201030072 六、發明說明： 【發明所屬之技術領域】 本發明係關於聚乳酸樹脂用結晶核劑及聚乳酸樹脂組成 物。近年，就從自然環境保護的立場，要求能在自然環境中 進行分解的生物分解性樹脂及其成形體，其中，聚乳酸樹脂 係除確立以農作物為原料的製造技術之外，溶融成形性與耐 熱性亦均優異，因而最受矚目。但是，雖聚乳酸樹脂的本質 係屬結晶性樹脂，但結晶化較慢’在實際的成形時將呈現近 似非晶性樹脂的行為，就成形性與所獲得成形體的物性方面 會有頗多困難處。為求改善該困難處，聚乳酸樹脂一般係在 其中添加結晶核劑，甚至更配合特定目的添加其他添加劑， 經調製成聚乳酸樹脂組成物之後，才提供進行成形。本發明 便關於該聚乳酸樹脂用結晶核劑及使用其之聚乳酸樹脂組 成物。 【先前技術】 習知如上述的聚乳酸樹脂用結晶核劑，已知有如下述：U 選擇自脂肪族叛酸醯胺類、脂肪族雙叛酸醢胺類、N-取代脂 肪族羧酸雙醢胺類及N-取代尿素類中，且熔點4〇〜300。(：的 化合物(例如參照專利文獻1) ; 2)諸如：均苯三曱酸三（第三 丁基醯胺）、1，4-環己烷二羧酸二苯胺、2,6_萘二羧酸二環己 基醯胺、N，N’-二苯甲醯基-1,4-二胺基環己烷、Ν,Ν，-二環己 烧幾基-1，5-二胺基萘等芳香族酿胺化合物（例如參照專利文 098137214 6 201030072 獻2) ; 3)磷酸酯金屬鹽及鹼性無機鋁化合物(例如參照專利 文獻3) ; 4)諸如滑石等無機粒子(例如參照專利文獻4)等。 但是，該等習知聚乳酸樹脂用結晶核劑’因為使用其所調製 之聚乳酸樹脂組成物的結晶化仍然嫌慢，因而需要長時間的 成形，僅此情形便會造成生產性惡化的問題。 所以，習知就經改善上述問題的聚乳酸樹脂用結晶核劑， 有提案如芳香族磺酸鹽(例如參照專利文獻5)。但是，該聚 ❹ 乳酸樹脂用結晶核劑實際上因平均粒徑的不同，在性能上會 有頗大差異，當將較大平均粒徑物，使用於由L-乳酸戶斤$ 成構成單位或由D-乳酸所形成構成單位，佔全構成單位中 達99莫耳％以上的聚乳酸樹脂時，雖可發揮相呼應的效果， 但若將相同物使用於由L-乳酸所形成構成單位或由D-乳酸 所形成構成單位，佔全構成單位中未滿99莫耳％的聚乳酸 樹脂時，則結晶化仍然緩慢，需要長時間的成形，會有生產 ⑩性差的問題；又，相反的，若使用平均粒徑過小的情況，不 僅會因處置時的揚塵所造成的作業環境惡化，就連對聚乳酸 樹脂的混練性亦會變差’結果會有連結晶化亦無法充分提升 的問題。 [專利文獻1]曰本專利特開平9-278991號公報 [專利文獻2]曰本專利特開平10_87975號公報 [專利文獻3]曰本專利特開2003_192883號公報 [專利文獻4]曰本專利特開平8-3432號公報 098137214 7 201030072 [專利文獻5]W〇2005/068554號公報 【發明内容】 (發明所欲解決之問題） 本發明所欲解決的課題在於提供：即便使用於由L-乳酸 所形成構成單位或由D -乳酸所形成構成單位的含有比例較 低之聚乳酸樹脂（即光學純度較低的聚乳酸樹脂），仍可充分 地提升結晶化’且處置時的作業性亦優異，亦不致使作業環 境惡化的聚乳酸樹脂用結晶核劑及聚乳酸樹脂組成物。 (解決問題之手段） 緣是，本發明者等為能解決上述課題而經深入鑽研，結果 發現將特定芳香族磺酸鹽調整於特定平均粒徑，便頗能正確 地適用為聚乳酸樹脂的結晶核劑。 即，本發明的聚乳酸樹脂用結晶核劑，係由下述化1所示 芳香族續酸鹽構成，且由將平均粒徑調整於範圍 内者構成。 [化1]201030072 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a crystal nucleating agent for a polylactic acid resin and a polylactic acid resin composition. In recent years, from the standpoint of natural environmental protection, biodegradable resins and their molded bodies which can be decomposed in the natural environment are required. Among them, polylactic acid resins are formed in addition to the manufacturing technology using crops as raw materials. It is also excellent in heat resistance and is therefore the most eye-catching. However, although the essence of the polylactic acid resin is a crystalline resin, the crystallization is slower. 'In the actual molding, the behavior of the amorphous resin is exhibited, and there are many aspects in terms of formability and physical properties of the obtained molded body. Difficulties. In order to improve the difficulty, the polylactic acid resin is generally added with a crystal nucleating agent, and even further additives are added for a specific purpose, and after the preparation into a polylactic acid resin composition, the forming is provided. The present invention relates to a crystal nucleating agent for a polylactic acid resin and a polylactic acid resin composition using the same. [Prior Art] Conventionally, the above-mentioned crystal nucleating agent for polylactic acid resin is known as follows: U is selected from aliphatic tartamines, aliphatic bis-indole amines, N-substituted aliphatic carboxylic acids. Among the biguanide and N-substituted ureas, and having a melting point of 4 to 300. (: compound (for example, refer to Patent Document 1); 2) For example: trimesic acid tris(t-butyldecylamine), 1,4-cyclohexanedicarboxylic acid diphenylamine, 2,6-naphthalene Dicyclohexyldecylamine carboxylic acid, N,N'-dibenylhydrazine-1,4-diaminocyclohexane, hydrazine, hydrazine, dicyclohexanyl-1,5-diaminonaphthalene An aromatic aromatic amine compound (for example, refer to Patent Document 098137214 6 201030072 2); 3) a phosphate metal salt and a basic inorganic aluminum compound (for example, refer to Patent Document 3); 4) inorganic particles such as talc (for example, refer to the patent literature) 4) Wait. However, these conventional crystal nucleating agents for polylactic acid resins are still too slow to be crystallized by using the polylactic acid resin composition prepared therefrom, and thus it takes a long time to form, and in this case, the problem of deterioration in productivity is caused. Therefore, a crystal nucleating agent for a polylactic acid resin which has been improved by the above-mentioned problems is known, such as an aromatic sulfonate (see, for example, Patent Document 5). However, the crystal nucleating agent for the polylactic acid lactic acid resin actually differs greatly in performance depending on the average particle diameter, and when a larger average particle diameter is used, it is used in a unit composed of L-lactic acid. Or a polylactic acid resin which is composed of D-lactic acid and which accounts for 99% by mole or more of the total constituent unit, although it can exert an effect corresponding to each other, if the same substance is used for a constituent unit formed of L-lactic acid Or a constituent unit formed of D-lactic acid, which is less than 99% by mole of the polylactic acid resin in the total constituent unit, the crystallization is still slow, and it takes a long time to form, which may cause a problem of poor production; If the average particle size is too small, the working environment will be deteriorated due to the dust during the treatment, and the kneading property of the polylactic acid resin will be deteriorated. As a result, even the crystallization cannot be sufficiently improved. problem. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polylactic acid resin having a low content ratio (that is, a polylactic acid resin having a low optical purity) which is formed by a constituent unit or a constituent unit formed of D-lactic acid can sufficiently enhance crystallization and is excellent in workability at the time of disposal. A polynuclear resin or a polylactic acid resin composition for a polylactic acid resin which does not deteriorate the working environment. (Means for Solving the Problem) The inventors of the present invention have intensively studied in order to solve the above problems, and as a result, it has been found that the specific aromatic sulfonate can be suitably applied to a polylactic acid resin by adjusting the specific aromatic sulfonate to a specific average particle diameter. Crystalline nucleating agent. In other words, the crystal nucleating agent for a polylactic acid resin of the present invention is composed of an aromatic acid salt represented by the following formula 1, and is composed of an average particle diameter adjusted to a range. [Chemical 1]
化1中， X :從苯中去除3個氫原子的殘基 R1、R2 :碳數1~6的烴基 098137214 8 201030072 Μ:鹼金屬原子或鹼土族金屬原子 η: 1或2’當]V[為驗金屬原子的情況便為η=1，當Μ為 驗土族金屬原子的情況便為η=2 再者’本發明的聚乳酸樹脂組成物，係含有：由L_乳酸 所形成構成單位或由D-乳酸所形成構成單位，佔全構成單 位中之95〜99莫耳％的聚乳酸樹脂’以及上述本發明聚乳酸 樹脂用結晶核劑而構成。 〇 【實施方式】 首先，針對本發明的聚乳酸樹脂用結晶核劑（以下簡稱「本 發明結晶核劑」）進行說明。本發明結晶核劑係由化丨所示 芳香族磺酸鹽構成。化1所示芳香族磺酸鹽係包括有：U 磺基鄰苯二曱酸二烷基的鹼金屬鹽、2)磺基間苯二曱酸二烷 基的鹼金屬鹽、3)磺基對苯二甲酸二烷基的鹼金屬鹽、句磺 基鄰苯二甲酸二烷基的鹼土族金屬鹽、5)磺基間苯二甲酸二 e烷基的鹼土族金屬鹽、6)磺基對苯二甲酸二烷基的鹼土族金 屬鹽、及7)以上1)〜6)的任意混合物。 化1所不芳香族磺酸鹽中，化1中的X係從笨中去除3 個氫原子的殘基。且，化i中的Ri及R2係有如：甲基、乙 基、丙基、異丙基、異丁基、戊基、己基、環戊基、環己基、 烯丙基、環己烯基等碳數丨〜6的烴基，其中較佳為碳數 的脂肪族烴基，更佳為甲基。 化1所不芳香族磺酸鹽中，化1中的Μ係有如：1)鋰原 098137214 9 201030072 子、鈉原子、鉀原子、铷原子、鉋原子等鹼金屬原子，2) 皱原子、鎂原子、鮮原子、錄原子、鎖原子等驗土族金屬原 子，其中較佳為鉀原子、铷原子、鋇原子、锶原子、鈣原子， 更佳為鉀原子與鋇原子。 化1所示芳香族磺酸鹽中，就磺基鄰苯二甲酸二烷基的鹼 金屬鹽具體例係可舉例如：1)4-磺基鄰苯二曱酸二甲基= 鋰、4-磺基鄰苯二曱酸二乙基=鋰、4-磺基鄰苯二曱酸二正 丙基=鋰、4-磺基鄰苯二曱酸二異丙基=鋰、4-磺基鄰苯二曱 ❿ 酸二正丁基=鋰、4-磺基鄰苯二曱酸二異丁基=鋰、4-磺基鄰 苯二甲酸二第三丁基=鋰、4-磺基鄰苯二甲酸二-2-甲基丙基 =鋰、4-磺基鄰苯二甲酸二正戊基=鋰、4-磺基鄰苯二曱酸二 -3-曱基丁基=鋰、4-磺基鄰苯二曱酸二-2-曱基丁基=鋰、4-磺基鄰苯二曱酸二-2,2-二甲基丙基=鋰、4-磺基鄰苯二甲酸 二正己基=鋰、4-磺基鄰苯二曱酸二-4-曱基戊基=鋰、4-磺基 鄰苯二曱酸二-3,3-二甲基丁基=鋰、4-磺基鄰苯二甲酸二 Θ -2,3-二曱基丁基=鋰、4-磺基鄰苯二甲酸二環己基=鋰等磺基 鄰苯二曱酸二烷基的鋰鹽；2)4-磺基鄰苯二曱酸二曱基= 鈉、4-磺基鄰苯二曱酸二乙基=鈉、4-磺基鄰苯二曱酸二正 丙基=鈉、4-磺基鄰苯二曱酸二異丙基=鈉、4-磺基鄰苯二曱 酸二正丁基=鈉、4-磺基鄰苯二甲酸二異丁基=鈉、4-磺基鄰 苯二甲酸二第三丁基=鈉、4-磺基鄰苯二曱酸二-2-曱基丙基 =鈉、4-磺基鄰苯二甲酸二正戊基=鈉、4-磺基鄰苯二曱酸二 098137214 10 201030072 -3-曱基丁基=納、4-石黃基鄰苯二甲酸二-2-曱基丁基=納、4_ 磺基鄰苯二曱酸二-2,2-二曱基丙基=鈉、4-磺基鄰苯二曱酸 二正己基=納、4-石黃基鄰苯二甲酸二-2-甲基戊基=納、4-橫基 鄰苯二曱酸二-3-甲基戊基=鈉、4-磺基鄰苯二甲酸二-4-甲基 戊基=納、4-續基鄰苯二曱酸二-3,3-二甲基丁基=鋼、4-續基 鄰苯二曱酸二-2,3-二曱基丁基=鈉、4-磺基鄰苯二曱酸二環 己基=納等續基鄰苯二曱酸二烧基的納鹽，3)4-績基鄰苯二 0 甲酸二曱基=鉀、4-磺基鄰苯二甲酸二乙基=鉀、4-磺基鄰苯 二曱酸二正丙基=鉀、4-磺基鄰苯二曱酸二異丙基=鉀、4-• 磺基鄰苯二曱酸二正丁基=鉀、4-磺基鄰苯二曱酸二異丁基= 鉀、4-磺基鄰苯二甲酸二第三丁基=鉀、4-磺基鄰苯二曱酸 二-2-曱基丙基=钟、4-礦基鄰苯二曱酸二JL戊基=卸、4-續基 鄰苯二曱酸二-3-曱基丁基=鉀、4-磺基鄰苯二甲酸二-2-甲基 丁基=卸、4-續基鄰苯二甲酸二-2,2-二甲基丙基=舒、4-續基 〇 鄰苯二甲酸正己基=鉀、4-磺基鄰苯二曱酸二-2-曱基戊基= 鉀、4-磺基鄰苯二曱酸二-3-曱基戊基=鉀、4-磺基鄰苯二曱 酸二-4-曱基戍基=钟、4-橫基鄰苯二曱酸二-3,3-二曱基丁基 =鉀、4-磺基鄰苯二曱酸二-2,3-二曱基丁基=鉀、4-磺基鄰苯 二曱酸二環己基=鉀等磺基鄰苯二曱酸二烷基的鉀鹽；4)4-磺基鄰苯二曱酸二甲基=鉋、4-磺基鄰苯二曱酸二乙基=鉋、 4-磺基鄰苯二甲酸二正丙基=鉋、4-磺基鄰苯二甲酸二異丙 基=鉋、4-磺基鄰苯二曱酸二正丁基=鉋、4-磺基鄰苯二曱酸 098137214 11 201030072 二異丁基=鉋、4-磺基鄰苯二曱酸二第三丁基=鉋、4-磺基鄰 苯二曱酸二-2-曱基丙基=鉋、4-磺基鄰苯二曱酸二正戊基= 铯、4-磺基鄰苯二曱酸二-3-曱基丁基=铯、4-磺基鄰苯二曱 酸二-2-曱基丁基=鉋、4-磺基鄰苯二曱酸二-2,2-二曱基丙基 =鉋、4-磺基鄰苯二曱酸二-2-曱基戊基=鉋、4-磺基鄰苯二曱 酸二-3-曱基戊基=铯、4-磺基鄰苯二曱酸二-4-曱基戊基= 铯、4-磺基鄰苯二甲酸二-3,3-二曱基丁基=鉋、4-磺基鄰苯 二甲酸二-2,3-二甲基丁基=鉋、4-磺基鄰苯二曱酸二環己基= 铯等磺基鄰苯二曱酸二烷基的鉋鹽等等。 化1所示芳香族磺酸鹽中，就磺基間苯二甲酸二烷基的鹼 金屬鹽具體例係可舉例如：1)5-磺基間苯二曱酸二曱基= 鋰、5-磺基間苯二曱酸二乙基=鋰、5-磺基間苯二曱酸二正 丙基=鋰、5-磺基間苯二曱酸二異丙基=鋰、5-磺基間苯二曱 酸二正丁基=經、5-績基間苯二曱酸二異丁基=經、5-績基間 苯二曱酸二第三丁基=鋰、5-磺基間苯二甲酸二-2-曱基丙基 =鋰、5-磺基間苯二甲酸二正戊基=鋰、5-磺基間苯二曱酸二 -3 -曱基丁基=鐘、5-石黃基間苯二曱酸二-2-曱基丁基=經、5_ 磺基間苯二甲酸二-2,2-二曱基丙基=鋰、5-磺基間苯二甲酸 二-4-曱基戊基=鋰、5-磺基間苯二曱酸二-3,3-二曱基丁基= 鋰、5-磺基間苯二甲酸二-2,3-二曱基丁基=鋰、5-磺基間苯 二曱酸二環己基=鋰等磺基間苯二曱酸二烷基的鋰鹽；2)5-磺基間苯二甲酸二曱基=鈉、5-磺基間苯二曱酸二乙基=鈉、 098137214 12 201030072 5-磺基間苯二甲酸二正丙基=鈉、5-磺基間苯二甲酸二異丙 基=納、5-續基間苯二甲酸二正丁基=納、5-續基間苯二曱酸 二異丁基=納、5-續基間苯二甲酸二第二丁基=納、5-續基間 苯二曱酸二-2-曱基丙基=鈉、5-磺基間苯二甲酸二正戊基= 納、5-續基間苯二曱酸二-3 -曱基丁基=納、5-績基間苯二甲 酸二-2-曱基丁基=鈉、5-磺基間苯二曱酸二-2,2-二曱基丙基 =納、5-續基間苯二曱酸二-2-曱基戍基=納、5-續基間苯二曱 ❿ 酸二-3-曱基戊基=鈉、5-磺基間苯二甲酸二-4-曱基戊基= 鈉、5-磺基間苯二曱酸二-3,3-二甲基丁基=鈉、5-磺基間苯 二曱酸二-2,3-二曱基丁基=鈉、5-磺基間苯二甲酸二環己基= 鈉等磺基間苯二甲酸二烷基的鈉鹽；3)5-磺基間苯二曱酸二 曱基=鉀、5-磺基間苯二甲酸二乙基=鉀、5-磺基間苯二甲酸 二正丙基=鉀、5-磺基間苯二甲酸二異丙基=鉀、5-磺基間苯 二曱酸二正丁基=鉀、5-磺基間苯二甲酸二異丁基=鉀、5-G 磺基間苯二甲酸二第三丁基=鉀、5-磺基間苯二曱酸二-2-甲 基丙基=鉀、5-磺基間苯二曱酸二正戊基=鉀、5-磺基間苯二 曱酸二-3-甲基丁基=鉀、5-磺基間苯二曱酸二-2-曱基丁基= 鉀、5-磺基間苯二曱酸二-2,2-二曱基丙基=鉀、5-磺基間苯 二甲酸二-2-曱基戊基=鉀、5-磺基間苯二曱酸二-3-曱基戊基 =鉀、5-磺基間苯二曱酸二-4-甲基戊基=鉀、5-磺基間苯二甲 酸二-3,3-二曱基丁基=鉀、5-磺基間苯二甲酸二-2,3-二曱基 丁基=鉀、5-磺基間苯二曱酸二環己基=鉀等磺基間苯二甲酸 098137214 13 201030072 二烷基的鉀鹽；4)5-磺基間苯-甲酴 苯二甲酸二乙基，、5_二' 甲基，、5_續基間 績基間苯二甲酸二異兩基:二二〜甲酸二正丙基=铯、5_ 鉋、5-磺基間笨二曱酸:異：基間苯二曱酸二正丁基= 第三丁基=铯、5_磺基 绝5_磺基間本-曱酸- 間苯二甲酸二正戊義—雜/酸…2、甲基丙基=链、5_石黃基 =絶、5-續基間笨二;酸二2=間笨二甲酸二基丁基 酸二-2,2-二甲基丙其^一甲基丁基=鉋、5-磺基間苯二曱 制侧笨甲酸叫^ 酸二_4_甲基戊基戍基％、5_續基間苯二甲 =鉋、5-磺基間笨二甲酸二:3間:二曱酸二_3,3_二曱基丁基 二甲酸援甲基丁基=絶、5-續基間本 甲酸一壤己基1等續基間苯 化1所示芳香族峰酸 酸一烧基的絶瓜等等 现就餉基對苯二甲酸二烷基的鹼 =塞體例係可舉例如，基對笨二 碩基對苯二甲酸_ ^ 文一乙基=鋰、磺基對苯二P酸二正丙基= « 苯—甲酸二異丙基=鋰、磺基對苯二甲酸二正丁 ^三^基對本二甲酸二異丁基=經、續基對苯二甲酸二 苯二尹二_ 4基對本二甲酸二_2_甲基丙基=鐘、續基對 -’文—正戊基=鋰、對苯二尹酸 链、績基對笨基丁純 :丁基- -2,2-二$基而Α ^ κ丞野本一 f酸二 ，美j 對苯二甲酸二基戍基=鐘、 續基對本二尹酸二越 098137214 © 〇 一 ，_一甲基丁基=鋰、磺基對笨二甲酸二 14 201030072 -2,3-二甲基丁細、磺基對苯二甲 對苯二甲酸二科的料；辦基對苯二” 基 :基對苯二甲酸二乙基,、私對苯 鈉、磺基對苯二甲酸一異而其知 丫醆一正丙基- 基=納、續基對苯二甲—酸異基^、績基對苯二？酸二正丁 第 甲酸-異丁基=鈉、磺基對苯二甲酸二 第一丁基=鈉、磺基對苯二 苯二甲酸二正戊基基二”基丙基=納、績基對 納、石黃基對苯二甲酸二_2 土丁基— f基•納、項基對·; :;n f酸二 續基對笨二甲酸二-3.甲基ΓΓ：： 基戊基=納、 ® # V, 土 績基對苯二甲酸二-4_ =基=納、續基對苯，二_3,3_二甲基丁基=納、續 二其 ，3-二甲基丁基=納、磺基對苯二f酸二環 參 酸二甲 基，二甲酸二貌基的納鹽；3)續基對苯二， 萨土-卸、％基對苯二甲酸二乙基=鉀、續基對苯二甲 =酸丙基=卸、續基對苯二甲酸二異丙基=鉀、續基對苯 ㈣-—正：基=卸、續基對苯二甲酸二異丁基=鉀、續基 一甲酸一第三丁基=鉀、磺基對苯 =卸、續基對苯二甲酸二正絲=鉀、對苯二;酸基= ^=，'縣«二甲酸二_2_甲基丁基=卸、續基對 本-甲酸二-2,2-二甲基丙基，、縣對苯二甲酸二正己其 =卸、縣對苯二甲酸二·2·甲基戊基=鉀、績基對苯二甲^ - Μ基戊㈣、續基對苯二甲酸二_4_甲基戊基會確 098137214 15 201030072 基對苯二尹酸二-3,3-二尹基丁基=卸、續基對苯二^酸二 -2’二二f基丁基=卸、績基對苯二甲酸二環己基=卸等續基 對本二’酸二烷基的鉀鹽；4)磺基對苯二m=鉋、 磺基對苯二甲酸二乙基=錄、績基對苯二f酸二正丙基= 鉋、續基對苯二甲酸二異丙基=鎚、續基對苯二甲酸二正丁 基=鏠、磺基對苯二甲酸二異丁基=鉋、磺基對苯二甲酸二 第三丁基ϋ基對苯m甲基丙基=铯、續基對 本-罗酸二正戊基=鏠、續基對苯二甲酸二_3_甲基丁爲= 鉋s基對苯一甲酸二_2_甲基丁基=錐、績基對笨二甲酸二 _:，2_二：基丙基务續基對笨二甲酸二_2_甲基戊基亦 %基對苯二甲酸二_3_甲基戊基=絶、績基對苯 :基，，苯二甲酸二*二甲基丁基二： 土士苯曱酸一-2,3-二甲基丁基=铯、磺基對苯二甲酸二产 己基-鎚等續基對笨二甲酸二燒基的銘鹽等等。 衣 土族金屬鹽具酸鹽中’就續基鄰苯二甲酸二燒基的鹼 、 八列係可舉例如：1)雙(4-磺基鄰笨二甲酸一 f :::::基鄰笨二甲酸一^ 雙㈣基鄰苯基鄰苯二甲酸二異丙基)=鎮、 一 文一正丁基)=鎂、雙(4-磺基鄰笨二甲酸 二正叫鎮、c、雙㈣基鄰笨二甲酸 芰(4-¾基鄰笨二甲酸二-3-T基丁基)=鎂、 098137214 16 201030072 雙(4-磺基鄰苯二曱酸二-2-曱基丁基)=鎂、雙(4-磺基鄰苯二 曱酸二-2,2-二曱基丙基)=鎂、雙(4-磺基鄰苯二曱酸二-4-甲 基戊基)=鎂、雙(4-磺基鄰苯二甲酸二-3,3-二曱基丁基)=鎂、 雙(4-磺基鄰苯二曱酸二-2,3-二甲基丁基)=鎂、雙(4-磺基鄰 苯二甲酸二環己基)=鎂等磺基鄰苯二甲酸二烷基的鎂鹽；2) 雙(4-磺基鄰苯二曱酸二甲基)=鈣、雙(4-磺基鄰苯二甲酸二 乙基)=鈣、雙(4-磺基鄰苯二甲酸二正丙基)=鈣、雙(4-磺基 φ 鄰苯二曱酸二異丙基)=鈣、雙(4-磺基鄰苯二曱酸二正丁基)= 鈣、雙(4-磺基鄰苯二曱酸二異丁基)=鈣、雙(4-磺基鄰苯二 曱酸二第三丁基)=鈣、雙(4-磺基鄰苯二曱酸二-2-曱基丙 基)=鈣、雙(4-磺基鄰苯二曱酸二正戊基)=鈣、雙(4-磺基鄰 苯二曱酸二-3-曱基丁基)=鈣、雙(4-磺基鄰苯二甲酸二-2-甲 基丁基)=名弓、雙(4-續基鄰苯二曱酸二-2,2-二曱基丙基)=妈、 雙(4-磺基鄰苯二甲酸二-2-曱基戊基)=鈣、雙(4-磺基鄰苯二 〇 曱酸二-3-曱基戊基)=鈣、雙(4-磺基鄰苯二曱酸二-4-曱基戊 基)==鈣、雙(4-磺基鄰苯二曱酸二-3,3-二甲基丁基)=鈣、雙(4-磺基鄰苯二曱酸二-2,3-二曱基丁基)=鈣、雙(4-磺基鄰苯二 曱酸二環己基)=鈣等磺基鄰苯二曱酸二烷基的鈣鹽；3)雙(4-磺基鄰苯二甲酸二曱基)=鋇、雙(4-磺基鄰苯二甲酸二乙基)= 鋇、雙(4·•磺基鄰苯二曱酸二正丙基)=鋇、雙(4-磺基鄰苯二 曱酸二異丙基)=鋇、雙(4-磺基鄰苯二曱酸二正丁基)=鋇、雙 (4-磺基鄰苯二曱酸二異丁基)=鋇、雙(4-磺基鄰苯二曱酸二 098137214 17 201030072 第三丁基)=鋇、雙(4-磺基鄰苯二甲酸二-2-曱基丙基)=鋇、 雙(4-磺基鄰苯二曱酸二正戊基)=鋇、雙(4-磺基鄰苯二甲酸 二-3-甲基丁基)=鋇、雙(4-磺基鄰苯二曱酸二-2-甲基丁基)= 鋇、雙(4-磺基鄰苯二曱酸二-2,2-二曱基丙基)=鋇、雙(4-磺 基鄰苯二曱酸二-2-曱基戊基)=鋇、雙(4-磺基鄰苯二曱酸二 -3-曱基戊基)=鋇、雙(4-磺基鄰苯二曱酸二-4-曱基戊基)= 鋇、雙(4-磺基鄰苯二曱酸二-3,3-二曱基丁基)=鋇、雙(4-磺 基鄰苯二曱酸二-2,3-二曱基丁基)=鋇、雙(4-磺基鄰苯二曱 酸二環己基=鋇等磺基鄰苯二曱酸二烷基的鋇鹽等等。 化1所示芳香族磺酸鹽中，就磺基間苯二甲酸二烷基的鹼 土族金屬鹽具體例係可舉例如：1)雙(5 -磺基間苯二曱酸二曱 基)=鎂、雙(5-磺基間苯二曱酸二乙基)=鎂、雙(5-磺基間苯 二曱酸二正丙基)=鎂、雙(5-磺基間苯二曱酸二異丙基)=鎂、 雙(5-磺基間苯二曱酸二正丁基)=鎂、雙(5_磺基間苯二曱酸 二異丁基)=鎂、雙(5-磺基間苯二曱酸二第三丁基)=鎂、雙(5-磺基間苯二曱酸二-2-曱基丙基)=鎂、雙(5-磺基間苯二曱酸 二正戊基)=鎂、雙(5-磺基間苯二甲酸二-3-甲基丁基)=鎂、 雙(5-磺基間苯二甲酸二-2-曱基丁基)=鎂、雙(5-磺基間苯二 曱酸二-2,2-二曱基丙基)=鎂、雙(5-磺基間苯二甲酸二-4-曱 基戊基)=鎂、雙(5-磺基間苯二曱酸二-3,3-二曱基丁基)=鎂、 雙(5-磺基間苯二曱酸二-2,3-二曱基丁基)=鎂、雙(5-磺基間 苯二甲酸二環己基)=鎂等磺基間苯二曱酸二烷基的鎂鹽；2) 098137214 18 201030072 雙(5-磺基間苯二曱酸二甲基)=鈣.、雙(5-磺基間苯二f酸二 乙基)=鈣、雙(5-磺基間苯二曱酸二正丙基)=鈣、雙(5-磺基 間苯二曱酸二異丙基)=鈣、雙(5-磺基間苯二曱酸二正丁基)= 鈣、雙(5-磺基間苯二甲酸二異丁基)=鈣、雙(5-磺基間苯二 甲酸二第三丁基)=鈣、雙（5-磺基間苯二曱酸二-2-甲基丙 基)=鈣、雙(5-磺基間苯二曱酸二正戊基)=鈣、雙(5-磺基間 苯二甲酸二-3-甲基丁基)=鈣、雙(5-磺基間苯二曱酸二-2-甲 ❹ 基丁基=妈、雙(5-石黃基間苯二甲酸二-2,2-二曱基丙基)=名弓、 雙(5-磺基間苯二曱酸二-2-曱基戊基)=鈣、雙(5-磺基間苯二 甲酸二-3-曱基戊基)=鈣、雙(5-磺基間苯二曱酸二-4-甲基戊 基)=鈣、雙(5-磺基間苯二曱酸二-3,3-二甲基丁基)=鈣、雙(5-磺基間苯二甲酸二-2,3-二甲基丁基)=鈣、雙(5-磺基間苯二 甲酸二環己基)=鈣等磺基間苯二曱酸二烷基的鈣鹽；3)雙(5-磺基間苯二曱酸二曱基)=鋇、雙(5-磺基間苯二甲酸二乙基)= ⑩ 鋇、雙(5-磺基間苯二甲酸二正丙基)=鋇、雙(5-磺基間苯二 甲酸二異丙基)=鋇、雙(5-磺基間苯二甲酸二正丁基)=鋇、雙 (5-磺基間苯二曱酸二異丁基)=鋇、雙(5-磺基間苯二曱酸二 第三丁基)=鋇、雙(5-磺基間苯二曱酸二-2-甲基丙基)=鋇、 雙(5-磺基間苯二曱酸二正戊基)=鋇、雙(5-磺基間苯二曱酸 二-3-曱基丁基)=鋇、雙(5-磺基間苯二曱酸二-2-曱基丁基)= 鋇、雙(5-磺基間苯二曱酸二-2,2-二曱基丙基)=鋇、雙(5-磺 基間苯二曱酸二-2-甲基戊基)=鋇、雙(5-磺基間苯二曱酸二 098137214 19 201030072 -3-曱基絲)=鋇、雙d基間苯二甲酸：_4·甲基 鋇、雙(5-磺基間苯二曱酸二3,3_二甲基丁基)=鋇 基間苯二甲酸二_2,3-二甲基丁基)=鋇、雙(5-磺基間苯二； 酸二環己基)=鋇等確基間笨二曱酸二垸基的鋇鹽等等。-化1所示芳香族磺酸鹽中，就磺基對笨二曱酸 土族金屬鹽具體例係可舉例如：1)雙(躲對笨的驗 基)=鎮、雙(續基對苯二甲酸二乙基)=鎂 酸一曱 酸二正丙基)=鎂、雙（石黃其對笨_ 、 R 土對笨二甲 A對苯一㈣ 異丙基㈣、雙㈣ 土對本一曱酸二正丁基)=鎂、雙（縣對笨二 基)=鎂、雙(磺基對笨二曱酸二第三丁美 一/、丁 二曱酸二-2-曱美κ 土 、、雙(磺基對笨 甲基丙基)=鎂、雙(磺基對笨二 鎂、雙(磺基對苯二〜正戍基)= 甲酸二1甲美丁其 基丁基)=鎮、雙(磺基對苯二 _ Μ 雙(磺基對苯二甲酸二办二甲美 丙基)=鎂、雙(磺基對苯二曱 土 對苯二甲酸二-33_二甲某丁々/基戊基)=鎮、雙嶋 一 ，-甲基丁基)’、雙(磺基對笨二曱酸二 續美2 鎂、細鞋H環己基)=鎮等 -曱酸―烧基的鎂鹽;2)雙(續基對苯二甲酸 基)=鈣、雙(磺基對苯二甲酸_ &其 酸-正雨其、你 ㈣-乙基卜鈣、雙(磺基對苯二甲 =丙基㈣、恤對苯二f酸二異丙基 2對本1酸二正丁基)，、雙(料對笨4酸二異丁 基)：、舰對笨二㈣二第三丁基)，、娜對笨 一 -2.甲基丙基)=妈、雙(項基對苯二f酸二正戊基)= 098137214 〇 ❹ 20 201030072 / 詞、雙(績基對苯m甲基丁基)♦雙(續基對苯二 甲酸二·2_甲基丁基)=鈣、雙(磺基對苯二甲酸二2,2 : 丙基)，、雙㈤基對苯二甲酸二_2_甲基戊基二 對苯二甲酸二·3·甲基戊基)脊雙(續基對苯二甲酸二= 基戊基Μ、雙(續基對苯二甲酸二·3,3_二甲基 ❹ 雙(續基對苯二甲酸二_2,3_二？基丁基)=舞、雙⑽基對笨二 甲酸二環己基)=妈等續基對苯二歹酸二燒基的約鹽⑽ (續基對苯二甲酸二▼基)=鋇、雙(續基對苯二甲酸 鋇、雙(續基對苯二尹酸二正丙基)=鋇、雙(續基對苯二甲^ 一異丙基)=鋇、雙(磺基對苯二甲酸二正丁㈣ 對苯二甲酸二異丁基）=鎖、雙（續基對苯二▼酸二第In the formula 1, X: residues R1 and R2 for removing three hydrogen atoms from benzene: hydrocarbon group having 1 to 6 carbon atoms 098137214 8 201030072 Μ: alkali metal atom or alkaline earth metal atom η: 1 or 2' when]V [In the case of a metal atom, it is η = 1, and when it is a metal atom of the soil test group, it is η = 2. Further, the polylactic acid resin composition of the present invention contains a constituent unit formed of L_lactic acid. Or a constituent unit formed of D-lactic acid, which is 95 to 99 mol% of the total constituent unit, and a crystal nucleating agent for a polylactic acid resin of the present invention. [Embodiment] First, a crystal nucleating agent for polylactic acid resin (hereinafter referred to as "the crystal nucleating agent of the present invention") of the present invention will be described. The crystal nucleating agent of the present invention is composed of an aromatic sulfonate represented by hydrazine. The aromatic sulfonate represented by the formula 1 includes an alkali metal salt of a dialkyl sulfophthalic acid dialkyl group, 2) an alkali metal salt of a dialkyl sulfoisophthalic acid dialkyl group, and 3) a sulfo group. An alkali metal salt of a dialkyl terephthalate, an alkaline earth metal salt of a dialkyl sulfophthalate, 5) an alkaline earth metal salt of a dialkyl alkyl sulfoisophthalate, 6) a sulfo group An alkaline earth metal salt of a dialkyl terephthalate, and 7) any mixture of the above 1) to 6). In the non-aromatic sulfonate of the first embodiment, the X system in the compound 1 removes the residue of three hydrogen atoms from the stupid one. Further, Ri and R2 in the formula i are as follows: methyl, ethyl, propyl, isopropyl, isobutyl, pentyl, hexyl, cyclopentyl, cyclohexyl, allyl, cyclohexenyl, etc. The hydrocarbon group having a carbon number of 丨6 or less, preferably an aliphatic hydrocarbon group having a carbon number, more preferably a methyl group. Among the non-aromatic sulfonates, the lanthanide in the chemical formula 1 is as follows: 1) lithium 098137214 9 201030072, an alkali metal atom such as a sodium atom, a potassium atom, a cesium atom or a planing atom; 2) a wrinkle atom, magnesium The atomic group, the fresh atom, the recorded atom, the locked atom and the like are metal atoms of the soil test group, and among them, a potassium atom, a helium atom, a helium atom, a helium atom, and a calcium atom are preferable, and a potassium atom and a helium atom are more preferable. In the aromatic sulfonate represented by the formula 1, the alkali metal salt of the dialkyl sulfophthalate is exemplified by, for example, 1) 4-sulfophthalic acid dimethyl group = lithium, 4 - sulfophthalic acid diethyl = lithium, 4-sulfophthalic acid di-n-propyl = lithium, 4-sulfophthalic acid diisopropyl = lithium, 4-sulfo Di-n-butyl phthalate = lithium, diisobutyl 4-sulfophthalate = lithium, di-t-butyl 4-sulfophthalate = lithium, 4-sulfo-o- Di-2-methylpropyl phthalate = lithium, di-n-pentyl 4-sulfophthalate = lithium, 4-sulfophthalic acid di-3-mercaptobutyl group = lithium, 4 - sulfophthalic acid di-2-mercaptobutyl group = lithium, 4-sulfophthalic acid di-2,2-dimethylpropyl group = lithium, 4-sulfophthalic acid Di-n-hexyl = lithium, 4-sulfophthalic acid di-4-mercaptopentyl = lithium, 4-sulfophthalic acid di-3,3-dimethylbutyl = lithium, 4 - lithium sulfophthalate - 2,3-dimercaptobutyl = lithium, 4-sulfophthalic acid dicyclohexyl = lithium sulfophthalic acid dialkyl lithium salt; 2) 4-sulfophthalic acid dinonyl group = sodium, 4-sulfo-o-phenylene Acid diethyl = sodium, 4-sulfophthalic acid di-n-propyl = sodium, 4-sulfophthalic acid diisopropyl = sodium, 4-sulfophthalic acid di-n-acid Butyl = sodium, diisobutyl 4-sulfophthalate = sodium, ditributyl 4-sulfophthalate = sodium, 4-sulfophthalic acid di-2-indole Propyl group = sodium, 4-sulfophthalic acid di-n-pentyl group = sodium, 4-sulfophthalic acid di 098137214 10 201030072 -3-mercaptobutyl group = sodium, 4-lithophthalyl phthalate Di-2-mercaptobutyl formate = nano, 4_ sulfophthalic acid di-2,2-dimercaptopropyl = sodium, 4-sulfophthalic acid di-n-hexyl = nano, 4 - Shihuang phthalic acid di-2-methylpentyl = sodium, 4-ylidene phthalic acid bis-3-methylpentyl = sodium, 4-sulfophthalic acid di-4-methyl Ylpentyl = nano, 4-thyl phthalic acid di-3,3-dimethylbutyl = steel, 4-thyl phthalic acid di-2,3-didecyl butyl = Sodium, 4-sulfophthalic acid dicyclohexyl = nano-sodium phthalate dihalogenated sodium salt, 3) 4-dibasic phthalic acid dihydrazinyl = potassium, 4- Sulfo phthalic acid diethyl = potassium, 4-sulfophthalic acid Propyl = potassium, 4-sulfophthalic acid diisopropyl = potassium, 4-• sulfophthalic acid di-n-butyl = potassium, 4-sulfophthalic acid diisobutyl Base = potassium, 4-sulfophthalic acid di-t-butyl = potassium, 4-sulfophthalic acid di-2-mercaptopropyl = bell, 4-mineryl phthalic acid JL pentyl = unloaded, 4-thyl phthalic acid di-3-mercaptobutyl butyl = potassium, 4-sulfophthalic acid di-2-methyl butyl = unloaded, 4-contiguous neighbor Di-2,2-dimethylpropyl phthalate = sulphate, 4-n-yl phthalic acid n-hexyl = potassium, 4-sulfophthalic acid di-2-mercaptopentyl = potassium , 4-sulfophthalic acid di-3-indolyl pentyl = potassium, 4-sulfophthalic acid di-4-indenyl fluorenyl = bell, 4-ylidene phthalic acid Bis-3,3-dimercaptobutyl@potassium, 4-sulfophthalic acid di-2,3-dimercaptobutyl-potassium, 4-sulfophthalic acid dicyclohexyl= Potassium salt of sulfophthalic acid dialkyl such as potassium; 4) 4-sulfophthalic acid dimethyl = planer, 4-sulfophthalic acid diethyl = planer, 4- Di-n-propyl sulfophthalate = planing, diisopropyl 4-sulfophthalate = planing, 4-sulfophthalic acid Di-n-butyl = planing, 4-sulfophthalic acid 098137214 11 201030072 Diisobutyl = planing, 4-sulfophthalic acid di-tert-butyl = planing, 4-sulfo-o-phenylene Di-2-mercaptopropyl phthalate = planing, di-n-pentyl 4-sulfophthalate = hydrazine, 4-sulfophthalic acid di-3-mercaptobutyl butyl = hydrazine, 4 - sulfophthalic acid di-2-mercaptobutyl group = planing, 4-sulfophthalic acid di-2,2-dimercaptopropyl = planing, 4-sulfophthalic acid Di-2-mercaptopentyl acid = planer, 4-sulfophthalic acid di-3-indolyl pentyl = hydrazine, 4-sulfophthalic acid di-4-mercaptopentyl = Bismuth, 4-sulfophthalic acid di-3,3-didecylbutyl = planing, 4-sulfophthalic acid di-2,3-dimethylbutyl = planing, 4-sulfoyl a dicyclohexyl phthalic acid = a sulfonium phthalic acid dialkyl sulfonate salt or the like. Specific examples of the alkali metal salt of a dialkyl sulfoisophthalate in the aromatic sulfonate represented by the formula 1 include, for example, 1) 5-sulfoisophthalic acid dinonyl group = lithium, 5 - sulfoisophthalic acid diethyl = lithium, 5-sulfoisophthalic acid di-n-propyl = lithium, 5-sulfoisophthalic acid diisopropyl = lithium, 5-sulfo Di-n-butyl phthalate = ketone, 5-di-m-phenylene phthalate diisobutyl = ketone, 5-dibasic meta-benzoic acid di-t-butyl = lithium, 5-sulfo Di-2-mercaptopropyl phthalate = lithium, di-n-pentyl 5-sulfoisophthalate = lithium, 5-sulfoisophthalic acid di-3 -mercaptobutyl group = clock, 5 - feldsparin di-2-mercaptobutyl phthalate = 5, sulfoisophthalic acid di-2,2-dimercaptopropyl = lithium, 5-sulfoisophthalic acid 4-mercaptopentyl = lithium, 5-sulfoisophthalic acid di-3,3-didecylbutyl = lithium, 5-sulfoisophthalic acid di-2,3-didecyl Butyl = lithium, 5-sulfoisophthalic acid dicyclohexyl = lithium sulfoisophthalic acid dialkyl lithium salt; 2) 5-sulfoisophthalic acid dimercapto = sodium, 5-sulfoisophthalic acid diethyldi-sodium, 098137214 12 201030072 5- Di-n-propyl sulfoisophthalate = sodium, diisopropyl 5-sulfoisophthalate = nano, 5-n-butyl di-n-butyl isophthalate = nano, 5-thyl-phenylene Diisobutyl phthalate = nano, 5-thyl isophthalic acid dibutyl butyl = nano, 5-thyl phthalic acid di-2-mercaptopropyl = sodium, 5-sulfo Di-n-pentyl phthalate = nano, 5-thyl-phenylene phthalate di-3-indenyl butyl = sodium, 5-hydroxyisophthalic acid di-2-indenyl butyl = sodium, 5 - sulfoisophthalic acid di-2,2-dimercaptopropyl=n,5-thyl-diphenylphthalic acid di-2-indenyl fluorenyl=nano, 5-retentyl benzodiazepine Di-3-nonylpentyl phthalate = sodium, 5-sulfoisophthalic acid di-4-mercaptopentyl = sodium, 5-sulfoisophthalic acid di-3,3-dimethyl Butyl = sodium, 5-sulfoisophthalic acid di-2,3-dimercaptobutyl = sodium, 5-sulfoisophthalic acid dicyclohexyl = sodium, etc. sulfoisophthalic acid dioxane Sodium salt; 3) 5-sulfoisophthalic acid dimercapto = potassium, 5-sulfoisophthalic acid diethyl = potassium, 5-sulfoisophthalic acid di-n-propyl = potassium , 5-sulfoisophthalic acid diisopropyl = potassium, 5-sulfoisophthalic acid di-n-butyl = potassium, diisobutyl 5-sulfoisophthalate = potassium, 5-G sulfoisophthalic acid di-t-butyl = potassium, 5-sulfoisophthalic acid di-2-methyl Propyl = potassium, 5-sulfoisophthalic acid di-n-pentyl = potassium, 5-sulfoisophthalic acid di-3-methylbutyl = potassium, 5-sulfoisophthalic acid Di-2-mercaptobutyl group = potassium, 5-sulfoisophthalic acid di-2,2-dimercaptopropyl group potassium, 5-sulfoisophthalic acid di-2-mercaptopentyl group = potassium, 5-sulfoisophthalic acid di-3-mercaptopentyl = potassium, 5-sulfoisophthalic acid di-4-methylpentyl = potassium, 5-sulfoisophthalene Di-3,3-didecyl butyl=potassium formate, di-2,3-didecylbutyl=potassium 5-sulfoisophthalate, dicyclohexyl 5-sulfoisophthalic acid= Potassium and other sulfoisophthalic acid 098137214 13 201030072 dialkyl potassium salt; 4) 5-sulfoisophthalic acid-methyl phthalic acid diethyl, 5 bis-methyl, 5 _ contiguous Dibasic isophthalic acid diiso-isoyl: di-di-dicarboxylic acid di-n-propyl = hydrazine, 5_ planing, 5-sulfo-p-dioxoic acid: iso: di-n-butyl phthalic acid = third Butyl = hydrazine, 5 sulfoyl 5 - sulfo-benzic acid - di-n-isophthalic acid义-杂/酸...2, methylpropyl=chain, 5_石黄基=绝,5-continuation between stupid base; acid 2 2=meta-dicarboxylic acid di-butyl bis- 2,2- Dimethyl propyl methacrylate = planer, 5-sulfoisophthalonitrile, side benzoic acid, acid _4_methylpentyl fluorenyl, 5, contiguous phthalic acid = Planing, 5-sulfo-p-dicarboxylic acid 2: 3: di-decanoic acid bis-3,3-didecyl butyl dicarboxylic acid methyl butyl = absolute, 5-thyl intermediate nitric acid The aryl group of the fluorenyl-terephthalic acid dialkyl group, such as the base group Phthalic acid _ ^ Wenyi ethyl = lithium, sulfo-p-phenylene di-P-acid di-n-propyl = « Benzene-formic acid diisopropyl = lithium, sulfo-terephthalic acid di-n-butyl ^ 3 ^ base pair two Diisobutyl carboxylic acid = trans, tert-butylene terephthalate di- -4-yl p-dicarboxylic acid di-2-methylpropyl = bell, contiguous pair - 'text - n-pentyl = lithium, pair Benzene acid chain, the base pair of stupyl butyl pure: butyl - 2, 2- nd yl and Α ^ κ 丞 本 一 f f acid II, US j terephthalic acid diyl fluorenyl = clock, continued Base pair Dipyroic acid di 098137214 © 〇一, _ monomethyl butyl = lithium, sulfo-p-benzoic acid di 14 201030072 -2,3-dimethylbutyl, sulfo-p-xylylene terephthalate The material of the family; the base of the benzenediyl group: diethyl terephthalate, private sodium p-phenylene, sulfo terephthalic acid, and its knowledge of a n-propyl group; Base to phthalic acid-acidic hetero group ^, Jiji to benzene? Di-n-butyl butyrate-isobutyl = sodium, sulfophthalic acid di-first butyl = sodium, sulfo-terephthalic acid di-n-pentyl dimethyl propyl = sodium, Nano, feldspar, terephthalic acid, tert-butyl phthalate, ketone, sodium, ketone, sodium, ketone, sodium, ketone, ketone =Na, ® # V, Physic-based terephthalic acid 2-4_ = base = nano, contiguous phenyl, bis-3,3-dimethyl butyl = sodium, continuation, 3-dimethyl Butyl = sodium, sulfo-p-phenylene di-acid dicyclohexanoic acid dimethyl, dicarboxylic acid dimorphic sodium salt; 3) contiguous p-phenylene, sul- unloading, % butyl terephthalate Base = potassium, contiguous p-xylylene = acid propyl = unloaded, dibasic terephthalic acid diisopropyl = potassium, contiguous to benzene (tetra) - positive: base = unloading, contiguous terephthalic acid Isobutyl group = potassium, contiguous monocarboxylic acid - tert-butyl group = potassium, sulfo-p-phenylene = unloading, dibasic terephthalic acid di-n-wire = potassium, p-phenylene; acid group = ^=, 'county« Di-2-methyl butyl dicarboxylate = unloading, contiguous pair of di- 2,2-dimethylpropyl benzoic acid, di-n-hexyl phthalate = unloading, county benzoic acid Acid di-2,methylpentyl=potassium, genomic p-xylylene^-mercaptopentyl (tetra), contigyl terephthalic acid bis-4-methylpentyl group 098137214 15 201030072 Bis-3,3-di-n-butyl butyl = unloading, contiguous p-benzoic acid di-2' bis-diyl butyl = unloading, dibasic terephthalic acid dicyclohexyl = unloading contiguous to the di-acid Potassium salt of dialkyl; 4) sulfo-p-phenylene m=planar, sulfo-terephthalate diethyl = record, base-p-phenylene b-acid di-n-propyl = planer, contiguous terephthalic acid Diisopropyl = hammer, contiguous di-n-butyl terephthalate = hydrazine, diisobutyl sulfo terephthalate = planing, sulfobutyl terephthalate di-tert-butyl fluorenyl-p-phenylene Propyl group 铯, 续 对 本 本 本 本 罗 鏠 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = Cone, base pair of benzoic acid di-:, 2_di: propyl propyl group, benzoic acid di-2-methylpentyl phthalate, bis-3-methylpentyl = Benzene: base, bis-dimethyl butyl phthalate: tert-benzoic acid--2,3-dimethylbutyl hydrazine, sulfo terephthalic acid A salt of a hexyl-hammer or the like, a salt of a dialkyl group of a benzoic acid, and the like. In the case of a sulphate metal salt, the base of the phthalic acid dialkyl group, the octagonal system, for example, ) bis(4-sulfo-o-p-dicarboxylic acid-f:::::yl-o-p-dicarboxylic acid-^bis(tetra)-o-phenylene phthalate diisopropyl)= town, mono-n-butyl) = Magnesium, bis(4-sulfo-o-p-benzoic acid di-n-shenzhen, c, bis(tetra)-yl-p-phenylidene dicarboxylate (4-3⁄4-yl-p-benzoic acid di-3-t-butyl)=magnesium, 098137214 16 201030072 Bis(4-sulfophthalic acid di-2-mercaptobutyl)=magnesium, bis(4-sulfophthalic acid di-2,2-dimercaptopropyl)=magnesium, Bis(4-sulfophthalic acid di-4-methylpentyl)=magnesium, bis(4-sulfophthalic acid di-3,3-didecylbutyl)=magnesium, double 4-sulfophthalic acid di-2,3-dimethylbutyl)=magnesium, bis(4-sulfophthalic acid dicyclohexyl)=magnesium sulfophthalate dialkyl Magnesium salt; 2) bis(4-sulfophthalic acid dimethyl) = calcium, bis(4-sulfophthalic acid diethyl) = calcium, bis(4-sulfo-o-phenylene) Di-n-propyl formate)=calcium, bis(4-sulfoφ phthalate Acid diisopropyl)=calcium, bis(4-sulfophthalic acid di-n-butyl)=calcium, bis(4-sulfophthalic acid diisobutyl)=calcium, double (4 - sulfophthalic acid di-t-butyl) = calcium, bis(4-sulfophthalic acid di-2-mercaptopropyl) = calcium, bis(4-sulfophthalic acid) Acid di-n-pentyl)=calcium, bis(4-sulfophthalic acid di-3-mercaptobutyl)=calcium, bis(4-sulfophthalic acid di-2-methylbutyl) ) = famous bow, bis (4- continued phthalic acid di-2,2-dimercaptopropyl) = mother, bis (4-sulfophthalic acid di-2-indenyl pentyl) = calcium, bis(4-sulfophthalic acid di-3-indolyl pentyl) = calcium, bis(4-sulfophthalic acid di-4-mercaptopentyl) == calcium , bis(4-sulfophthalic acid di-3,3-dimethylbutyl)=calcium, bis(4-sulfophthalic acid di-2,3-didecylbutyl) = calcium, bis(4-sulfophthalic acid dicyclohexyl) = calcium salt of sulfophthalic acid dialkyl such as calcium; 3) bis(4-sulfophthalic acid dinonyl) )=钡, bis(4-sulfophthalic acid diethyl)=钡, bis(4·•sulfophthalic acid di-n-propyl)=钡, bis(4-sulfo-o-phenylene) Diisopropyl phthalate = 钡Bis(4-sulfophthalic acid di-n-butyl)=钡, bis(4-sulfophthalic acid diisobutyl)=钡, bis(4-sulfophthalic acid) 098137214 17 201030072 Third butyl)=钡, bis(4-sulfophthalic acid di-2-mercaptopropyl)=钡, bis(4-sulfophthalic acid di-n-pentyl)= Bismuth, bis(4-sulfophthalic acid bis-3-methylbutyl)=indole, bis(4-sulfophthalic acid di-2-methylbutyl)=钡, double (4 - sulfophthalic acid di-2,2-dimercaptopropyl)=indole, bis(4-sulfophthalic acid di-2-mercaptopentyl)=钡, double (4- Sulfophenylphthalic acid di-3-indolylpentyl)=indole, bis(4-sulfophthalic acid di-4-mercaptopentyl)=indole, bis(4-sulfo-o-benzene) Di-3,3-dimercaptobutyl phthalate = bismuth, bis(4-sulfophthalic acid di-2,3-didecylbutyl)=indole, bis(4-sulfoyl) Anthracene salt of dialkylhexyl phthalate = sulfophthalic acid dialkyl such as hydrazine. In the aromatic sulfonate represented by the formula 1, the alkaline earth metal salt of the dialkyl sulfoisophthalate is exemplified by, for example, 1) bis(5-sulfoisophthalic acid dimethylene). = magnesium, bis(5-sulfoisophthalic acid diethyl) = magnesium, bis(5-sulfoisophthalic acid di-n-propyl) = magnesium, bis(5-sulfoisophthalene Acid diisopropyl)=magnesium, bis(5-sulfoisophthalic acid di-n-butyl)=magnesium, bis(5-sulfoisophthalic acid diisobutyl)=magnesium, double (5 - sulfoisophthalic acid di-t-butyl) = magnesium, bis(5-sulfoisophthalic acid di-2-mercaptopropyl) = magnesium, bis(5-sulfoisophthalene Acid di-n-pentyl)=magnesium, bis(5-sulfoisophthalic acid bis-3-methylbutyl)=magnesium, bis(5-sulfoisophthalic acid di-2-mercaptobutyl) = magnesium, bis(5-sulfoisophthalic acid di-2,2-dimercaptopropyl) = magnesium, bis(5-sulfoisophthalic acid di-4-indolyl)-magnesium , bis(5-sulfoisophthalic acid di-3,3-didecylbutyl)=magnesium, bis(5-sulfoisophthalic acid di-2,3-didecylbutyl) = magnesium, bis(5-sulfoisophthalic acid dicyclohexyl) = magnesium salt of sulfoisophthalic acid dialkyl such as magnesium; 2) 098137214 18 2010300 72 bis(5-sulfoisophthalic acid dimethyl)=calcium, bis(5-sulfoisophthalic acid diethyl)=calcium, bis(5-sulfoisophthalic acid II N-propyl) = calcium, bis(5-sulfoisophthalic acid diisopropyl) = calcium, bis(5-sulfoisophthalic acid di-n-butyl) = calcium, bis (5-sulfonate) Diisobutyl phthalate = calcium, bis(tributary butyl sulphonate) = calcium, bis(5-sulfoisophthalic acid di-2-methylpropane) Base) = calcium, bis(5-sulfoisophthalic acid di-n-pentyl) = calcium, bis(5-sulfoisophthalic acid bis-3-methylbutyl) = calcium, double (5- Sulfophenylisophthalic acid di-2-methylindenyl butyl = mother, bis (5-diglyme isophthalic acid di-2,2-dimercaptopropyl) = famous bow, double (5- Sulfosylisophthalic acid di-2-mercaptopentyl)=calcium, bis(5-sulfoisophthalic acid di-3-indolylpentyl)=calcium, bis(5-sulfoisophthalene) Di-4-methylpentyl phthalate)=calcium, bis(5-sulfoisophthalic acid di-3,3-dimethylbutyl)=calcium, bis(5-sulfoisophthalic acid) Di-2,3-dimethylbutyl)=calcium, bis(5-sulfoisophthalic acid dicyclohexyl)=calcium sulfoisophthalic acid dialkyl calcium salt; 3) double ( 5-sulfoisophthalic acid Dimethyl phthalate)=钡, bis(5-sulfoisophthalic acid diethyl)= 10 钡, bis(di-propyl 5-sulfoisophthalate)=钡, bis (5-sulfonate) Diisopropyl) isophthalic acid = hydrazine, bis(di-butyl 5-sulfoisophthalate) = hydrazine, bis(diisobutyl 5-sulfoisophthalate) = hydrazine, Bis(di-tert-butyl 5-sulfoisophthalic acid)=钡, bis(5-sulfoisophthalic acid di-2-methylpropyl)=钡, bis(5-sulfo group Di-n-pentyl phthalate)=钡, bis(5-sulfoisophthalic acid di-3-indolyl butyl)=钡, bis(5-sulfoisophthalic acid di-2-) Mercaptobutyl) = bismuth, bis(5-sulfoisophthalic acid di-2,2-dimercaptopropyl)=indole, bis(5-sulfoisophthalic acid di-2-methyl) Ylpentyl)=钡, bis(5-sulfoisophthalic acid di 098137214 19 201030072 -3-fluorenyl filament)=钡, double d-based isophthalic acid: _4·methyl hydrazine, double (5- Sulfo-isophthalic acid di 3,3-dimethylbutyl)=mercaptoisophthalic acid di-2,3-dimethylbutyl)=indole, bis(5-sulfoisophthalic acid; Acid dicyclohexyl) = hydrazine, etc. In the aromatic sulfonate represented by the formula 1, the specific examples of the sulfo group to the stearic acid earth metal salt include, for example, 1) double (hiding to the stupid base) = town, double (renewed to benzene) Diethyl diformate = di-n-propyl magnesium monodecanoate) = magnesium, double (stone yellow, stupid _, R, earth, stupid, dimethyl, p-benzoic acid) Di-n-butyl phthalate = Magnesium, Shuang (county to stupid base) = Magnesium, bis (sulfo-p-benzoic acid di-n-butadiene-/, succinic acid di-2-indole κ soil , bis(sulfo-p-methylpropyl)=magnesium, bis(sulfo-p-bromo-di-magnesium, bis(sulfo-p-phenylene-n-decyl)=carboxylic acid di-l-methyl-butyryl-butyl)= town, Bis(sulfo-p-phenylene bismuth bis(sulfo-terephthalic acid dimethylene methacrylate)=magnesium, bis(sulfo-p-phenylene terephthalate terephthalate di-33_ dimethyl butyl hydrazine / Ylpentyl) = town, biguanide, -methylbutyl)', double (sulfo-p-benzoic acid, two-dimensional magnesium, fine shoe H-cyclohexyl) = town, etc. - citric acid-burning Magnesium salt; 2) bis (contigyl terephthalate) = calcium, bis (sulfo terephthalic acid _ & its acid - positive rain, you (four) - ethyl calcium, bis (sulfo-p-benzene) Dimethyl = propyl (tetra), t-p-phenylene f-acid diisopropyl 2 to di-n-butyl of 1 acid, double (material to di-butyl 4-isobutyl): ship to stupid two (four) two third Butyl), 娜对笨一-2. Methylpropyl)=Mom, bis(m-phenylene-f-acid di-n-pentyl)= 098137214 〇❹ 20 201030072 / word, double (performance base to benzene m Methyl butyl) ♦ bis (contigyl di-terephthalic acid di-2-methyl butyl) = calcium, bis(sulfophthalic acid di 2,2: propyl), bis(penta)-p-phenylene Di-2-methylammonyl diterephthalate di-3·methylpentyl) ridge bis (contigyl terephthalic acid bis = pentyl hydrazine, bis (contiguous terephthalic acid bis-2) , 3_ dimethyl hydrazine bis (contigyl phthalic acid di-2,3 bis- butyl) = dance, bis (10) phenyl p-dicyclohexyl dicarboxylic acid) = mom et al. About salt of acid dialkyl (10) (contigyl di-terephthalic acid diheptyl) = bismuth, bis (contiguous bismuth terephthalate, bis (contiguous p-terphenyl yanoyl di-n-propyl) = 钡, double (Continuation of p-xylylene^-isopropyl)=钡, bis(di-n-butyl sulfo-terephthalate (tetra) diisobutyl terephthalate)=locked, double (renewed p-terephthalic acid) First
酸雙酸二基丙基，基對 本-甲酸—正戍基)=鋇、雙(縣對苯H 參 餘鋇、雙《基對苯基丁基)=鋇、__ 本一’酸二-2,2_二甲基丙基)，、雙(磺基對苯二子酸二 =㈣、_瓣項：· U基對本二甲酸二基戊基)=鋇、雙(續基對苯二甲酸二 _3,3_一甲基丁基)=鋇、雙(磺基對苯二u f雙(續基對苯二尹酸二環己基>=鋇等續基對笨二 酸二烷基的鋇鹽等等。 —尹 如上朗的们所衫㈣顧縣身 法進行合成。可❹日本彻—97“= 098137214 21 201030072 載的方法。 本發明結晶核劑係如上說明的芳香族磺酸鹽，且平均粒徑 調整於0_1〜10/mi範圍内，較佳調整於〇 5〜5 〇Alms圍内， 更佳調整於0.8〜3.0μηι範圍内。此處所謂「平均粒徑」係指 依照雷射繞射•散射法所測得的5〇%體積粒徑（中間粒徑）。 若芳香族績酸鹽的平均粒徑大於1〇从m，將便將其使用於由 L-乳酸所形成構成單位、或由D_乳酸所形成構成單位，佔 全構成單位中95〜99莫耳％的聚乳酸樹脂中，仍無法充分提❹ 升結晶化。反之，若芳香族磺酸鹽的平均粒徑小於〇 Mm， 則即使將其使用於同樣的聚乳酸樹脂，不僅會因處置時的揚 塵而導致作業環境變差，且與聚乳酸樹脂間的混練性亦差， 結果便無法充分地提升結晶化。 將當作結晶核劑用的芳香族磺酸鹽平均粒徑，調整於 0.1〜10/im的方法，係有如：將芳香族磺酸鹽，G提供給諸 如喷射粉碎機、球磨機、珠賴、旋風粉碎機等乾式粉碎機，⑬ 而進行平均粒徑調整的方法；2)一起使用諸如水、有機溶 劑、或水與有機溶劑的混合溶液等，提供給諸如砂輪機、球 磨機、珠磨機等濕式粉碎機，而進行平均粒徑調整的方法， 但就從生產性的觀點，較佳為上述丨）之方法。 其次，針對本發明的聚乳酸樹脂組成物（以下簡稱「本發 明組成物」）進行說明。本發明組成物係含有：由^乳酸所 形成構成單位或由D_乳酸卿成構成單位，佔全構成單位 098137214 22 201030072 中95〜99莫耳％的聚乳酸樹脂，以及上述本發明結晶核劑而 構成。就從所獲得聚乳酸樹脂組成物之物性的觀點，較佳係 由L-乳酸所形成構成單位佔全構成單位中96〜99莫耳％的 聚乳酸樹脂，更佳係由L-乳酸所形成構成單位佔全構成單 位中98〜99莫耳％的聚乳酸樹脂。 聚乳酸樹脂本身係可依照公知方法進行合成。可例如日本 專利特開平7-33861號公報、特開昭59-96123號公報、高 ❿ 分子討論會預稿集第44卷中第3198-3199頁所記載，1)將 乳酸直接施行脫水縮合反應的方法；2)將乳酸的交酯進行開 環聚合之方法等。上述1)的方法係可使用L-乳酸、D-乳酸、 DL-乳酸、或該等混合物中之任一種乳酸。上述2)的方法係 可使用L-交酯、D-交酯、DL-交酯、内消旋-交酯、或該等 混合物中之任一種交酯❶原料交酯的合成、精製及聚合方 法，亦是可適用公知方法。可例如美國專利號說明 © 書、公開歐洲專利出願第261572號說明書、Polymer Bulletin， 14, 491-495(1985)、Macromol. Chem” 187, 1611-1628(1986) 等所記載的方法。 本發明組成物所使用的聚乳酸樹脂較佳係將質量平均分 子量(依凝膠滲透色層分析儀進行分析的聚苯乙烯換算值， 以下亦同）設為80000以上、更佳設為10〇〇〇〇以上、特佳設 為110000〜200000。若聚乳酸樹脂的質量平均分子量未滿 80000，則所獲得成形體的強度、彈性模數等機械特性容易 098137214 23 201030072 不足，呈現質量平均分子量越高，此種機械特性有越提升的 傾向。又，若聚乳酸樹脂的質量平均分子量在2〇〇〇〇〇以下， 便呈現適於成形的流動性。 本發明組成物所使用的聚乳酸樹脂，較佳係將其所含的殘 存單體設為5000ppm以下、更佳4〇〇〇ppm以下、特佳 3000PPm以下。若聚乳酸樹脂中的殘存單體量超過 5000PPm，因域存频具有水解的簡魏，因而即便添 加諸如碳二醯亞胺系化合物、哼唑啉系化合物、異氰酸酯 化合物等已知水解抑制劑，仍無法充分發揮效果，、容易導致⑬ 耐濕熱老化性與财熱性不足。且，呈現聚乳酸中的殘存單體 越低，耐濕熱老化性與耐熱性越提升的傾向。 本發明組成物中，上述本發明結晶核劑的含有比例，較佳 係聚乳酸樹脂每刚質量份，設為〇 〇1〜1〇質量份、更佳 〇.卜5質量份、特佳〇.5〜3 f量份。理由係任—情況均能充 分發揮在聚乳酸樹脂中添加結晶核劑之化i所示芳香族續〇 酸鹽的添加#罢。 本發明組祕餘結晶_亦可—起含有化1所示芳香 族續酸鹽’以及上述公知有撫备从。 有機系結晶核劑及/或無機系結晶 核劑。該有機系結晶核劑中軔4 π 〇人士旦私“ 為知肪族酿胺與芳香族醯 胺’且含有量較佳係設為與化1所一# W不方香族磺酸鹽含有量同 等或以下。此外，無㈣結晶_中_係滑石，且含有比 例較佳係設為聚乳酸樹脂每1〇〇 寫重份含有1〜20質量份。 098137214 24 201030072 本發明組成物係就從剛性、柔軟性、耐熱性、耐久性等物 性提升的觀點，亦可含有其他樹脂。該其他樹脂的具體例， 就合成樹脂射舉例如：聚碳酸自旨、聚對苯二f酸乙二醋、 料苯二甲酸丁二自旨、聚萘二甲酸乙二自旨等雜；聚苯醚、 聚乙烯聚丙烯、聚氯乙稀、聚縮酸、聚苯硫、樹脂、 樹月曰HIPS等聚苯乙烯系樹脂；聚甲基丙婦酸甲醋等丙 稀酸系樹脂；以及聚_等。該㈣可單獨使用、或組合使 用^種以上。其中，就從與聚乳酸樹脂間之相溶性觀點，較 佳係具有諸如6旨鍵結、碳酸g旨鍵結等含縣鍵結的樹脂，更 佳為ABS樹脂、聚對苯二曱酸丁二酯、聚碳酸酯。 本發明組成物配合特定目的尚可含有其他添加劑。該其他 添加劑係可舉例如：可塑劑、抗氧化劑、熱安定劑、光安定 幻糸外線吸收劑、顏料、著色劑、各種填料、抗靜電劑、 脫模劑、香料、滑劑、難燃劑、發泡劑、填充劑、抗菌•防 ® 霉劑等。 以上所說明的本發明組成物係可依照公知方法進行調 製。可例如：1)將粉末或顆粒狀聚乳酸樹脂、與結晶核劑、 以及視需要的其他添加劑，同時施行乾式摻合後，再施行混 練的方法；2)將粉末或顆粒狀聚乳酸樹脂、與結晶核劑施行 預摻合，更視需要將其他添加劑施行乾式摻合後，再施行混 練的方法等。該乾式摻合的裝置係可舉例如：輥磨機(mill roll)、班布瑞混合機、快速混合機(SUper mixer)等。此外， 098137214 25 201030072 混練機係可舉例如單螺桿或雙螺桿擠出機等。混練機的混練 溫度通常設為120〜22(TC程度。在聚乳酸樹脂的聚合階段 中’亦可添加結晶核劑、或視需要的其他添加劑，且亦可預 先製作依高濃度含有結晶核劑或視需要的其他添加劑之濃 縮物後’再將其添加於聚乳酸樹脂中。 (發明效果） 若使用本發明結晶核劑，即使對由L-乳酸所形成構成單 位、或由D-乳酸所形成構成單位之含有比例偏低的聚乳酸 樹脂（即光學純度較低的聚乳酸樹脂）’仍可充分提升結晶 化’且處置時的作業性優異，亦不致使作業環境惡化。 以下’為將本發明的構成及效果具體化而舉實施例等’惟 本發明並不僅侷限於該等實施例。此外’以下實施例及比較 例中，「份」係指「質量份」，而「％」係指「質量％」。 [實施例] 試驗分類1 (聚乳酸樹脂用結晶核劑的合成與調整） 依如下述合成聚乳酸樹脂用結晶核劑，並進行調整。其内 容整理於表1中。此外，聚乳酸樹脂用結晶核劑的平均粒徑 係依如下進行測定。 •平均粒徑 將聚乳酸樹脂用結晶核劑〇.〇ig與異丙醇2〇〇g裝填入燒 杯中’經施行10分鐘超音波處理後，使用雷射繞射式粒度 分佈儀（堀場製作所公司製LA-920)，施行聚乳酸樹脂用結 098137214 26 201030072 晶核劑的平均粒徑(50%體積徑)測定。 •實施例1{聚乳酸樹脂用結晶核劑(C-1)的合成與調整} 在安裝有冷卻管的1L可分離式燒瓶中，裝填入5_磺基間 苯二甲酸二甲基=鈉85.8g(〇.29莫耳)與離子交換水772.0g， 一邊施行擾拌一邊加熱至内溫80°C。另外，將氣化鋇•二 水合物35.7g(0.15莫耳）一邊加熱一邊溶解於離子交換水 94.2g中。待確認5-績基間苯二甲酸二甲基=鈉已溶解後， ❹一邊將内溫保持於80°C，一邊將氯化鋇水溶液歷時35分鐘 滴下，再一邊將内溫保持80°C—邊進行攪拌3小時後，獲 得含雙(5-磺基間苯二曱酸二甲基)=鋇的固形份漿料。急冷 至内溫30°C以下之後，從該漿料中過濾出固形份，再添加 100g離子交換水而施行水洗處理。接著，將經水洗處理過 的固形份與離子交換水430g，裝填入1L可分離式燒瓶中， 於内溫80°C下進行3小時攪拌。待急冷至内溫30°C以下之 ❹後，從該漿料中過濾出固形份，並利用l〇〇g離子交換水施 行水洗處理。將經水洗處理過的固形份利用l〇5°C熱風乾燥 機施行4小時乾燥，獲得白色粉末90.1g。最後，將所獲得 白色粉末使用喷射粉碎機（SEISHIN企業公司製商品名 SINGLE TRACK喷射粉碎機STJ-200型），依粉碎壓力 0.7Mpa條件施行粉碎處理。將此設為實施例1的聚乳酸樹 脂用結晶核劑(C-1)。 •實施例2~5{聚乳酸樹脂用結晶核劑(C-2)〜(C-5)的合成與 098137214 27 201030072 調整} 如同實施例1的聚乳酸樹脂用結晶核劑(c·1)般，獲得實 施例2〜5的聚乳酸樹脂用結晶核劑(C-2)〜(C-5) ° •比較例1、3及5{聚乳酸樹脂用結晶核劑(R-l)、（R-3)及 (R-5)的合成} 除未施行利用喷射粉碎機施行的粉碎處理之外’其餘均如 同實施例2、3及5的聚乳酸樹脂用結晶核劑(C-l)、（C-3) 及(C-5)般，獲得比較例1、3及5的聚乳酸樹脂用結晶核劑 (R-l)、（R-3)及(R-5)。 •比較例2{聚乳酸樹脂用結晶核劑(R-2)的合成} 在安裝有冷卻管的1L可分離式燒瓶中，裝填入5-續基間 苯二甲酸二曱基=鈉85.7g(0.29莫耳)與離子交換水772.0g， 一邊施行攪拌一邊加熱至内溫80°C。另外，將氣化錤•二 水合物35.7g(0.15莫耳）一邊加熱一邊溶解於離子交換水 94.2g中。待確認5-磺基間苯二甲酸二曱基=鈉已溶解後， 一邊將内溫保持於80°C , —邊將氯化鋇水溶液歷時35分鐘 滴下，再一邊將内溫保持80°C—邊進行攪拌3小時後，獲 得含雙(5-磺基間苯二曱酸二甲基)=鋇的固形份漿料。急冷 至内溫30 C以下之後，將該槳料使用珠磨機(ΙΜΕχ公司製） 施行粉碎處理。從經粉碎處理過的漿料中過濾出固形份，再 添加100g離子交換水而施行水洗處理。接著，將經水洗處 理過的固形份與離子交換水430g，裝填入1L可分離式燒瓶 098137214 28 201030072 中，於内溫80°C下進行3小時攪拌。待急冷至内溫30°C以 下之後，從該漿料中過濾出固形份，並利用l〇〇g離子交換 水施行水洗處理。將經水洗處理過的固形份利用l〇5°C熱風 乾燥機施行4小時乾燥，獲得白色粉末83.2g。最後’將所 獲得白色粉末使用喷射粉碎機(SEISHIN企業公司製商品名 SINGLE TRACK喷射粉碎機STJ-200型），依粉碎壓力 0.7Mpa條件施行粉碎處理。將此設為比較例2的聚乳酸樹 ❹ 脂用結晶核劑(R-2)。 •比較例4{聚乳酸樹脂用結晶核劑(R-4)的合成} 如同比較例2的聚乳酸樹脂用結晶核劑(R-2)般’獲得比 較例4的聚乳酸樹脂用結晶核劑(R-4)。 [表1] 分類 化1所示芳香族磺酸鹽 平均粒徑 種類 R1 R2 Mn+ (μιη) 實施例1 C-1 甲基 曱基 鋇 2.1 2 C-2 甲基 甲基 鉀 1.3 3 C-3 甲基 甲基 鈣 4.7 4 C-4 乙基 乙基 锶 8.5 5 C-5 異丙基 異丙基 伽 0.6 比較例1 R-1 甲基 甲基 鉀 ^ 16 2 R-2 甲基 甲基 鋇 0.08 3 R-3 甲基 甲基 鈣 14 4 R-4 乙基 乙基 勰 0.06 5 R-5 異丙基 異丙基 敍〇 13 試驗分類2 (聚乳酸樹脂組成物的調製及其作業性評估） •實施例6〜26及比較例6〜10 將由L-乳酸所形成構成旱位佔全構成單位中98.6%的聚 乳酸樹脂（光學純度98.6%之聚乳酸樹脂、質量平均分子量 098137214 29 201030072 160000)20kg、及雙(磺基間苯二甲酸二甲基>=鋇〇 lkg，投 入於200L顛動筒中，進行15分鐘旋轉後，從原料排出口 中抽取出混合物。該聚L-乳酸樹脂與結晶核劑的混合作業 之作業性，係依下述基準進行評估。結果整理如表2。 •作業性評估 AA :粉塵飛散少、作業環境良好。 A:粉塵飛散雖多少有發生’但作業環境大致良好。 B :粉塵飛散多、作業環境惡化。 試驗分類3 (聚乳酸樹脂組成物的結晶性評估） 依表2所記載内容’將聚乳酸樹脂及依試驗分類1所獲得 聚乳酸樹脂用、结晶核劑的化1所示芳香族磺酸鹽等，投入實 驗塑膠撞擊研磨機（東洋精機公司製）中，於200。(：下施行5 分鐘混練，調製之聚乳酸樹脂組成物。將所調製之聚乳酸樹 脂組成物利用熱壓機（東洋精機公司製）依200°C施行成形 後，經利用水施行急冷，便製得厚2mm的薄片。針對所製 得薄片，求取結晶化提升程度（結晶化度及結晶化速度的提 升程度)指標之結晶化尖峰溫度。即，將所製得薄片於1〇〇 °C下施行2小時除濕乾燥而呈絕乾狀態後，採取試料，依下 述微分掃描熱量計的條件求取結晶化尖峰溫度。然後，依以 下基準施行評估。結果整理如表2。 公司製 •微分掃描熱量計的條件 使用微刀婦描熱量計（Seiko Instruments 098137214 201030072 DSC-6200)，將試料3mg填充於鋁槽中，依30°C/分從室溫 升溫至200°C後，經保持5分鐘後，再依30°C/分的降溫速 度進行測定。 •結晶化尖峰溫度的評估 AAA :結晶化尖峰溫度達110°C以上。 AA :結晶化尖峰溫度達100°C以上、且未滿ll〇°C。 A :結晶化尖峰溫度達80°C以上、且未滿l〇〇°C。 φ B :結晶化尖峰溫度達60°C以上、且未滿80°C。 098137214 31 201030072 [表2]Acid diacid dipropyl, bis-p-formic acid-n-decyl)=钡, bis (counter-p-benzene H 参 钡, bis-p-phenylene)=钡, __ 本一酸2 , 2_ dimethylpropyl), bis (sulfo-p-phenylene diacid II = (four), _-valve: · U-based pair of di-diylpentyl dicarboxylate) = bismuth, bis (contiguous terephthalic acid) _3,3_monomethylbutyl)=钡, bis(sulfo-p-phenylene uf bis(contigyl-p-phenylenedionate dicyclohexyl)= 钡 钡 续 对 对 对 对Salt, etc. - Yin Yilang's shirts (four) Guxian body method for synthesis. Can be used in Japan Che-97 "= 098137214 21 201030072. The crystal nucleating agent of the present invention is an aromatic sulfonate as described above, And the average particle size is adjusted in the range of 0_1~10/mi, preferably within the range of 〇5~5 〇Alms, and more preferably in the range of 0.8~3.0μηι. Here, the "average particle size" refers to the 5 〇 % by volume (intermediate particle size) measured by diffraction and scattering method. If the average particle size of the aromatic acid salt is greater than 1 〇 from m, it will be used to form L-lactic acid. Constituent unit, or formed by D_lactic acid In the polylactic acid resin of 95 to 99 mol% of the total constituent unit, the crystallization is not sufficiently enhanced. Conversely, if the average particle size of the aromatic sulfonate is less than 〇Mm, even if it is used in The same polylactic acid resin not only causes deterioration of the working environment due to dust during the treatment, but also has poor kneading property with the polylactic acid resin, and as a result, crystallization cannot be sufficiently enhanced. The average particle size of the group sulfonate is adjusted to 0.1 to 10/im, for example, the aromatic sulfonate, G is supplied to a dry pulverizer such as a jet mill, a ball mill, a bead, a cyclone, or the like, 13 And a method of performing average particle size adjustment; 2) using a mixed solution such as water, an organic solvent, or water and an organic solvent together, and supplying it to a wet pulverizer such as a grinder, a ball mill, a bead mill, or the like, and performing average granulation The method of diameter adjustment, but from the viewpoint of productivity, it is preferably the method of the above. Next, the polylactic acid resin composition (hereinafter referred to as "the composition of the present invention") of the present invention will be described. The composition of the present invention comprises: a constituent unit formed of lactic acid or a constituent unit composed of D_lactate, and 95 to 99 mol% of the total constituent unit 098137214 22 201030072, and the above-mentioned crystal nucleating agent of the present invention. And constitute. From the viewpoint of the physical properties of the obtained polylactic acid resin composition, it is preferred that the constituent unit composed of L-lactic acid accounts for 96 to 99 mol% of the total constituent unit, and more preferably L-lactic acid. The constituent unit accounts for 98 to 99 mol% of the polylactic acid resin in the entire constituent unit. The polylactic acid resin itself can be synthesized in accordance with a known method. For example, Japanese Laid-Open Patent Publication No. Hei 7-33861, JP-A-59-96123, pp. 3198-3199 of the 44th volume of the sorghum molecular discussion group, 1) direct dehydration condensation reaction of lactic acid Method; 2) a method of ring-opening polymerization of lactide of lactic acid. The method of the above 1) may be L-lactic acid, D-lactic acid, DL-lactic acid, or any of these mixtures. The method of the above 2) may be the use of L-lactide, D-lactide, DL-lactide, meso-lactide, or the synthesis, purification and polymerization of the lactide lactone of any of the mixtures. The method is also applicable to a known method. The method described in, for example, U.S. Patent No. PCT Publication No. 261,572, Polymer Bulletin, 14, 491-495 (1985), Macromol. Chem. 187, 1611-1628 (1986), etc. The polylactic acid resin to be used for the composition is preferably a mass average molecular weight (polystyrene equivalent value analyzed by a gel permeation chromatography analyzer, the same applies hereinafter) of 80,000 or more, and more preferably 10 〇〇〇. When the mass average molecular weight of the polylactic acid resin is less than 80,000, the mechanical properties such as the strength and elastic modulus of the obtained molded article are easily insufficient, and the mass average molecular weight is higher. Further, when the mass average molecular weight of the polylactic acid resin is 2 Å or less, the fluidity suitable for molding is exhibited. The polylactic acid resin used in the composition of the present invention is more The residual monomer contained in the system is 5,000 ppm or less, more preferably 4 〇〇〇 ppm or less, and particularly preferably 3,000 ppm or less. If the amount of residual monomers in the polylactic acid resin exceeds 5,000. PPm, because the domain storage frequency has a simple hydrolysis, even if a known hydrolysis inhibitor such as a carbodiimide compound, an oxazoline compound or an isocyanate compound is added, the effect is not fully exerted, and it is easy to cause 13 resistance. The hygrothermal aging property and the heat-reducing property are insufficient. The lower the residual monomer in the polylactic acid, the higher the resistance to moist heat aging and the heat resistance. In the composition of the present invention, the content ratio of the crystal nucleating agent of the present invention is higher. Each of the good-quality polylactic acid resins is set to 〇〇1 to 1 〇 parts by mass, more preferably 〇. 5 parts by mass, and more than 5% to 5 parts by volume. The reason is that the conditions can be fully utilized. Addition of a nucleating agent to the polylactic acid resin, the addition of the aromatic sulfonate shown in the formula i. The secret crystal of the present invention may also contain the aromatic acid salt represented by the formula 1 and the above-mentioned There are organic crystal nucleating agents and/or inorganic crystal nucleating agents. In the organic crystal nucleating agent, 轫4 π 〇 旦 私 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为The best system is set to be the same as the 1st one. Acid or the like containing the same amount or less. Further, there is no (iv) crystal_zhong_ talc, and the content ratio is preferably 1 to 20 parts by mass per 1 liter of the polylactic acid resin. 098137214 24 201030072 The composition of the present invention may contain other resins from the viewpoints of improvement in physical properties such as rigidity, flexibility, heat resistance, and durability. Specific examples of the other resin include, for example, a polycarbonate, a poly(p-phenylene terephthalate), a phthalic acid, and a polyethylene naphthalate; a polystyrene resin such as phenyl ether, polyethylene polypropylene, polyvinyl chloride, polyacetal, polyphenylene sulfide, resin, Hashiki HIPS; or acrylic resin such as polymethyl ketone methyl vinegar; Poly_ et al. The (4) may be used alone or in combination of two or more. Among them, from the viewpoint of compatibility with the polylactic acid resin, it is preferred to have a resin having a county bond such as a bond of 6 or a bond of carbonic acid, and more preferably an ABS resin or a polybutylene terephthalate. Diester, polycarbonate. The compositions of the present invention may contain other additives in conjunction with specific purposes. The other additives may be, for example, a plasticizer, an antioxidant, a thermal stabilizer, a light stabilizer, an external absorbent, a pigment, a colorant, various fillers, an antistatic agent, a release agent, a fragrance, a slip agent, and a flame retardant. , foaming agent, filler, antibacterial, anti-mold, etc. The composition of the present invention described above can be modified in accordance with a known method. For example, 1) a powder or granular polylactic acid resin, a crystal nucleating agent, and optionally other additives may be simultaneously subjected to dry blending, followed by a kneading method; 2) powder or granular polylactic acid resin, Pre-blending with the crystal nucleating agent, and further drying the other additives as needed, and then performing the kneading method. The dry blending apparatus may, for example, be a mill roll, a Banbury mixer, a SUper mixer or the like. Further, the 098137214 25 201030072 kneading machine may be, for example, a single screw or a twin screw extruder. The kneading temperature of the kneading machine is usually set to 120 to 22 (degree of TC. In the polymerization stage of the polylactic acid resin, a crystal nucleating agent or other additives as needed may be added, and a crystal nucleating agent containing a high concentration may be prepared in advance. Or adding the concentrate of other additives as needed, and then adding it to the polylactic acid resin. (Effect of the invention) When the crystal nucleating agent of the present invention is used, even if it is a constituent unit formed of L-lactic acid or by D-lactic acid The polylactic acid resin having a low content ratio of the constituent units (that is, the polylactic acid resin having a low optical purity) can be sufficiently improved in crystallization, and the workability at the time of handling is excellent, and the working environment is not deteriorated. The present invention is not limited to the embodiments, and the present invention is not limited to the embodiments. In the following examples and comparative examples, "parts" means "parts by mass" and "%" Refers to "% by mass". [Examples] Test classification 1 (Synthesis and adjustment of crystal nucleating agent for polylactic acid resin) The crystal nucleating agent for polylactic acid resin was synthesized and adjusted as follows. The contents are as shown in Table 1. In addition, the average particle diameter of the crystalline nucleating agent for polylactic acid resin is determined as follows: • The average particle diameter is a crystal nucleating agent for polylactic acid resin 〇.〇ig and isopropanol 2〇〇g Filled in a beaker, after performing ultrasonic treatment for 10 minutes, using a laser diffraction type particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), the average particle size of the nucleating agent for the polylactic acid resin is 098137214 26 201030072. (50% by volume) measurement. Example 1 {Synthesis and adjustment of crystal nucleating agent (C-1) for polylactic acid resin} In a 1 L separable flask equipped with a cooling tube, 5 sulfo group was charged. Dimethyl isophthalate = 85.8 g (〇.29 mol) and 772.0 g of ion-exchanged water were heated to an internal temperature of 80 ° C while stirring. In addition, 35.7 g of vaporized hydrazine dihydrate was added. (0.15 mol) was dissolved in 94.2 g of ion-exchanged water while heating. After confirming that 5-methoxy dimethyl isophthalate was dissolved, the inner temperature was maintained at 80 ° C while chlorine was added. The aqueous solution of hydrazine was dropped for 35 minutes, and the internal temperature was maintained at 80 ° C while stirring for 3 hours. A solid slurry containing bis(5-sulfoisophthalic acid dimethyl)=钡. After quenching to an internal temperature of 30 ° C or lower, the solid fraction is filtered from the slurry, and 100 g of ion-exchanged water is further added. Then, the water-washing treatment was carried out, and then 430 g of the water-washed solid portion and ion-exchanged water were placed in a 1 L separable flask, and stirred at an internal temperature of 80 ° C for 3 hours, and then quenched to an internal temperature of 30 °. After C or less, the solid fraction was filtered from the slurry, and washed with 1 g of ion-exchanged water. The washed solid portion was dried by a hot air dryer at 10 ° C for 4 hours. 90.1 g of a white powder was obtained. Finally, the obtained white powder was subjected to a pulverization treatment using a jet mill (trade name: SINGLE TRACK jet mill STJ-200, manufactured by SEISHIN CORPORATION) under the conditions of a crushing pressure of 0.7 Mpa. This was designated as the crystal nucleating agent (C-1) for polylactic acid resin of Example 1. • Examples 2 to 5 {Synthesis of Crystal Nucleating Agent (C-2) to (C-5) for Polylactic Acid Resin and 098137214 27 201030072 Adjustment} Crystallization nucleating agent for polylactic acid resin as in Example 1 (c·1) In general, crystal nucleating agents (C-2) to (C-5) ° for polylactic acid resins of Examples 2 to 5 were obtained. • Comparative Examples 1, 3 and 5 {Crystal nucleating agents (Rl), (R for polylactic acid resins) -3) and (R-5) Synthesis} The crystal nucleating agent (Cl) for polylactic acid resin of Examples 2, 3 and 5 was used except that the pulverization treatment by the jet mill was not carried out. In the same manner as in the case of (C-5), the crystal nucleating agents (R1), (R-3) and (R-5) for the polylactic acid resins of Comparative Examples 1, 3 and 5 were obtained. •Comparative Example 2 {Synthesis of Crystal Nucleating Agent (R-2) for Polylactic Acid Resin} In a 1 L separable flask equipped with a cooling tube, 5-n-butylisophthalic acid = sodium 85.7 was charged. g (0.29 mol) and 772.0 g of ion-exchanged water were heated to an internal temperature of 80 ° C while stirring. Further, 35.7 g (0.15 mol) of vaporized hydrazine dihydrate was dissolved in 94.2 g of ion-exchanged water while heating. After confirming that di-sulfonyl 5-sulfoisophthalate = sodium has been dissolved, while maintaining the internal temperature at 80 ° C, the aqueous solution of ruthenium chloride is dripped for 35 minutes, and the internal temperature is maintained at 80 ° C. - After stirring for 3 hours, a solid slurry containing bis(5-sulfoisophthalic acid dimethyl) = hydrazine was obtained. After quenching to an internal temperature of 30 C or less, the slurry was pulverized using a bead mill (manufactured by Nippon Steel Co., Ltd.). The solid fraction was filtered from the pulverized slurry, and 100 g of ion-exchanged water was further added thereto to carry out a water washing treatment. Next, 430 g of the washed solid portion and ion-exchanged water were placed in a 1 L separable flask 098137214 28 201030072, and stirred at an internal temperature of 80 ° C for 3 hours. After quenching to an internal temperature of 30 ° C or less, the solid fraction was filtered from the slurry, and subjected to a water washing treatment using 1 g of ion-exchanged water. The water-treated solid portion was dried by a hot air dryer at 10 ° C for 4 hours to obtain 83.2 g of a white powder. Finally, the obtained white powder was subjected to a pulverization treatment using a jet mill (trade name SINGLE TRACK jet mill STJ-200, manufactured by SEISHIN Co., Ltd.) under the conditions of a crushing pressure of 0.7 Mpa. This was designated as a crystal nucleating agent (R-2) for polylactic acid resin of Comparative Example 2. -Comparative Example 4 {Synthesis of Crystal Nucleating Agent (R-4) for Polylactic Acid Resin] The crystal nucleus for polylactic acid resin of Comparative Example 4 was obtained as in the case of the crystalline nucleating agent (R-2) for polylactic acid resin of Comparative Example 2. Agent (R-4). [Table 1] The average particle diameter of the aromatic sulfonate shown in Classification 1 is R1 R2 Mn+ (μιη) Example 1 C-1 Methylmercaptopurine 2.1 2 C-2 Methylmethylpotassium 1.3 3 C-3 Methylmethyl calcium 4.7 4 C-4 Ethylethyl hydrazine 8.5 5 C-5 Isopropyl isopropyl Glycol 0.6 Comparative Example 1 R-1 Methylmethyl potassium ^ 16 2 R-2 Methylmethyl hydrazine 0.08 3 R-3 methylmethyl calcium 14 4 R-4 ethyl ethyl hydrazine 0.06 5 R-5 isopropyl isopropyl ruthenium 13 test classification 2 (modulation of polylactic acid resin composition and evaluation of its workability • Examples 6 to 26 and Comparative Examples 6 to 10 Polylactic acid resin (98.6% of polylactic acid resin having an optical purity of 98.6%, mass average molecular weight 098137214 29 201030072 160000) formed of L-lactic acid. 20 kg, and bis (sulfoisophthalic acid dimethyl > = 钡〇lkg, put into a 200 L transfer barrel, and after 15 minutes of rotation, the mixture was extracted from the raw material discharge port. The poly-L-lactic acid resin and The workability of the mixing operation of the crystal nucleating agent was evaluated according to the following criteria. The results are summarized in Table 2. • Operational evaluation AA: powder A: The dust is scattered and the working environment is good. A: Although the dust is scattered, the working environment is generally good. B: The dust is scattered and the working environment is deteriorated. Test classification 3 (Evaluation of crystallinity of polylactic acid resin composition) According to Table 2 In the case of the polylactic acid resin and the aromatic sulfonate of the polylactic acid resin obtained by the test classification 1 and the crystal nucleating agent, it is put into an experimental plastic impact grinding machine (manufactured by Toyo Seiki Co., Ltd.) at 200 (: A polylactic acid resin composition prepared by kneading for 5 minutes, and the prepared polylactic acid resin composition was formed by a hot press (manufactured by Toyo Seiki Co., Ltd.) at 200 ° C, and then quenched by water. A sheet having a thickness of 2 mm was obtained. For the obtained sheet, the crystallization peak temperature of the degree of crystallization (degree of crystallization and the degree of crystallization) was determined. That is, the obtained sheet was placed at 1 Torr. After being dehumidified and dried for 2 hours at ° C, the sample was taken, and the crystallization peak temperature was determined according to the following differential scanning calorimeter. Then, the evaluation was performed according to the following criteria. The results are summarized in Table 2. The conditions of the company/differential scanning calorimeter were measured using a microknife calorimeter (Seiko Instruments 098137214 201030072 DSC-6200), and 3 mg of the sample was filled in an aluminum tank at 30 ° C / min. After the temperature was raised to 200 ° C, the temperature was measured for 5 minutes, and then measured at a temperature drop rate of 30 ° C / minute. • Evaluation of crystallization peak temperature AAA: The crystallization peak temperature is above 110 °C. AA: The crystallization peak temperature is 100 ° C or more and less than 〇 ° ° C. A: The crystallization peak temperature is 80 ° C or more and less than 10 ° C. φ B : The crystallization peak temperature is 60 ° C or more and less than 80 ° C. 098137214 31 201030072 [Table 2]
聚乳酸樹脂組成物 分類 聚乳酸樹脂 化1所示芳香 族磺酸鹽 併用的其他 結晶核劑 其他 評估 光學 光學 使用量 種類 使用量 種類 使用量 機 使用量 作 結晶化尖 純度 業 活性 (%) (份） (份） (份） (份） 性 峰溫度 實施例ό L體 98.6 100 C-1 0.5 ΑΑ AAA 7 L體 98.6 100 C-1 1.0 ΑΑ AAA 8 L體 96.2 100 C-1 2.0 ΑΑ ΑΑ AA 9 L體 98.6 100 C-2 1.5 AAA 10 L體 98.6 100 C-2 3.0 ΑΑ AAA 11 L體 96.2 100 C-2 3.0 ΑΑ AA 12 L體 98.6 100 C-3 4.5 ΑΑ AA 13 L體 96.2 100 C-3 5.0 ΑΑ A 14 L體 98.6 100 C-4 4.5 ΑΑ AA 15 L體 96.2 100 C-4 5.0 ΑΑ A 16 D體 98.9 100 C-5 3.0 A AA 17 D體 96.8 100 C-5 5.0 A AA 18 L體 98.6 100 C-1 0.5 ΑΑ AAA C-2 0.5 19 L體 98.6 100 C-1 1.0 D-1 1 ΑΑ AAA 20 L體 98.6 100 C-2 1.0 D-2 10 ΑΑ AAA 21 L體 98.6 70 C-1 2.0 D-3 30 ΑΑ AAA 22 L體 98.6 70 C-1 2.0 D-4 30 ΑΑ AAA 23 L體 98.6 80 C-2 3.0 D-5 20 ΑΑ AA 24 L體 98.6 70 C-1 2.0 D-1 1 D-3 30 ΑΑ AAA 25 L體 98.6 80 C-1 2.0 D-2 10 D4 20 ΑΑ AAA i 26 L體 98.6 70 C-2 3.0 D-2 10 D-5 30 ΑΑ AA 比較例6 L體 96.2 100 R-1 5.0 ΑΑ B 7 L體 96.2 100 R-2 1.0 A A 8 L艎 96.2 100 R-3 5.0 D-1 1 B 9 L體 96.2 100 R-4 1.0 D-2 10 A 10 L體 96.2 70 R-5 5.0 D-1 1 D-3 30 B 32 098137214 201030072 表2中， C-1〜C-5、R-1〜R-5 :表1所記載物 • D-1 :醯胺系結晶核劑（日本化成公司製商品名SLIPAXH : : 乙烯雙-12-羥基硬脂酸醯胺） D-2 .滑石系結晶核劑（Nippon Talc公司製商品名Polylactic acid resin composition classification Polylactic acid resin 1 Other nucleating agent used in combination with other aromatic sulfonates. Other evaluation Optical optical usage type Type of use The amount used is used for crystallization sharpness purity activity (%) ( Parts) (parts) (parts) (parts) Sex peak temperature example ό L body 98.6 100 C-1 0.5 ΑΑ AAA 7 L body 98.6 100 C-1 1.0 ΑΑ AAA 8 L body 96.2 100 C-1 2.0 ΑΑ ΑΑ AA 9 L body 98.6 100 C-2 1.5 AAA 10 L body 98.6 100 C-2 3.0 ΑΑ AAA 11 L body 96.2 100 C-2 3.0 ΑΑ AA 12 L body 98.6 100 C-3 4.5 ΑΑ AA 13 L body 96.2 100 C- 3 5.0 ΑΑ A 14 L body 98.6 100 C-4 4.5 ΑΑ AA 15 L body 96.2 100 C-4 5.0 ΑΑ A 16 D body 98.9 100 C-5 3.0 A AA 17 D body 96.8 100 C-5 5.0 A AA 18 L Body 98.6 100 C-1 0.5 ΑΑ AAA C-2 0.5 19 L body 98.6 100 C-1 1.0 D-1 1 ΑΑ AAA 20 L body 98.6 100 C-2 1.0 D-2 10 ΑΑ AAA 21 L body 98.6 70 C- 1 2.0 D-3 30 ΑΑ AAA 22 L body 98.6 70 C-1 2.0 D-4 30 AAA AAA 23 L body 98.6 80 C-2 3.0 D-5 20 ΑΑ AA 24 L body 98.6 70 C-1 2.0 D-1 1 D-3 30 ΑΑ AAA 25 L body 98.6 80 C-1 2.0 D-2 10 D4 20 ΑΑ AAA i 26 L body 98.6 70 C-2 3.0 D-2 10 D-5 30 ΑΑ AA Comparative example 6 L body 96.2 100 R-1 5.0 ΑΑ B 7 L body 96.2 100 R-2 1.0 AA 8 L艎96.2 100 R-3 5.0 D-1 1 B 9 L body 96.2 100 R-4 1.0 D-2 10 A 10 L body 96.2 70 R-5 5.0 D-1 1 D-3 30 B 32 098137214 201030072 In Table 2, C-1 to C-5, R-1 to R-5: The materials described in Table 1 • D-1: a guanamine-based crystal nucleating agent (trade name: SLIPAXH, manufactured by Nippon Kasei Co., Ltd.: : Ethylene bis-12-hydroxystearate) Acid amide amine D-2. talc crystal nucleating agent (trade name of Nippon Talc Co., Ltd.
MicroAceP-6、平均粒徑 4/im) D-3 : ABS 樹脂（TORAY 公司製商品名 TOYOLAC® 250) ❹ D-4 :聚對苯二曱酸丁二酯（三菱工程塑膠公司製商品名 NOVADURAN® 5010TRXA) D-5 :聚碳酸酯（三菱工程塑膠公司製商品名JUPILON S-3000) 由表2中得知，若使用本發明結晶核劑，即便使用於光學 純度95〜99%的聚乳酸樹脂’仍可充分提升結晶化，且作業 性佳，作業環境亦良好。 ❿ 098137214 33MicroAceP-6, average particle size 4/im) D-3 : ABS resin (TOYOLAC® 250, manufactured by TORAY Corporation) ❹ D-4: polybutylene terephthalate (trade name NOVADURAN, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) ® 5010TRXA) D-5 : Polycarbonate (trade name JUPILON S-3000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) It is known from Table 2 that if the crystal nucleating agent of the present invention is used, it is used even in polylactic acid having an optical purity of 95 to 99%. Resin' can still fully enhance crystallization, and it has good workability and good working environment. ❿ 098137214 33