^一乳化欽。根據上述量測方法， 理特性。結果係示於下列表2中。 比較例1至3 以實施例1之相同方法 於並未使用乙二酸二酿肼， 2所示。根據上述量測方法 結果係示於下列表2中。 製備各個測試片，其差異係在 以及碳黑之用量變化係如下表 ，量測該測試片之物理特性。 92491 18 200422343 表1 量測方法 (ASTM) 量測條件 單位 實施例1 物理特性 比重水吸收率 D792 D570 23〇C 23〇C，60% RH % 1.41 0.22 熱 Ml D1238 190°C 克/10分鐘 9.8 性質 熔點 DSC - °c 165 機械特性 抗張強度 伸長率 D638 23± 2°C 50± 5% RH Kgf/cm2 % 600 60 撓曲強度 撓曲模數 Izod衝擊強度 (有凹口的） D790 D256 23土 2°C 50± 5% RH 有凹口 t = 3.2 mm Kgf/cm2 Kgf/cm2 Kgf/cm 860 25000 7.0 成形收縮率 (t 5 mm? Φ100 mm) 流動方向 - % 2.0 表2 實例 編號 P0M (重量份） 碳黑 (重量份） 熱穩定劑 (重量份） 上色顏料 (重量份） L比 甲醛 氣體 釋放 (ppm) 雷射標記部 分的顏色 底色 1 100 0.15 OADH 1.0 二氧化鈦0.05 2.5 3.4 白色 黑色 2 100 0.20 0ADH 1.0 二氧化鈦 〇.〇5，群青藍 0.5 - 3.9 白色 群青藍 3 100 0.20 0ADH 1.0 酞青藍0.5 - 4.3 藍色 群青藍 4 100 0.15 0ADH 1.0 - 2.0 3.6 白色 黑色 比較 例1 100 0.15 - 二氧化鈦0.05 2.4 9.0 白色 黑色 比較 例2 100 0.4 0ADH 1.0 - 0.52 4.7 灰色 黑色 比較 例3 100 0.4 - - 0.47 11.3 灰色 黑色 [工業應用性] 如上述所揭示者，本發明係提供一種雷射標記用之聚 19 92491 200422343 縮醛樹脂組成物，該組成物所形成之模製品具有較佳的雷 射I且具有増強之耐磨耗性、财久性、抗化學腐 蚀性m彳疲勞性，該組成物賴由使用二醯肼作為熱 女疋劑而增進了模製品的熱安定性，並減少了製造過程中 的曱醛釋放。再者’此種模製品係利用則：雷射進 行田射才不„己II以在办色製品上顯現出白色或彩色的形 式；同樣地，相較於習用的印刷方法，該種雷射製程亦可 快速地進行’而不需要預處理以及後處理。再者，透過邀 電腦繪圖輔助軟體的連線可以不受限地修改，因此； 以使模製品之雷射標記具有所需的品質。 雖然已揭示本發明之較佳具體實例說明本發明之功 效，惟，熟習該項技術者仍可在未择離後文之申請專 圍所界^之精神與範心進行各種修飾、新增以及替換。Physical characteristics. The results are shown in Table 2 below. Example 4 'The difference is that the test piece was measured and the test piece was prepared in the same manner as in Example 1 without using an emulsifier. According to the above measurement method, the physical properties are analyzed. The results are shown in Table 2 below. Comparative Examples 1 to 3 are shown in the same manner as in Example 1 without using oxalic acid bishydrazine. The results according to the above measurement methods are shown in Table 2 below. The difference between the preparation of each test piece and the change in the amount of carbon black used are shown in the following table to measure the physical characteristics of the test piece. 92491 18 200422343 Table 1 Measurement method (ASTM) Measurement conditions Unit Example 1 Physical characteristics Specific gravity Water absorption rate D792 D570 23 ° C 23 ° C, 60% RH% 1.41 0.22 Thermal Ml D1238 190 ° C g / 10 minutes 9.8 Properties Melting point DSC-° c 165 Mechanical properties Tensile strength elongation D638 23 ± 2 ° C 50 ± 5% RH Kgf / cm2% 600 60 Flexural strength Flexural modulus Izod Impact strength (with notch) D790 D256 23 Soil 2 ° C 50 ± 5% RH Notched t = 3.2 mm Kgf / cm2 Kgf / cm2 Kgf / cm 860 25000 7.0 Forming shrinkage (t 5 mm? Φ100 mm) Flow direction-% 2.0 Table 2 Example No. P0M ( Parts by weight) Carbon black (parts by weight) Thermal stabilizer (parts by weight) Colored pigments (parts by weight) L ratio formaldehyde gas release (ppm) Color background of laser marking part 1 100 0.15 OADH 1.0 Titanium dioxide 0.05 2.5 3.4 White black 2 100 0.20 0ADH 1.0 titanium dioxide 0.05, ultramarine blue 0.5-3.9 white ultramarine blue 3 100 0.20 0ADH 1.0 phthalocyanine blue 0.5-4.3 blue ultramarine blue 4 100 0.15 0ADH 1.0-2.0 3.6 white black comparative example 1 100 0.15- Titanium dioxide 0.05 2.4 9.0 white to black ratio Example 2 100 0.4 0ADH 1.0-0.52 4.7 Gray and black Comparative Example 3 100 0.4--0.47 11.3 Gray and black [Industrial applicability] As disclosed above, the present invention provides a polymer for laser marking 19 92491 200422343 Acetal resin The composition, the molded product formed by the composition has better laser I and has sturdy abrasion resistance, longevity, chemical resistance, and fatigue resistance. The composition depends on the use of dihydrazine as the The hot female tincture enhances the thermal stability of the molded product and reduces the release of formaldehyde during the manufacturing process. Furthermore, the use of this type of molded product is as follows: the laser is not used for field shooting, so that it appears white or colored on the color product; similarly, compared with the conventional printing method, this type of laser The process can also be performed quickly without pre-processing and post-processing. Furthermore, the connection of the computer-aided drawing software can be modified without restriction, so that the laser marking of the molded product has the required quality Although the preferred specific examples of the present invention have been disclosed to illustrate the effectiveness of the present invention, those skilled in the art can still make various modifications and additions in the spirit and ambition of the application that has not left the application area. And replace.

92491 2092491 20

Claims (1)

200422343 拾、申请專利範圍·· 于才不°己用之聚縮駿樹脂組成物，該組成物係包括 100重量份92至QQ去曰 王重量％之聚縮醛、〇·〇1至3.0重量 份之碳黑、以及Ο η 1 • 1至5 · 0重量份之二醯肼化合物。 2·如申請專利範圍箆 弟1項之組成物，其中，該碳黑具有i 〇 至50 nm之顆粒尺 〜才，以及每100毫克之DBP(鄰笨二 曱酸二丁酯）油> w 及收量為4〇至100 cc，且該碳黑係覆 有-◦ Η基團。 3 ·如申請專利範圍楚 .之組成物，其中，該二醯肼化合物 係選自由乙二酸二 Bi± . ^ —駄胼、丙二酸二醯肼、丁二酸二醯 肼、己二酸二醯肼、 g ^, ^ ^ d $ 一 8夂一 肼、十二烷酸二醯肼、 硏哌嗪N，N，_二醯肼、間-苯_ 及對-本-二酿肼所構成之組群。 4. 如申請專利範圍第】至3 Ti〇2 〇 、 項之組成物，復包括 5. 如申請專利範圍第〗 無機顏料，該&機声：' S 一項之組成物，復包括 # 4係選自鈷綠、鈷藍、、 釦顏枓、鎳/鉻鈦酸鹽 乳化" 組群。 1 或其混合物所構成之 6·如申請專利範圍第4項之组 ^ 無機顏料係選自鈷 ·’ ，设包括無機顏料，該 J、㈢姑綠、叙該 鉻鈦酸鹽、群主1 皿乳化鉻綠、鎘顏料、銘/ 人如申請專利皿、或其混合物所構成之組群。 L月專利祀圍第】至3 有機顏料，哕右她#員之組成物，復包括 有“料係選嚷、駄青藍、献青綠、 9249) 21 200422343 鉻駄紅（chromophthal red)、或其混合物所構成之組群。 8.如申請專利範圍第4項之組成物，復包括有機顏料，該 有機顏料係選自蒽醒、駄青藍、駄青綠、鉻it紅 (chromophthal red)、或其混合物所構成之組群。200422343 Scope of patent application: Yucai does not use the polycondensate resin composition, which is composed of 100 parts by weight of 92 to QQ weight percent polyacetal, 0.001 to 3.0 weight Parts of carbon black, and 0 η 1 • 1 to 5.0 parts by weight of the dihydrazide compound. 2. The composition according to item 1 of the scope of the patent application, wherein the carbon black has a particle size of 50 to 50 nm and a DBP (dibutyl ortho-dibenzoate) oil per 100 mg > w and the yield are 40 to 100 cc, and the carbon black is coated with a -◦ Η group. 3. The composition according to the scope of the patent application, wherein the dihydrazine compound is selected from the group consisting of Bi ±. Succinate, dihydrazine malonate, dihydrazine succinate, and adipic acid. Acid dihydrazine, g ^, ^ ^ d $ one 8 hydrazine, dodecanoic acid dihydrazine, piperazine N, N, _ dihydrazine, m-benzene_ and p-benzyl-dihydrazine The group formed. 4. If the scope of the application for patents] to 3 Ti〇2 〇, the composition, including 5. In the case of the scope of the patent application for inorganic pigments, the & machine sound: 'S a composition, including # The 4 series is selected from the group consisting of cobalt green, cobalt blue, cyanide, nickel / chromotitanate emulsification. 1 or a mixture thereof 6. · As set in the fourth scope of the patent application ^ The inorganic pigment is selected from the group of cobalt · ', and includes inorganic pigments, the J, the green, the chromotitanate, the group owner 1 Group consisting of chrome-emulsion chrome green, cadmium pigment, Ming / Ren patenting plate, or mixtures thereof. No. of patents for the month of the month] to 3 organic pigments, the composition of the right members, including "material selection, cyan blue, cyan green, 9249) 21 200422343 chromophthal red, or The group consisting of its mixture. 8. If the composition in the scope of patent application No. 4 includes an organic pigment, the organic pigment is selected from the group consisting of anthracene, cyanine blue, cyanine green, chromophthal red, Or groups of mixtures. 9249】 200422343 柒、指定代表圖：本案無圖式 (一） 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件代表符號簡單說明: 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式：9249] 200422343 柒. Designated Representative Map: There is no schema in this case (1) The designated representative map in this case is: (). (2) Brief description of the element representative symbols of this representative map: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 4 924914 92491