TWI374896B

TWI374896B -

Info

Publication number: TWI374896B
Application number: TW95113713A
Authority: TW
Inventors: Imai Daisuke; Nakata Yoshitomo
Priority date: 2005-04-19
Filing date: 2006-04-18
Publication date: 2012-10-21
Also published as: JP4738046B2; JP2006299043A; WO2006115116A1; TW200704655A

Description

1374896 九、發明說明：【發明所屬之技術領域】本發明係關於乙烯基吡咯烷明系共聚物及其製造方法’該乙烯基吼咯烷酮系共聚物，係以N_乙烯基吡咯烷酮、與（曱基）丙烯酸2-羥基乙酯等含羥基之（曱基）丙烯酸酯作為必須構成成分。【先前技術】 N-乙稀基吼洛烷酮與（甲基）丙烯酸2·羥基乙酯之共聚物（以下亦稱為「NVP/HE(M)A共聚物」），由於同時帶有親水性的吡咯烷酮基、及能與異氰酸酯等交聯劑反應的水酸基，已知適用於例如：作為製得兼備耐水性及親水性膜之硬化性樹脂組成物之原料聚合物等。例如作為硬化性樹脂組成物（參照專利文獻丨，其必須構成成分包含：具 N-乙烯醯胺單位之聚合物、具2個以上與活性氫反應的官能基之化合物、多價金屬化合物）中之較佳聚合物。 nvp/he(m)a共聚物，習知係於含有N_乙烯基吡咯烷酮與聚合起始劑之水（溶劑）中，添加（曱基）丙烯酸2-羥基乙酯使其聚合來製得，而NVP/HE(M)A共聚物之製造方法’ 一般係採用該方法。專利文獻1 :曰本特開2003_286381號公報。【發明内容】然而，習知技術所製得之NVP/HE(M)A共聚物，將以 /、為原料I σ物之硬化樹脂組成物製膜而交聯時，所形成之交聯塗膜之表面平滑性差，於交聯後為了除去未反應原 1374896 料等而施以水洗時’會產生凝膠膨潤等問題，此外，所形成之父聯塗膜亦會產生均一度降低之問題。又，以習知之 NVP/HE(M)A共聚物作為原料聚合物之交聯塗膜，亦有耐水性低之問題。以上之問題，係以包含（曱基）丙烯酸2-羥基已酯之含經基之（曱基）丙烯酸酯作為一原料單體之乙烯基吡咯烷酮系共聚物共通之問題。鳙因此’本發明所欲解決之課題，係提供一種乙烯基吡哈烧綱系共聚物及容易製得其之製造方法，該乙烯基吡咯烧嗣系共聚物可得到不會產生上述問題之良好交聯塗膜，且其必須構成成分包含：1乙烯基吡咯烷酮、（曱基）丙烯酸2-經基乙酯等含羥基之（甲基）丙烯酸酯。本發明人’為解決上述課題而深入探討。結果發現，用習知之NVP/HE(M)A共聚物作為原料聚合物使用時，引起上述問題之原因，係由於（甲基）丙烯酸2_羥基乙酯於聚 φ 合中容易受到交聯反應，而使水不溶分（即凝膠分）增多、分子量分布變廣。亦即，將習知技術所製得之Nvp/HE(M)A 共聚物作為原料聚合物的硬化性樹脂組成物製膜而交聯時，由於水不溶分多，而使交聯塗臈之表面平滑性惡化，而於交聯後之水洗時產生凝膠膨潤等問題，除此之外，由於分子量分布變廣，而產生交聯塗膜之均一度降低等問題。本發明人’更發現交聯塗膜之耐水性會受nvp/he(m)a 共聚物之K值影響。因此，本發明人針對可達成水不溶分含有率低及/或低 1374896 分散度之乙烯基°比咯烷酮系共聚物（即使以N_乙烯基°比哈炫酿I、與含經基之（甲基）丙浠酸醋作為必須構成成分）以及容易製得其之製造方法，進行各種研究、重複實驗的結果獲得下述認知’而完成本發明。亦即，將N-乙稀基°比洛院酮、與含羥基之（甲基）丙烯酸酯之共聚合比設定於特定範圍，並且在進行共聚合時，i)藉由於特定量之鏈轉移劑的存在下進行聚合、或於含一定量以上之特定醇的溶劑中進行聚合，可製得水不溶分極少之共聚物；ii)使用巯基化合物作為鏈轉移劑，藉由於特定量之該鏈轉移劑的存在下進行聚合、或於含一定量以上之特定醇的溶劑中進行聚合，可製得分散度極低之共聚物；且iii) N-乙烯基吡咯烷酮/含羥基之（曱基）丙烯酸酯共聚物，其以菲肯齊爾 (Fikentscher)法所測得之κ值為12以上，而完成本發明。因此’本發明之第一乙烯基吡咯烷酮系共聚物，其特徵在於’來自N-乙烯基吡咯烷酮之構成單位與來自含羥基之（甲基）丙烯酸酯之構成單位（B)以對於兩者合計量之比率來表不時，係含有該（A)5〇〜95質量％、該（B)5〇〜5質里％之比例，而以菲肯齊爾法所測得之K值為12以上，且水不溶分為0_5質量％ (固體成分基準）以下。本發明之第二乙烯基吡咯烷酮系共聚物，其來自义乙烯基比咯烷酮之構成單位與來自含羥基之（甲基）丙烯酸酯之構成單位(B)以對於兩者合計量之比率來表示時，係含有該（A)50〜95質量％ '該（B)5〇〜5質量％之比例，而以菲肯 1374896 齊爾法所測得之K值為12以上，且分散度為丨.8以下。而本發明之第三乙烯基吡咯烷酮系共聚物，其來自Ν_ 乙烯基。比咯烷酮之構成單位（Α)與來自含羥基之（甲基）丙烯酸酯之構成單位（Β)以對於兩者合計量之比率來表示時，係含有該（Α)50〜95質量％、該（Β)50〜5質量％之比例，而以菲肯齊爾法所測得之Κ值為12以上、水不溶分為〇·5質量0/〇 (固體成分基準）以下、且分散度為1.8以下。其次，本發明之第一乙烯基吡咯烷酮系共聚物之製造方法，Ν-乙烯基吡咯烷酮（a)與含羥基之（甲基）丙烯酸酯以對於兩者合計量之比率來表示時，含有該0)5〇〜95質量 /°、忒（b)50〜5質量％比例之單體成分進行聚合時，係於對單體成分存在0·01質量％以上之鏈轉移劑下進行聚合。該製is·方法中’特別佳之態樣係使用疏基化合物作為鏈轉移劑者。而本發明之第二乙烯基吡咯烷酮系共聚物之製造方法 N_乙稀基"比咯烷酮（a)與含羥基之（甲基）丙烯酸酯（b)以對於兩者合計量之比率來表示時，含有該（a)50〜95質量％、忒（b)50〜5質量％比例之單體成分進行聚合時，係於含碳數 1〜5之醇10質量％ (對溶劑總量之比例）以上之溶劑中進行聚合者。藉由本發明，即使以N-乙烯基吡咯烷酮、與含羥基之 (甲基）丙烯酸酯作為必須構成成分，亦容易製得可達成水不》谷分含有率低及/或低分散度之乙烯基。比咯烷酮系共聚物’亦即’容易製得可得到良好交聯塗膜之N_乙烯基吡咯 1374896 院明、與含羥基之（曱基）丙烯酸酯之共聚物。【實施方式】以下，詳細說明本發明之乙烯基吡咯烷酮系共聚物及其製造方法，但本發明之範圍並不受限於該等說明，除以下例示以外，亦可於不損及本發明之主旨範圍内適當地改變實施。 [乙烯基"比咯烷酮系共聚物] 髒本發明之乙烯基吡咯烷酮系共聚物（包含第一、第二及第三乙烯基吡咯烷酮系共聚物；以下也簡稱「本發明之乙烯基°比咯烷酮系共聚物」）’其來自Ν·乙烯基吡咯烷酮之構成單位（Α)與來自含羥基之（曱基）丙烯酸酯之構成單位 (Β)以對於兩者合計量之比率來表示時，係含有該（Α)5〇〜95 質量％、該（Β)50〜5質量％之比例。較佳為，該（Α)60〜9〇質 3： %、該（Β)40〜10質量％，更佳為，該（Α)65〜85質量％、該（Β)3 5〜15質量。/〇。只要來自Ν-乙烯基。比咯烷酮之構成單 φ 位（A)、與來自含羥基之（甲基）丙烯酸酯之構成單位（B)的比例（共聚合比）為上述範圍，則可得到適於製得例如兼備耐水性與親水性之良好交聯塗膜的共聚物。若來自N—乙烯基吡咯烷酮之構成單位（A)較上述範圍多（來自含羥基之 (曱基）丙烯酸酯之構成單位（B)較上述範圍少），則難以發揮來自含羥基之（曱基）丙烯酸酯之與交聯劑反應性高之優點，相反的，若來自N-乙烯基吡咯烷酮之構成單位（A)較上述範圍少（來自含羥基之（甲基）丙烯酸酯之構成單位較上述範圍多），則易引起凝膠化而變成水不溶分多之共 1374896 聚物、或分散度高（分子量分布廣）之共聚物β 本發明之乙烯基吡咯烷酮系共聚物，除來自Ν·乙烯基。比洛燒酮之構成單位（Α)與來自含羥基之（曱基）丙烯酸酯之構成單位（Β)之外，亦可具有隨後在[乙烯基比咯烷酮系共聚物之製造方法]欄敘述之來自能與Ν_乙烯基吡咯烷酮共聚合之單體之構造單位。同時具有來自其他單體之構造單位時’該來自其他單體之構造單位的比例，對於全構造單位以未滿20質量％為佳、未滿1〇質量％為更佳。以上之構成中，本發明之第一乙烯基吡咯烷酮系共聚物’係以固體成分基準計之水不溶分為〇.5質量％以下（亦即’固體成分基準計水不溶分含有率為〇.5質量％以下）者。較佳為0.3質量％以下、更佳為〇丨質量％以下。如此，只要固體成分基準計之水不溶分含有率為〇 5質量％以下，則可避免例如於製膜並交聯時，所形成之交聯塗膜表面平滑性惡化、及施行除去交聯後未反應原料所需之水洗時的凝膠膨潤等問題。又以固體成分基準計之共聚物之水不溶分含有率’係藉實施例中後述之方法來測定。本發明之第一乙烯基吡咯烷酮系共聚物，可藉由後述之本發明的第一或第二乙烯基吡咯烷酮系共聚物之製造方1374896 IX. Description of the Invention: [Technical Field] The present invention relates to a vinylpyrrolidine-based copolymer and a process for producing the same, the vinyl pyrrolidone copolymer, which is N-vinylpyrrolidone, and A hydroxyl group-containing (mercapto) acrylate such as 2-hydroxyethyl acrylate is an essential constituent. [Prior Art] Copolymer of N-ethylene oxaloxanone and 2, hydroxyethyl (meth) acrylate (hereinafter also referred to as "NVP/HE (M) A copolymer)) The pyrrolidone group and the hydrous acid group which can react with a crosslinking agent, such as an isocyanate, are known, for example, as a raw material polymer which can be used as a curable resin composition which has both a water resistance and a hydrophilic film. For example, in the case of a curable resin composition (refer to the patent document, the constituent component includes a polymer having N-vinylamine units, a compound having two or more functional groups reactive with active hydrogen, and a polyvalent metal compound). Preferred polymer. Nvp/he(m)a copolymer, which is prepared by adding 2-hydroxyethyl (meth) acrylate to water (solvent) containing N-vinylpyrrolidone and a polymerization initiator, and polymerizing it. The method of producing NVP/HE(M)A copolymer is generally employed in this method. Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-286381. SUMMARY OF THE INVENTION However, the NVP/HE(M)A copolymer obtained by the prior art is formed by crosslinking a cured resin composition of the raw material I σ to form a crosslinked coating. The surface smoothness of the film is poor, and when the water is washed in order to remove the unreacted raw material 1374896 after cross-linking, problems such as gel swelling occur, and the formed father-joint coating film also has a problem of uniformity reduction. Further, the conventional NVP/HE(M)A copolymer is used as a crosslinked coating film of a raw material polymer, which also has a problem of low water resistance. The above problem is in common with a vinylpyrrolidone copolymer containing a mercapto group-containing (fluorenyl) acrylate as a raw material monomer. Therefore, the problem to be solved by the present invention is to provide a vinylpyrazine copolymer and a process for producing the same, which is excellent in that the above problems are not caused by the vinylpyrrole oxime copolymer. The cross-linking coating film and the constituent components thereof include: a vinyl group-containing (meth) acrylate such as vinylpyrrolidone or 2-mercaptoacetic acid. The inventors of the present invention have intensively studied to solve the above problems. As a result, it has been found that the use of the conventional NVP/HE(M)A copolymer as a base polymer causes the above problems because the 2-hydroxyethyl (meth)acrylate is susceptible to cross-linking reaction in the poly-oxime. In addition, the water insoluble fraction (ie, gel fraction) is increased, and the molecular weight distribution is broadened. In other words, when the Nvp/HE(M)A copolymer obtained by the prior art is used as a film of a curable resin composition of a base polymer to form a film and crosslinked, since the water is insoluble, the crosslinked coating is applied. The surface smoothness is deteriorated, and problems such as swelling of the gel during water washing after crosslinking are caused, and in addition to this, the molecular weight distribution is broadened, and the uniformity of the crosslinked coating film is lowered. The inventors have found that the water resistance of the crosslinked coating film is affected by the K value of the nvp/he(m)a copolymer. Therefore, the present inventors have directed a vinylpyrrolidone-based copolymer which can achieve a low water-insoluble content and/or a low dispersion of 1,374,896 (even with N-vinyl-pyrene-I, and with a mercapto group). The (meth)propionate vinegar is an essential component and a production method which is easy to obtain, and various studies and repeated experiments are carried out to obtain the following findings. The present invention has been completed. That is, the copolymerization ratio of N-ethylene dipyridyl ketone and hydroxyl group-containing (meth) acrylate is set to a specific range, and when copolymerization is carried out, i) by a specific amount of chain transfer Polymerization in the presence of a solvent, or polymerization in a solvent containing a certain amount or more of a specific alcohol, to obtain a copolymer having little water insoluble; ii) using a mercapto compound as a chain transfer agent, due to a specific amount of the chain Polymerization in the presence of a transfer agent, or polymerization in a solvent containing a specific amount of a specific alcohol, to obtain a copolymer having an extremely low degree of dispersion; and iii) N-vinylpyrrolidone/hydroxyl-containing (fluorenyl) The acrylate copolymer having a K value of 12 or more as measured by the Fikenscher method is completed. Therefore, the first vinylpyrrolidone copolymer of the present invention is characterized in that 'the constituent unit derived from N-vinylpyrrolidone and the constituent unit (B) derived from the hydroxyl group-containing (meth)acrylate are combined for both The ratio is from time to time, including the ratio of (A) 5 〇 to 95% by mass, and (B) 5 〇 to 5 5% by mass, and the K value measured by the Fiknijker method is 12 or more. And the water insoluble is divided into 0 to 5 mass% (solid content basis) or less. The second vinylpyrrolidone-based copolymer of the present invention, which comprises a constituent unit derived from a vinylidene-pyrrolidone and a constituent unit (B) derived from a hydroxyl group-containing (meth)acrylate in a ratio of the total amount of the two In the case of the expression, the ratio of (A) 50 to 95% by mass of the (B) 5 〇 to 5 mass% is obtained, and the K value measured by the Philippine 1374896 ziel method is 12 or more, and the dispersion is丨.8 or less. The third vinylpyrrolidone copolymer of the present invention is derived from a ruthenium-vinyl group. When the constituent unit (Α) of the pyrrolidone and the constituent unit (Β) derived from the hydroxyl group-containing (meth) acrylate are expressed by the ratio of the total amount of the two, the (Α) 50 to 95% by mass is contained. The ratio of 50% to 5% by mass, and the Κ value measured by the Fenkenzier method is 12 or more, and the water is insoluble, 〇·5 mass 0/〇 (solid component basis), and dispersed. The degree is 1.8 or less. Next, in the method for producing the first vinylpyrrolidone copolymer of the present invention, the oxime-vinylpyrrolidone (a) and the hydroxyl group-containing (meth) acrylate are represented by a ratio of the total amount of the two, and the 0 is contained. When the monomer component having a ratio of 5 to 95 mass% and 忒(b) of 50 to 5 mass% is polymerized, the polymerization is carried out under a chain transfer agent in which the monomer component is present in an amount of 0.01 mass% or more. The particularly preferred aspect of the is method is the use of a sulfhydryl compound as a chain transfer agent. The method for producing the second vinylpyrrolidone copolymer of the present invention is a ratio of N-ethylidene "pyrrolidone (a) to hydroxyl group-containing (meth)acrylate (b) to the total amount of both In the case of the monomer component containing 50% to 95% by mass of the (a) and 50 to 5% by mass of the bismuth (b), the polymerization is carried out in an amount of 10% by mass of the alcohol having 1 to 5 carbon atoms (to the total solvent) The ratio of the amount of the above is the polymerization of the solvent. According to the present invention, even if N-vinylpyrrolidone and a hydroxyl group-containing (meth) acrylate are essential constituents, it is easy to obtain a vinyl group which can achieve a low water content and/or a low dispersion. . The pyrrolidone-based copolymer 'is also' is a copolymer of N-vinylpyrrole 1374896 which is a good crosslinked coating film and a hydroxyl group-containing (fluorenyl) acrylate. [Embodiment] Hereinafter, the vinylpyrrolidone-based copolymer of the present invention and a method for producing the same will be described in detail, but the scope of the present invention is not limited to the description, and the present invention may be omitted without exemplifying the present invention. The implementation is appropriately changed within the scope of the subject matter. [Vinyl "pyrrolidone-based copolymer] The vinylpyrrolidone-based copolymer of the present invention (including the first, second and third vinylpyrrolidone-based copolymers; hereinafter also referred to as "the vinyl group of the present invention" The pyrrolidone-based copolymer ") is represented by a ratio of a constituent unit (Α) derived from Ν·vinylpyrrolidone to a constituent unit (Β) derived from a hydroxyl group-containing (fluorenyl) acrylate. The ratio of the (Α) 5〇 to 95% by mass and the (Β) 50 to 5 mass% is contained. Preferably, the (Α) 60 to 9 enamel 3:%, the (Β) 40 to 10% by mass, more preferably, the (Α) 65 to 85% by mass, the (Β) 3 5 to 15 mass . /〇. Just come from Ν-vinyl. When the ratio of the constituent φ position (A) of the pyrrolidone to the constituent unit (B) derived from the hydroxyl group-containing (meth) acrylate (copolymerization ratio) is in the above range, it is possible to obtain a suitable one, for example. A copolymer of a water-resistant and hydrophilic good cross-linked coating film. If the constituent unit (A) derived from N-vinylpyrrolidone is more than the above range (the constituent unit (B) derived from the hydroxyl group-containing (fluorenyl) acrylate is smaller than the above range), it is difficult to exhibit a hydroxyl group-containing The advantage that the acrylate has high reactivity with the crosslinking agent. Conversely, if the constituent unit (A) derived from N-vinylpyrrolidone is smaller than the above range (the constituent unit derived from the hydroxyl group-containing (meth) acrylate is the above In a wide range, it is easy to cause gelation and becomes a total of 1374896 polymer which is insoluble in water, or a copolymer having a high degree of dispersion (large molecular weight distribution) β. The vinylpyrrolidone copolymer of the present invention, except for Ν·ethylene base. In addition to the constituent unit (Α) of pirone and the constituent unit (Β) derived from a hydroxyl group-containing (fluorenyl) acrylate, it may have a subsequent step in the [method of producing a vinylpyrrolidone copolymer] column. The structural unit derived from a monomer copolymerizable with Ν-vinylpyrrolidone is described. At the same time, when there is a structural unit derived from another monomer, the ratio of the structural unit derived from the other monomer is preferably less than 20% by mass and less than 1% by mass for the entire structural unit. In the above configuration, the first vinylpyrrolidone-based copolymer of the present invention has a water-insoluble content of 5% by mass or less based on the solid content (that is, the solid content-based water-insoluble content ratio is 〇. 5 mass% or less). It is preferably 0.3% by mass or less, more preferably 〇丨% by mass or less. When the water-insoluble content of the solid content is 5% by mass or less, it is possible to avoid deterioration of the surface smoothness of the formed cross-linked coating film, for example, after film formation and crosslinking, and after removal of cross-linking. Problems such as gel swelling during water washing required for unreacted raw materials. Further, the water insoluble content ratio of the copolymer based on the solid content is measured by the method described later in the examples. The first vinylpyrrolidone copolymer of the present invention can be produced by the first or second vinylpyrrolidone copolymer of the present invention to be described later.

以下者’較佳為1.75以下、更佳為1.70以下。如此，只要分散度為1.8以下所形成之交聯塗犋均一，則可避免例如於製膜並交聯時，度惡化之問題。又，分散度，係以 1374896 重量平均分子量/數量平均分子量所求得之參數，可藉實施例中後述之方法來測定。本發明之第二乙烯基吡咯烷酮系共聚物，可藉由後述之本發明之第一乙烯基吡咯烷酮系共聚物之製造方法中特別將疏基化合物作為鏈轉移劑使用之方法（上述特佳之態樣）、或後述之本發明之第二乙烯基吡咯烷酮系共聚物之製造方法容易地製得，但並不限定於此。本發明之第三乙烯基吡咯烷酮系共聚物，係水不溶分為〇·5質量％ (固體成分基準）以下、且分散度為1 8以下者。亦即’本發明之第三乙烯基吡咯烷酮系共聚物，係同時滿足上述本發明之第一乙烯基吡咯烷酮系共聚物之要件 (水不溶分含有率）、與上述本發明之第二乙烯基吡咯烷酮系共聚物之要件（分散度）者，可謂本發明之最佳態樣。此處，水不溶分與分散度，分別同樣適用上述之說明。本發明之乙烯基吡咯烷酮系共聚物及後述之其製造方法中，帶來構成單位（B)之含羥基（甲基）丙烯酸酯（b)，可舉例如（曱基）丙烯酸2-羥基乙酯、（曱基）丙烯酸羥基丙酯、（甲基）丙稀酸經基丁酯、（甲基）丙稀酸2-經基乙氧乙酯等，其中，從與交聯劑的反應性、交聯塗膜之耐水性的觀點考量，則以（甲基）丙烯酸2-羥基乙酯為佳。（甲基）丙烯酸2_經基乙醋’雖可為甲基丙烯酸2-羥基乙酯（HEMA)，但以丙稀酸2-經基乙g旨（HE A)為較佳。丙稀酸2 -經基乙醋（HE A)，由於親水性高，而可提昇以其作為原料單體之乙烯基吡咯烷酮系共聚物所製得之交聯塗膜的親水性，且可提昇未交The following is preferably 1.75 or less, more preferably 1.70 or less. Thus, as long as the cross-linking coating formed by the dispersion degree of 1.8 or less is uniform, the problem of deterioration in the degree of film formation and crosslinking, for example, can be avoided. Further, the degree of dispersion is a parameter obtained by using 1,374,896 weight average molecular weight/number average molecular weight, which can be measured by the method described later in the examples. The second vinylpyrrolidone-based copolymer of the present invention can be used as a chain transfer agent by a method for producing a first vinylpyrrolidone-based copolymer of the present invention to be described later (the above-mentioned excellent aspect) The method for producing the second vinylpyrrolidone copolymer of the present invention to be described later is easily produced, but is not limited thereto. The third vinylpyrrolidone-based copolymer of the present invention has a water-insoluble content of 5% by mass (based on solid content) and a degree of dispersion of 18 or less. That is, the third vinylpyrrolidone-based copolymer of the present invention satisfies the requirements of the first vinylpyrrolidone-based copolymer of the present invention (water-insoluble content) and the above-mentioned second vinylpyrrolidone of the present invention. The requirement (dispersion) of the copolymer is the best aspect of the invention. Here, the water insolubles and the degree of dispersion are equally applicable to the above description. In the vinylpyrrolidone-based copolymer of the present invention and the method for producing the same, the hydroxyl group-containing (meth)acrylate (b) constituting the unit (B) may be mentioned, and for example, 2-hydroxyethyl (meth) acrylate may be mentioned. , (mercapto) hydroxypropyl acrylate, (meth) acrylic acid via butyl acrylate, (meth) acrylate 2- ethoxyethyl ethoxylate, etc., wherein, from the reactivity with the crosslinking agent, From the viewpoint of water resistance of the crosslinked coating film, 2-hydroxyethyl (meth)acrylate is preferred. The (meth)acrylic acid 2_-based ethyl acetoacetate may be 2-hydroxyethyl methacrylate (HEMA), but it is preferably acrylic acid 2-ethylidene (HE A). Acetic acid 2--ethyl acetonate (HE A), because of its high hydrophilicity, can improve the hydrophilicity of the crosslinked coating film prepared by using the vinylpyrrolidone copolymer as a raw material monomer, and can be improved Not paid

11 1374896 « 聯部之水洗性，除具上述優點之外，由於其交聯反應性佳，故具有提高乙烯基吡咯烷酮系共聚物及與交聯劑反應性之優點。本發明之第三乙烯基吡咯烷酮系共聚物，與上述第二 • 乙烯基吡咯烷酮系共聚物相同，可藉由後述之本發明之第 • —乙烯基吡咯烷酮系共聚物之製造方法中特別將巯基化合物作為鏈轉移劑使用之方法（上述特佳之態樣）、或後述 _ 之本發明之第二乙烯基吡咯烷酮系共聚物之製造方法容易地製得，但並不限定於此。本發明之乙烯基吡咯烷酮系共聚物，以菲肯齊爾法所測得之K值必須為12以上，以15以上為佳，2〇以上更佳。其係因若K值未滿12 ,則作成交聯塗膜時有耐水性降低之傾向。本發明之乙烯基吡咯烷酮系共聚物其K值之上限，雖不拘，但以90以下為佳，80以下為更佳。以菲肯齊爾法所測得之K值若超過90，則例如於作成交聯塗臈時有製 φ 膜後之水洗性不足等之傾向。又，本發明中，K值，係將乙烯基0比洛烧酮系共聚物，乂 1質畺0/〇之濃度溶解於可溶解聚合物之任意溶劑中，於 • 25 C下以毛細管黏度計測定該溶液之黏度、將該測定值以下述菲肯齊爾式計算所得之值。 (log η rel)/C= [(75 0K02)/(1 + 1.5K0C)] + Κ0 Κ= 1000 κ〇其中，C係表示溶液j 00mL中乙烯基吡咯烷綱系共聚 12 1374896 物之g數’ 7? rel係表示溶液對溶劑之黏度。本發明之乙烯基吡咯烷酮系共聚物，並不限制其用途，可使用於所有的用途中。若舉其用途例，有各種無機物或有機物之分散劑、凝集劑、增黏劑、黏著劑、接著劑、表面塗布劑、交聯性組成物等’更具體而言有泥土分散劑、水泥材料分散劑、水泥材料用增黏劑、洗劑用辅助劑、洗幻用抗脫色劑、重金屬補足劑（supplement)、金屬表面處理劑、染色助劑、染料固定劑、泡床安定劑、乳化安定劑、墨水染料分散劑、水性墨水安定劑' 塗料用顏料分散劑、塗料用增稠劑、感壓接著劑、紙用接著劑、黏著糊、醫療用接著劑、貼附劑用黏著劑、化妝面膜用黏著劑、樹脂用填料分散劑、記錄紙用塗布劑、t墨紙用表面處理劑、感光性樹脂用分散劑、抗靜電劑、保濕劑、吸水性樹脂用原 :、肥料用黏合劑、高分子交聯冑、樹脂相容劑、相片試藥添加劑、化妝用調配劑添加劑、整髮劑助劑、喷霧型整髮劑添加劑、防€組成物用添加劑等，而最有效活用其特，之用途，係例如製得兼備耐水性及親水性膜之硬化性樹成物的原料聚合物，而利用作為交聯塗膜等。本發明之乙烯基吡咯烷酮系共聚物，來自⑷乙烯基吡各坑酮之構成單位（A)與來自含經基之（甲基）丙稀酸醋之構成單位⑻’以佔總構成單位中之8G質量％以上為佳。藉由使（A)與（B)佔總構成單位中之大部分，可成為親水性高、且與各種基材之密合性皆優異（起因於⑷）、及與交聯劑之反應性高（起因於⑻）之乙縣料㈣系共聚物。若 13 1374896 未滿80質量％ ’貝_!有成為不具足夠親纟性肖各種基材之密合性、及與交聯劑之反應性的乙烯基吡咯烷酮系共聚物之虞。 [乙烯基吡咯烷酮系共聚物之製造方法] 本發明之乙烯基I»比哈烧酮系共聚物之製造方法（包含第一及第二乙烯基吡咯烷酮系共聚物之製造方法；以下也簡稱「本發明之乙烯基吡咯烷酮系共聚物之製造方法」）， N-乙烯基吼咯烷酮與含羥基之（甲基）丙烯酸酯以對於兩者合計量之比率來表示時，係將含有該（a)5〇〜95質量0/〇、該（b)50〜5質量❶/◦比例之單體成分進行聚合。較佳為，該 (a)60〜90質量％、該（b)40〜1〇質量％，更佳為，該（a)65〜85 質量％ '該（b)3 5〜15質量％。只要N_乙烯基吡咯烷酮（〇與含羥基之（甲基）丙烯酸酯（b)為上述範圍，即可製得水不溶分少（後述之範圍）之共聚物。若N_乙烯基吡咯烷酮（a) 較上述範圍多（含羥基之（甲基）丙烯酸酯（b)較上述範圍少），則所得之共聚物難以發揮來自含羥基之（甲基）丙烯酸醋之與交聯劑反應性高之優點，相反的，若N_乙烯基吡略烧酮（a)較上述範圍少（含經基之（曱基）丙稀酸酯（b)較上述範圍多）’則易引起凝膠化使所得共聚物變成水不溶分多、且所得共聚物之分散度高（分子量分布廣）。上述單體成分，係以N-乙稀基》比洛烧晒（a)與含經基之 (曱基）丙稀酸酯（b)為必須成分，此外，亦可含有可與ν·乙烯基。比咯烷酮共聚合之單體（其他單體）❶其他單體，並不特別限定，具體而言，可舉例如：1)(甲基）丙烯酸甲酯、 1374896 (曱基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸環己酯等之（曱基）丙烯酸酯類；2)(甲基）丙烯醯胺、及N_單甲基（曱基）丙稀酿胺、N -單乙基（甲基）丙稀酿胺、n，N-二甲基（甲基）丙稀酿胺等之（曱基）丙稀酿胺衍生物類；3)(甲基）丙稀酸二甲基胺基乙酯、二甲基胺基乙基（曱基）丙烯酿胺、乙烤基11比咬、乙稀基咪唾等之驗性不飽和單體；4)乙稀基甲醯胺、乙烯基乙醯胺、乙烯基噁唑等之乙烯基醯胺類； 5)(甲基）丙烯酸、衣康酸、馬來酸、富馬酸等之含羧基不飽和單體；6)馬來酸酐、衣康酸酐等之不飽和酸酐類；7)丙酸乙煉酯、乙酸乙稀酯等之乙稀酯類；8)碳酸乙稀乙酯及其衍生物，9)苯乙稀及其衍生物；1〇)(甲基）丙稀酸_2_績酸乙醋及其衍生物；11)乙烯磺酸及其衍生物；12)曱基乙稀醚、乙基乙烯醚、丁基乙烯醚等之乙烯醚類；13)乙稀、丙烯、庚烯、丁二烯等之烯烴類等。該等單體之中，由與N-乙稀基。比咯烷酮之共聚合性等的觀點考量，以1)〜8) 為特佳。上述其他單體，可僅為丨種、亦可為2種以上。當該單體成分含有上述之其他單體時，該其他單體之含量’對總單體成分以未滿20質量％為佳，未滿1〇質量％為更佳。本發明之第一乙烯基吡咯烷酮系共聚物之製造方法中’在對於單體成分存在0.01質量％以上之鏈轉移劑下進行聚σ係重要。本發明之第二乙烯基吡咯烷酮系共聚物之製1^方法中’同樣的，使用對單體成分之0.01質量％以上之鏈轉移齊j亦當然為較佳態樣。又，如後述當逐次添加 15 13/4896 鏈轉移劑時’於進行聚合中無論任何時點，皆以使鏈轉移劑對單體成分之比為上述範圍（換言之於進行聚合之間的全部時點，在各時點反應系内所存在之鍵轉移劑，對該時點反應系内所存在之單體成分之比為上述範圍）為佳。上述鏈轉移劑，可舉例如疏基化合物、次填酸及其鹽、亞硫酸氫鹽、酸式亞硫酸鹽等。纟中，以巯基化合物、次碟酸及其鹽為較佳。鏈轉移劑，可僅為^、亦可為2種以上。11 1374896 « In addition to the above advantages, the water-washing property of the joint has the advantage of improving the reactivity of the vinylpyrrolidone copolymer and the crosslinking agent because of its good cross-linking reactivity. The third vinylpyrrolidone-based copolymer of the present invention is the same as the above-mentioned second vinylpyrrolidone-based copolymer, and a mercapto compound can be particularly used in the production method of the vinyl-pyrrolidone-based copolymer of the present invention to be described later. The method of using the chain transfer agent (the above-described particularly preferred aspect) or the method for producing the second vinylpyrrolidone copolymer of the present invention described later is easily produced, but is not limited thereto. The vinylpyrrolidone-based copolymer of the present invention must have a K value of 12 or more as measured by the Fiknijker method, preferably 15 or more, more preferably 2 or more. If the K value is less than 12, the water resistance tends to decrease when the film is crosslinked. The upper limit of the K value of the vinylpyrrolidone copolymer of the present invention is preferably 90 or less, and more preferably 80 or less. When the K value measured by the Fenzenzier method exceeds 90, for example, when the cross-linking is applied, there is a tendency that the water-washing property after the φ film is insufficient. Further, in the present invention, the K value is obtained by dissolving a concentration of a vinyl group 0 of a ketone ketone-based copolymer, 乂1 mass 畺0/〇 in any solvent which can dissolve a polymer, and a capillary viscosity at 25 C. The viscosity of the solution was measured, and the measured value was calculated by the following Fiknijker formula. (log η rel)/C= [(75 0K02)/(1 + 1.5K0C)] + Κ0 Κ = 1000 κ〇 where C is the number of g of vinylpyrrolidine copolymer 12 1374896 in solution j 00mL ' 7? rel is the viscosity of the solution to the solvent. The vinylpyrrolidone-based copolymer of the present invention is not limited to its use and can be used in all applications. Examples of the use thereof include various inorganic or organic dispersants, aggregating agents, tackifiers, adhesives, adhesives, surface coating agents, cross-linking compositions, etc. More specifically, soil dispersants and cement materials. Dispersing agent, tackifier for cement materials, adjuvant for lotion, anti-decoloring agent for washing, heavy metal supplement, metal surface treatment agent, dyeing auxiliary, dye fixing agent, bubble bed stabilizer, emulsion stability Agents, ink dye dispersants, aqueous ink stabilizers, pigment dispersants for coatings, thickeners for coatings, pressure-sensitive adhesives, adhesives for paper, adhesives, adhesives for medical use, adhesives for adhesives, makeup Adhesive for mask, filler for resin, coating agent for recording paper, surface treatment agent for t-paper, dispersant for photosensitive resin, antistatic agent, humectant, water-absorbent resin: adhesive for fertilizer , polymer cross-linking enamel, resin compatibilizer, photo reagent additive, cosmetic preparation additive, hair styling auxiliary, spray-type hair styling additive, anti-component additive, etc. For the purpose of utilizing the most useful ones, for example, a raw material polymer having a water-resistant and hydrophilic film curable structure is used, and it is used as a crosslinked coating film. The vinylpyrrolidone-based copolymer of the present invention, which comprises (4) a constituent unit (A) of vinylpyridone and a constituent unit (8)' derived from a (meth)acrylic acid-containing vinegar in a total constituent unit. 8G mass% or more is preferred. By making (A) and (B) a majority of the total constituent units, it is highly hydrophilic and excellent in adhesion to various substrates (caused by (4)) and reactivity with a crosslinking agent. High (caused by (8)) of the B material (four) copolymer. If 13 1374896 is less than 80% by mass, it is a vinylpyrrolidone-based copolymer which is not compatible with various substrates and has a reactivity with a crosslinking agent. [Method for Producing Vinylpyrrolidone-Based Copolymer] A method for producing a vinyl I»bihafenone-based copolymer of the present invention (including a method for producing a first and second vinylpyrrolidone-based copolymer; In the method for producing a vinylpyrrolidone copolymer of the invention"), when N-vinylpyrrolidone and a hydroxyl group-containing (meth)acrylate are expressed in a ratio of the total amount of the two, the 5〇~95 mass 0/〇, the monomer component of the (b) 50 to 5 mass ❶/◦ ratio is polymerized. Preferably, the (a) is 60 to 90% by mass, the (b) is 40 to 1% by mass, and more preferably, the (a) is 65 to 85% by mass of the (b) 3 5 to 15% by mass. As long as N_vinylpyrrolidone (〇 and the hydroxyl group-containing (meth) acrylate (b) are in the above range, a copolymer having a small water-insoluble content (the range described later) can be obtained. If N-vinylpyrrolidone (a) When the amount is more than the above range (the hydroxyl group-containing (meth) acrylate (b) is less than the above range), the obtained copolymer is difficult to exhibit high reactivity with the crosslinking agent derived from the hydroxyl group-containing (meth)acrylic acid vinegar. Advantages, conversely, if N_vinylpyrrolidone (a) is less than the above range (containing more than the above range of (meth) acrylate (b)), it is easy to cause gelation. The obtained copolymer has a large amount of water insoluble, and the obtained copolymer has a high degree of dispersion (a wide molecular weight distribution). The above monomer component is an N-ethylene group, and the base is contained (a) and contains a base (曱). The acrylic acid ester (b) is an essential component, and may further contain a monomer (other monomer) which is copolymerizable with ν·vinyl group and pyrrolidone, and other monomers, and is not particularly limited. For example, 1) methyl (meth)acrylate, 1374896 (mercapto) ethyl acrylate, (Methyl) acrylate, (meth) acrylate such as cyclohexyl (meth) acrylate; 2) (meth) acrylamide, and N-monomethyl (mercapto) acrylamide , (N-monoethyl (meth) acrylamide, n, N-dimethyl (meth) acrylamide and other (mercapto) acrylamide derivatives; 3) (methyl) Anhydrous dimethylaminoethyl acrylate, dimethylaminoethyl (mercapto) acrylamide, ethyl bake 11, bite, ethylene, and the like; 4) a vinyl decylamine such as dilute carbamide, vinyl acetamide or vinyl oxazole; 5) a carboxyl group-containing unsaturated monomer such as (meth)acrylic acid, itaconic acid, maleic acid or fumaric acid 6) unsaturated anhydrides such as maleic anhydride and itaconic anhydride; 7) ethylene esters such as ethyl acetate propionate and ethylene acetate; 8) ethylene carbonate and its derivatives, 9 ) styrene and its derivatives; 1 〇) (methyl) acrylic acid _2 _ acid vinegar and its derivatives; 11) ethylene sulfonic acid and its derivatives; 12) thiol ether, B Vinyl ethers such as vinyl ether and butyl vinyl ether; 13) ethylene, propylene, Alkenyl, butadiene, olefins, etc. and the like. Among these monomers, it is composed of an N-ethylene group. The viewpoint of the copolymerization property of pyrrolidone and the like is particularly preferable as 1) to 8). The other monomer may be used alone or in combination of two or more. When the monomer component contains the other monomer described above, the content of the other monomer is preferably less than 20% by mass based on the total monomer component, and more preferably less than 1% by mass. In the method for producing a first vinylpyrrolidone-based copolymer of the present invention, it is important to carry out a poly-sigma system under a chain transfer agent having a monomer component of 0.01% by mass or more. In the method of the second vinylpyrrolidone-based copolymer of the present invention, it is a preferred embodiment to use a chain transfer of 0.01% by mass or more of the monomer component. Further, when the 15 13/4896 chain transfer agent is added one by one as described later, the ratio of the chain transfer agent to the monomer component is set to the above range at any time in the polymerization (in other words, all the time points between polymerizations are carried out, It is preferred that the ratio of the monomer transfer agent present in the reaction system at each time point to the monomer component present in the reaction system at the time point is the above range. The chain transfer agent may, for example, be a sulfhydryl compound, a sub-acid and a salt thereof, a hydrogen sulfite or an acid sulfite. Among them, a mercapto compound, a secondary acid, and a salt thereof are preferred. The chain transfer agent may be used alone or in combination of two or more.

使用锍基化合物作為上述鏈轉移劑之態樣，由於可容易製得分散度低之共聚物，故係本發明之第一乙烯基吡咯烷酮系共聚物之製造方法中之特佳態樣，藉此，容易製得上述本發明之第一或第三乙烯基η比咯烷酮系共聚物。作為鏈轉移劑使用之較佳巯基化合物，可舉例如2_疏基乙醇、1，3-酼基丙醇、丨_硫甘油等疏基醇、3_酼基丙酸、巯基琥珀酸、酼基乙酸等巯基羧酸及其鹽、乙基_2_酼基乙酸醋、半胱胺酸、正十二烷基硫醇，其中，以酼基醇較佳、 2-巯基乙醇更佳。上述鏈轉移劑之使用量，只要對單體成分為〇〇1質量〇/0以上即可’而較佳為，對單體成分為〇〇5〜5質量％。本發明之第二乙烯基吡咯烷酮系共聚物之製造方法中’於含有碳數1〜5之醇10質量％ (對溶劑總量之比例）以上之溶劑（以下’亦稱為「特定溶劑」）中進行聚合很重要。藉此’可製得水不溶分少、分散度低之共聚物。本發明之第一乙烯基吡咯烷酮系共聚物之製造方法中，同樣的於上述特定溶劑中進行聚合亦當然為較佳態樣。又， t後述，當逐次添加溶劑時，於進行聚合中無論任何時點，皆以使特定溶劑對溶劑總量之比為上述範圍（換言之，於聚合之間的全部時點，在各時點反應系内所存在之特疋冷劑’對該時點反應系内所存在之溶劑總量之比為上述範圍）為佳。上述碳數1〜5之醇，可舉例如甲醇、乙醇、異丙醇、 2·甲基小丙醇等1碳數卜5之醇，可僅為丨種、亦可為 2種以上。曰X炭數1〜5之醇，以對溶劑總量之比例計只要含有^ 〇質ΐ %以上（換·r之，特定溶劑中質量％以上）即可，但較佳為含有15質量％以上、更佳為含有20質量％以上。該特定溶劑之較佳態樣，可舉例如上述碳數卜5之醇 :水的混合溶劑。水以含有3〇質量％以上為佳含有5〇以上為更佳。特定溶劑中之水若未㉟鄉，則聚合乙烯基°比咯烷酮的反應會有變慢的傾向。當該特定溶劑亦含有該碳數1〜5謂以外的溶劑（其 ^容劑）0寺，該其他溶劑，以水為佳（本發明之第-乙稀土吡°各烧，系共聚物之製造方法中，f未使用該含特定量炭數1〜5之醇的特定溶劑時，以於主成分為水之溶劑中 n行聚合為佳）。上述特定溶劑、或本發明之第-乙稀基 0各院酮系共聚物之製诰古仏、取初方法中之溶劑，含有水以外之其溶劑當然亦可，於該情形，係以對溶劑總量之1〇質量% 以下之範圍内為佳。 17 1374896 該水以外之其他溶劑’可舉例如丨_庚醇等碳數6以上之醇；丙二醇單f基乙酸醋、二乙二醇單曱基乙酸酯等之烧樓乙二醇之謎（乙酸g旨）類；二甲基甲醯胺、N甲基吡咯院_等之醯胺類；乙酸乙酯、乙酸丁醋、丁内醋等之酯類；己烷、辛烷等之脂肪族烴類；環己烷等脂環式飽和烴類；環己烯等之脂環式不飽和烴類；苯、曱苯、二甲苯等之芳香族烴類；丙酮、甲乙酮等之酮類；二氯乙烷、氯仿、四氯化碳等之齒素化烴類；二甲醚、二噁烷、四氫呋喃等之醚類；二曱亞礙等續酸酯類；碳酸二甲酯、碳酸二乙酯等之碳酸酯類；碳酸伸乙酯、碳酸伸丙酯等之脂環式碳酸酯類等。上述特定溶劑之使用量、及本發明之第一乙烯基吡咯烷酮系共聚物製造方法中所使用之溶劑的使用量，並無特別限定，考量生產性等來適當設定㈣，而以單體成；之濃度為10質量％以上為佳。By using a mercapto compound as the above-mentioned chain transfer agent, since a copolymer having a low degree of dispersion can be easily obtained, it is a particularly preferable aspect in the method for producing the first vinylpyrrolidone copolymer of the present invention. It is easy to obtain the above first or third vinyl 比 pyrrolidone copolymer of the present invention. Preferred mercapto compounds for use as the chain transfer agent include, for example, 2, mercaptoethanol, 1,3-mercaptopropanol, mercapto-thioglycerol, etc., 3-mercaptopropionic acid, mercapto succinic acid, hydrazine A mercaptocarboxylic acid such as a vinyl acetate or a salt thereof, ethyl 2-hydrinoacetic acid vinegar, cysteine, or n-dodecyl mercaptan, wherein a mercapto alcohol is preferred, and 2-mercaptoethanol is more preferred. The amount of the chain transfer agent used may be 〇〇 1 mass 〇 / 0 or more, and preferably, the monomer component is 〜 5 to 5 % by mass. In the method for producing a second vinylpyrrolidone copolymer of the present invention, a solvent containing 10% by mass or more of the alcohol having a carbon number of 1 to 5 (the ratio of the total amount of the solvent) (hereinafter referred to as "specific solvent") It is important to carry out the polymerization. By this, a copolymer having less water insoluble content and low dispersion can be obtained. In the method for producing the first vinylpyrrolidone copolymer of the present invention, it is a preferred embodiment to carry out the polymerization in the above specific solvent. Further, t will be described later, when the solvent is added successively, the ratio of the specific solvent to the total amount of the solvent is in the above range at any time during the polymerization (in other words, at all time points between the polymerizations, at each time point in the reaction system) It is preferred that the specific coolant is present in the ratio of the total amount of the solvent present in the reaction system at the time point to the above range. The alcohol having 1 to 5 carbon atoms may, for example, be an alcohol having 1 carbon number, such as methanol, ethanol, isopropanol or 2, methyl-propanol, and may be used alone or in combination of two or more. The alcohol having a carbon number of 1 to 5 in terms of the total amount of the solvent may be contained in a ratio of the total amount of the solvent, and may be contained in an amount of more than 5% by mass or more (% by mass or more in a specific solvent), but preferably 15% by mass. The above is more preferably 20% by mass or more. A preferred embodiment of the specific solvent may, for example, be a mixed solvent of the above-mentioned carbon number: alcohol: water. It is more preferable that the water contains 3 〇% by mass or more, preferably 5 Å or more. If the water in the specific solvent is not 35, the reaction of the polymerized vinyl group with the pyrrolidone tends to be slow. When the specific solvent also contains a solvent other than the carbon number of 1 to 5 (the solvent), the other solvent is preferably water (the first -b rare earth pyridinium of the present invention, the copolymer) In the production method, when a specific solvent containing a specific amount of alcohol having a carbon number of 1 to 5 is not used, f is preferably polymerized in a solvent having a main component of water. The specific solvent or the solvent of the ketene-based copolymer of the present invention, or the solvent of the initial method, may be a solvent other than water, and in this case, It is preferred that the total amount of the solvent is in the range of 1% by mass or less. 17 1374896 Other solvents other than water may include, for example, an alcohol having a carbon number of 6 or more such as hydrazine-heptanol; and a mystery of burning ethylene glycol such as propylene glycol mono-f-acetic acid vinegar or diethylene glycol monodecyl acetate. (Acetyl acetate); guanamines such as dimethylformamide, N-methylpyrrole, etc; esters of ethyl acetate, butyl acetate, butane vinegar, etc.; fats such as hexane and octane a hydrocarbon; an alicyclic saturated hydrocarbon such as cyclohexane; an alicyclic unsaturated hydrocarbon such as cyclohexene; an aromatic hydrocarbon such as benzene, toluene or xylene; a ketone such as acetone or methyl ethyl ketone; a dentate hydrocarbon such as dichloroethane, chloroform or carbon tetrachloride; an ether such as dimethyl ether, dioxane or tetrahydrofuran; a phthalate such as diterpene; a dimethyl carbonate; A carbonate such as an ethyl ester; an alicyclic carbonate such as an ethyl carbonate or a propyl carbonate; and the like. The amount of the specific solvent to be used and the amount of the solvent used in the method for producing the first vinylpyrrolidone-based copolymer of the present invention are not particularly limited, and may be appropriately set in consideration of productivity (4), and may be formed as a monomer; The concentration is preferably 10% by mass or more.

不發明之乙烯基吡咯烷醐系共聚物之製造方法中，石使用習知之聚合起始劑。該聚合起始劑，可舉例如2U 虱雙異丁腈、2,2’-偶氮雙(2·甲基丙脒)二鹽酸鹽、 2,2 -偶氮雙異丁酉楚醋、4,4’_偶氮雙（4_氰基戊酸）系聚合起始劑’·苯酿基過氧化物或過氧化氫等過氧化之自由基聚合系聚合起始劑；三氣化硼鐵⑼、二乙基氯化錄、二乙基辞、雜多I心土氯化陽離子聚合系聚合起始料。其中，偶以白土等之聚合效率觀點上較佳，特別是，二甲基 18 1374896 酯為更佳。聚合起始劑，可僅為1種、亦可為2種以上。關於該聚合起始劑之使用量，並無特別限定，但以對單體成分A 0.05質量％以上為佳。更佳為，對單體成分為 0.1質量％以上。若聚合起始劑之使用量未滿〇〇5質量％: 則有殘存大量未反應單體之虞。本發明之乙烯基吡咯烷酮系共聚物之製造方法中，可適當地視需要將任意助觸媒、pH調節劑、緩衝劑等與該聚合起始劑一同使用。本發明之乙烯基吡咯烷酮系共聚物之製造方法中，單體成分、聚合起始劑、溶劑（特定溶劑）、鏈轉移劑等加入方法，並無特別限制，但尤其是關於單體成分該含羥基之（甲基）丙烯酸酯（b)係以經由逐次添加投入反應器内為佳。若該含羥基之（甲基）丙烯酸酯（b)非逐次添加而為一次添加時，則有生成多量水不溶分之虞。具體而言，所謂逐次添加，可為連續地添加（例如，以一定時間滴下之態樣）、可為斷續地添加（例如’將原料分為數次投入之態樣）、亦可為組合兩組來添加。本發明之第一及第二乙烯基吡咯烷酮系共聚物之製造方法中’進行該聚合之際之聚合溫度（反應液之溫度），以50 c以上為佳、60°C以上為更佳。本發明之乙烯基吡咯烷酮系共聚物之製造方法中，亦可藉由對上述聚合所得之反應液施以蒸餾，以製得經除去未反應之含經基之（甲基）丙烯酸酯、及溶劑中水以外成分後之水溶液。 € 19 本發明之乙烯基吡咯烷酮系共聚物，如前述，係以菲肯齊爾法所測得之K值為12以上者，若K值增大，則水不溶分容易増加、分子量分布亦容易變廣，而若依上述本發明之製造方法，則不易引起如此之問題。當用以製得本發明之乙烯基啦咯烷酮系共聚物之原料單體之其一之含羥基之（甲基）丙烯酸酯’為（甲基）丙烯酸2-&基乙S曰時，如前述，使用丙烯酸2-羥基乙酯（he A)較甲基丙烯酸2_羥基乙酯（HEMA)為佳。丙烯酸2-羥基乙酯 (HEA)，交聯反應性高，因此，可提高將其作為原料單體之乙烯基吡咯烷酮系共聚物之交聯反應性。然而，相反的，丙烯酸2-羥基乙酯（HEA)，於用以製得乙烯基吡咯烷酮系共聚物之聚合中，更易受到交聯反應，故通常難以製得水不溶分少、分子量分布窄之共聚物，但若藉由上述本發明之製造方法，則可克服以丙烯酸2-羥基乙酯（HEA)作為原料單體場合之該困難性。本發明之乙烯基吡咯烷酮系共聚物之製造方法較佳為，該N-乙烯基吡咯烷酮（a)與含羥基之（甲基）丙烯酸酯佔供聚合單體成分巾8G f量％以上。藉由使⑷與（b)佔供聚合單體成分中大部分，可製得親水性高且與各種基材之费合性優異（起因於⑷）、與交聯劑反應性高（起因於⑻）之乙烯基吡咯烷酮系共聚物。為了製造如此之乙烯基吡咯院綱系共聚物’⑷與（b)必須佔供聚合單體成分巾8〇質量 %左右。若未滿80質量❶/。，則有無法製得具有足夠親水性、與各種基材之密合性、及與交聯劑之反應性之乙稀基d比洛 20In the method for producing a vinylpyrrolidinium-based copolymer which is not invented, a conventional polymerization initiator is used as the stone. The polymerization initiator may, for example, be 2U 虱bisisobutyronitrile, 2,2'-azobis(2·methylpropionamidine) dihydrochloride, 2,2-azobisisobutyl phthalic acid, 4 , 4'-azobis(4-cyanovaleric acid)-based polymerization initiator', phenyl-brenyl peroxide or hydrogen peroxide and other free radical polymerization polymerization initiator; tri-carbo-boron (9), diethyl chloride, diethyl, heteropoly I core clay cation polymerization polymerization starting materials. Among them, the polymerization efficiency of clay or the like is preferred, and in particular, dimethyl 18 1374896 ester is more preferable. The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is not particularly limited, but it is preferably 0.05% by mass or more based on the monomer component A. More preferably, the monomer component is 0.1% by mass or more. If the amount of the polymerization initiator used is less than 〇 5% by mass: there is a large amount of unreacted monomers remaining. In the method for producing a vinylpyrrolidone copolymer of the present invention, any of a promoter, a pH adjuster, a buffer, and the like may be used together with the polymerization initiator as needed. In the method for producing a vinylpyrrolidone-based copolymer of the present invention, a method of adding a monomer component, a polymerization initiator, a solvent (specific solvent), a chain transfer agent, or the like is not particularly limited, but particularly relates to a monomer component. The hydroxyl (meth) acrylate (b) is preferably added to the reactor via sequential addition. When the hydroxyl group-containing (meth) acrylate (b) is added one by one without adding it in a single step, a large amount of water-insoluble matter is formed. Specifically, the sequential addition may be continuously added (for example, in a state of dropping for a certain period of time), may be intermittently added (for example, 'the raw material is divided into several injections), or may be a combination of two Group to add. In the method for producing the first and second vinylpyrrolidone copolymers of the present invention, the polymerization temperature (temperature of the reaction liquid) at the time of carrying out the polymerization is preferably 50 c or more, more preferably 60 ° C or more. In the method for producing a vinylpyrrolidone copolymer of the present invention, the reaction liquid obtained by the above polymerization may be subjected to distillation to obtain an unreacted transmiscible (meth) acrylate and a solvent. An aqueous solution after the ingredients other than water. The vinylpyrrolidone copolymer of the present invention has a K value of 12 or more as measured by the Fenkenzier method as described above, and if the K value is increased, the water insoluble matter is easily added and the molecular weight distribution is also easy. It becomes wider, and if it is according to the manufacturing method of the present invention described above, such a problem is not easily caused. When the hydroxyl group-containing (meth) acrylate which is used to obtain the raw material monomer of the vinyl palladinone copolymer of the present invention is (meth)acrylic acid 2-& As described above, 2-hydroxyethyl acrylate (he A) is preferred over 2-hydroxyethyl methacrylate (HEMA). Since 2-hydroxyethyl acrylate (HEA) has high crosslinking reactivity, the crosslinking reactivity of the vinylpyrrolidone copolymer which is a raw material monomer can be improved. However, conversely, 2-hydroxyethyl acrylate (HEA) is more susceptible to crosslinking reaction in the polymerization for preparing a vinylpyrrolidone-based copolymer, so it is generally difficult to obtain a water-insoluble fraction and a narrow molecular weight distribution. The copolymer, however, by the above-described production method of the present invention, the difficulty in the case of using 2-hydroxyethyl acrylate (HEA) as a raw material monomer can be overcome. In the method for producing a vinylpyrrolidone copolymer of the present invention, it is preferred that the N-vinylpyrrolidone (a) and the hydroxyl group-containing (meth) acrylate account for 8 % by weight or more of the monomer to be polymerized. By making (4) and (b) account for most of the monomer components to be polymerized, it is possible to obtain high hydrophilicity and excellent compatibility with various substrates (caused by (4)) and high reactivity with a crosslinking agent (caused by (8)) A vinylpyrrolidone copolymer. In order to manufacture such a vinyl pyrene-based copolymer, '(4) and (b) must be about 8 % by mass of the monomer to be polymerized. If it is less than 80 mass ❶ /. However, it is impossible to obtain a vinyl group d, which has sufficient hydrophilicity, adhesion to various substrates, and reactivity with a crosslinking agent.

烷酮系共聚物之虞。【實施例】 ’但本發明並質量份」僅記以下，藉由實施例以更具體說明本發不受限於此。以下，除特別說明以外，將為「份」、「質量％」僅記為「％」。以下記方式測定水不溶分含有率實施例與比較例中及分散度。 <水不溶分含有率> 將調整為10%濃度之乙烯基吡咯烷酮系共聚物溶液 5〇〇g (聚合物固體成分5〇g)，以JIS Z88〇i規定之篩（公稱尺寸45μιη、直徑75mm、深度20mm)過濾，將殘存於 4上之凝膠以l〇〇〇g離子交換水洗淨。將該篩以8(rc乾燥 1小時後，測定其重量’求出過濾前後之重量增加分（Xg)，根據下式a十算出水不溶分含有率。水不溶分含有率（％)=[重量增加分（Xg)/聚合物固體成 •分（50g)]xl00 <分散度> 所製得之乙烯基吡咯烷酮系共聚物溶液，以下述條件以凝膠透析層析（GPC )進行分析，藉此以聚苯乙烯換算求出重ΐ平均分子量（Mw )與數量平均分子量（Μη )，根據（Mw ) / ( Μη )計算出分散度。管枉：昭和電工（株）製「ShodexKD-G」、「Shodex LF804」、「ShodexKDSOl, 21 1374896 溶析液（eluent) ··含0.1 %溴化經之二p基甲酿胺溶液溶析液流量：0.8mL/分鐘注入量：1〇叫The oxime of the alkanone copolymer. [Embodiment] The present invention is not limited to the following, and the present invention is not limited thereto. Unless otherwise specified, "parts" and "% by mass" are only referred to as "%". The water insoluble content ratio in the examples and comparative examples and the degree of dispersion were measured by the following methods. <Water insoluble content rate> 5 〇〇g (polymer solid content: 5 〇g) of a vinylpyrrolidone copolymer solution adjusted to a concentration of 10%, and a sieve specified by JIS Z88〇i (nominal size: 45 μm, Filtered by a diameter of 75 mm and a depth of 20 mm), and the gel remaining on 4 was washed with 100 g of ion-exchanged water. The sieve was subjected to 8 (the rc was dried for 1 hour, and the weight was measured) to determine the weight gain component (Xg) before and after the filtration, and the water-insoluble content ratio was calculated according to the following formula a. The water-insoluble content ratio (%) = [ Weight gain point (Xg) / polymer solids (minutes (50 g)] xl00 <dispersion> The prepared vinylpyrrolidone-based copolymer solution was analyzed by gel dialysis chromatography (GPC) under the following conditions. Then, the average molecular weight (Mw) and the number average molecular weight (Μη) of the heavy enthalpy were calculated in terms of polystyrene, and the degree of dispersion was calculated from (Mw) / ( Μη ). Tube 枉: Shodex KD-made by Showa Denko Co., Ltd. G", "Shodex LF804", "ShodexKDSOl, 21 1374896 Eluent (eluent) · · 0.1% brominated dip-based amide solution solution flow rate: 0.8mL / min Injection volume: 1 〇

管柱加熱器：40°C 檢測器：折射率檢測器（RI ) 樣品濃度：0.5% (實施例1 ) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水7〇份，邊攪拌邊導入氮氣作成氮氣環境氣氛。將聚合容器以油浴加熱使内溫為98後，將混合有 Ν·乙烯基η比咯烷酮（NVP)33.7份、丙烯酸2-羥基乙酯 (HEA)7.9份、25%氨水〇.5份、30%次磷酸水溶液1.26份、離子交換水7.2份之單體溶液（A1)、與混合溶解有4,4，_偶氮雙-4-氰戊酸（曰寶化學公司製「nc25」）0.24份、三乙醇胺0.26份、離子交換水丨7 6份之起始劑溶液（八丨），分別以1小時連續地滴下。接著，將於離子交換水26份中浴解有丙稀酸2-羥基乙酯（HEA)0.5份之單體溶液（B1)，以1 5分鐘加入β再者，於持續加熱攪拌丨〇5分鐘之間，將於離子交換水3份中溶解有4,4，-偶氮雙_4_氰戊酸（曰寶化學公司製「NC25」）〇.〇7份 '三乙醇胺〇〇8份之起始劑溶液（Β 1)，分三次投入，製得NVp/HEa共聚物之溶液（無色透明、固體成分3〇 1%)。所製得之溶液中的NVp/HEA共聚物，K值為28.0、水不溶分含有率〇.09%、重量平均分子量為7764〇、數量 22 1374896 平均分子量38969、分散度1.99。 (實施例2 ) 使用單體溶液（A2)取代實施例1中之單體溶液（A1)，該單體溶液（A2)混合有N-乙烯基吡咯烷酮（NVP)29.5份、丙烯酸2-羥基乙酯（HEA)l 1.9份、25%氨水0.5份、30%次磷酸水溶液1.26份、離子交換水7.2份；使用單體溶液（B2) 取代實施例1中之單體溶液（B1)，該單體溶液（B2)係於離子交換水2.6份中溶解有丙烯酸2-羥基乙酯（HEA)0.76份而得，除此之外係以和實施例1同樣之方式，製得NVP/HEA 共聚物之溶液（無色透明、固體成分29_9%)。所製得之溶液中的NVP/HEA共聚物，K值為26.2、水不溶分含有率0.11%、重量平均分子量為75832、數量平均分子量41883、分散度1.81。 (實施例3) 使用甲基丙烯酸2-羥基乙酯（HEMA)取代實施例1中之丙烯酸2-經基乙酯（HEA)，除此之外係以和實施例1相同之方式，製得NVP/HEMA共聚物之溶液（無色透明、固體成分29.5%)。所製得之溶液中的NVP/HEMA共聚物，K值為28.5、水不溶分含有率0.08%、重量平均分子量為82286、數量平均分子量45329、分散度1.82。 (實施例4) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水50份，邊攪拌邊導入氮氣作成氮氣環境Column heater: 40 °C Detector: refractive index detector (RI) Sample concentration: 0.5% (Example 1) In a polymerization vessel equipped with a condenser, a nitrogen inlet line, and a thermometer, 7 parts of ion-exchanged water was added. Nitrogen was introduced into the nitrogen atmosphere while stirring. After the polymerization vessel was heated in an oil bath to have an internal temperature of 98, 33.7 parts of ruthenium vinyl ene pyrrolidone (NVP), 7.9 parts of 2-hydroxyethyl acrylate (HEA), and 25% ammonia hydrazine were mixed. a portion, 1.26 parts of a 30% aqueous solution of hypophosphorous acid, 7.2 parts of a monomer solution (A1) of ion-exchanged water, and 4,4,-azobis-4-cyanovaleric acid ("25" manufactured by Sakai Chemical Co., Ltd.) 0.24 parts, 0.26 parts of triethanolamine, and 71 parts of an initiator solution (eight bars) of ion-exchanged water hydrazine were successively dropped for 1 hour. Next, a monomer solution (B1) of 0.5 parts of 2-hydroxyethyl acrylate (HEA) was dissolved in 26 parts of ion-exchanged water, and β was added in 15 minutes, and the mixture was continuously heated and stirred. Between the minutes, 4,4,-azobis-4-cyanovaleric acid ("NC25" manufactured by Sakai Chemical Co., Ltd.) was dissolved in 3 parts of ion-exchanged water. 〇7 parts of 'triethanolamine 〇〇8 parts The initiator solution (Β 1) was charged in three portions to prepare a solution of NVp/HEa copolymer (colorless transparent, solid component 3〇1%). The NVp/HEA copolymer in the obtained solution had a K value of 28.0, a water insoluble content ratio of 〇.09%, a weight average molecular weight of 7764 Å, a quantity of 22 1374896, an average molecular weight of 38,969, and a degree of dispersion of 1.99. (Example 2) The monomer solution (A1) in Example 1 was replaced with a monomer solution (A2) mixed with N-vinylpyrrolidone (NVP) 29.5 parts, 2-hydroxyethyl acrylate Ester (HEA) l 1.9 parts, 25% ammonia water 0.5 parts, 30% aqueous hypophosphorous acid solution 1.26 parts, ion exchange water 7.2 parts; using monomer solution (B2) instead of the monomer solution (B1) in Example 1, the single The NVP/HEA copolymer was obtained in the same manner as in Example 1 except that the body solution (B2) was obtained by dissolving 0.76 parts of 2-hydroxyethyl acrylate (HEA) in 2.6 parts of ion-exchanged water. Solution (colorless and transparent, solid content 29_9%). The NVP/HEA copolymer in the obtained solution had a K value of 26.2, a water-insoluble content of 0.11%, a weight average molecular weight of 75,832, a number average molecular weight of 41,883, and a degree of dispersion of 1.81. (Example 3) The same procedure as in Example 1 was carried out except that 2-hydroxyethyl methacrylate (HEMA) was used instead of 2-ethylidene ethyl acrylate (HEA) in Example 1. A solution of NVP/HEMA copolymer (colorless and transparent, solid content 29.5%). The NVP/HEMA copolymer in the obtained solution had a K value of 28.5, a water insoluble content of 0.08%, a weight average molecular weight of 82286, a number average molecular weight of 45,329, and a degree of dispersion of 1.82. (Example 4) 50 parts of ion-exchange water was added to the polymerization container provided with the condensation tube, the nitrogen gas introduction line, and the thermometer, and nitrogen gas was introduced into the nitrogen atmosphere with stirring.

23 1374896 氣氛。將聚合容器以油浴加熱使内溫為9〇。〇後將混合有 N-乙烯基吡咯烷酮（Nvp)33 6份、丙烯酸2羥基乙酯 (HEA)7.9份、2-巯基乙醇0.13份、離子交換水34份之單體/合液（A4)、與混合溶解有二甲基_2,2’偶氮雙異丁酸酯（和光純藥公司製「V601」）0.42份、異丁醇2.3份、離子交換水1.5份之起始劑溶液（A4)，分別以i小時連續地滴下。接著，將於離子交換水9·6份中溶解有丙烯酸2_羥基乙酯 (ΗΕΑ)〇.5份之單體溶液（Β4)，以15分鐘加入。再者，於持續加熱攪拌135分鐘之間，將於離子交換水〇 3份及異丁醇〇.45份令溶解有二甲基_2,2’_偶氮雙異丁酸酯（和光純藥公司製「V601」）〇·〇8份之起始劑溶液（Β4)，分四次投入，製得NVP/HEA共聚物之溶液（無色透明、固體成分 30.1%) 〇所製得之溶液中的NVP/HEA共聚物，κ值為w o、水不溶分含有率〇·〇〇%、重量平均分子量為93316、數量平均分子量593 64、分散度1.5 7。 (實施例5) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水10份、乙醇1〇份，邊攪拌邊導入氮氣作成氮氣環境氣氛》將聚合容器以油浴加熱使内溫為8〇<>c 後’將混合有N-乙烯基吡咯烷酮（NVP)16.8份、丙稀酸2_ 經基乙醋（HEA)4.2份、離子交換水丨1份 '乙醇丨丨份之單體溶液（A5)、與混合溶解有二甲基_2,2，_偶氮雙異丁酸酯（和光純藥公司製「V601」）〇·21份、乙醇34份、離子交換 24 I37489623 1374896 Atmosphere. The polymerization vessel was heated in an oil bath to have an internal temperature of 9 Torr. After mixing, a mixture of 33 parts of N-vinylpyrrolidone (Nvp), 7.9 parts of 2-hydroxyethyl acrylate (HEA), 0.13 parts of 2-mercaptoethanol, and 34 parts of ion-exchanged water (A4), A solution of 0.42 parts of dimethyl 2,2' azobisisobutyrate ("V601" manufactured by Wako Pure Chemical Industries, Ltd.), 2.3 parts of isobutanol, and 1.5 parts of ion-exchanged water (A4) ), successively dripping in i hours. Next, a monomer solution (Β4) of 2-hydroxyethyl acrylate (5 parts) was dissolved in 9 parts of the ion-exchanged water, and the mixture was added over 15 minutes. In addition, during continuous heating and stirring for 135 minutes, 3 parts of ion exchanged water and 异45 parts of isobutanol will dissolve dimethyl 2,2'-azobisisobutyrate (and pure light). Pharmacopoeia "V601") 〇·〇8 parts of the initiator solution (Β4), divided into four times, to obtain a solution of NVP/HEA copolymer (colorless transparent, solid content 30.1%) 〇 prepared solution The NVP/HEA copolymer has a kappa value of wo, a water insoluble content ratio of 〇·〇〇%, a weight average molecular weight of 93316, a number average molecular weight of 593 64, and a dispersion degree of 1.57. (Example 5) In a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer, 10 parts of ion-exchanged water and 1 part of ethanol were added, and nitrogen gas was introduced into a nitrogen atmosphere while stirring. The polymerization vessel was heated in an oil bath. After the internal temperature is 8 〇<>c, 'The mixture will be mixed with 16.8 parts of N-vinylpyrrolidone (NVP), 2% of ethyl acetoacetate (HEA), and 1 part of ion exchanged hydrazine. The monomer solution (A5) and the mixed solution of dimethyl 2,2,-azobisisobutyrate ("V601" manufactured by Wako Pure Chemical Industries, Ltd.), 21 parts, 34 parts of ethanol, and ion exchange 24 I374896

水3.4份之起始劑溶液（A5)，分別以2小時連續地滴下。再者’持續加熱攪拌2小時，製得NVP/HEA共聚物之溶液（無色透明、固體成分30.1%)。所製得之溶液中的NVP/HEA共聚物，K值為35.1、水不溶分含有率0.04%、重量平均分子量為127069、數量平均分子量78385、分散度丨.62。 (實施例6 )3.4 parts of the initiator solution (A5) of water was continuously dropped over 2 hours. Further, the mixture was continuously heated and stirred for 2 hours to obtain a solution of NVP/HEA copolymer (colorless transparent, solid content: 30.1%). The NVP/HEA copolymer in the obtained solution had a K value of 35.1, a water-insoluble content of 0.04%, a weight average molecular weight of 127069, a number average molecular weight of 78,385, and a degree of dispersion of 6262. (Example 6)

於具備冷凝管、氮氣導入管線、溫度計之聚合容器中’ 加入離子交換水1 7份、乙醇3 ·3份，邊攪拌邊導入氮氣作成氮氣環境氣氛。將聚合容器以油浴加熱使内溫為8 0 °C 後’將混合有N-乙烯基吡咯烷酮（NVP) 1 6.8份、丙烯酸2-經基乙酯（ΗΕΑ)3·8份、2-酼基乙醇〇_〇2份、離子交換水 H4、乙醇6·2份之單體溶液（Α6)、與混合溶解有二甲基· 2,2’-偶氮雙異丁酸酯（和光純藥公司製「ν6(Η」）〇.2ι份、乙醇4份之起始劑溶液（A6)，分別以2 γ ^心靖吧例接著，將於離子交換水2.6份及乙醇1.1份中溶解有丙烯酸2-羥基乙酯（HEA)0.42份之單體溶液（B6),以1小時加入。接著，投入於乙醇0.4份中溶解二甲基_2,2,偶氮雙異丁酸酯（和光純藥公司製「V601」）〇.〇2份之起始劑溶液 (B6)之後，使内溫升溫至85它，並且持續加熱攪拌分鐘。其次’加人離子交換水20份，安裝蒸館裝置，將油浴升溫至125。(：開始蒸餾。於餾出量為2〇份之時點，再加入離子交換水ίο份’繼續蒸顧。之後，於再餾出ι〇份之時點（合計餾出量A 30份之時點）將聚合容器冷卻，製 25 1374896 • 得NVP/HEA共聚物之溶液（無色透明、固體成分30.8%)。所製得之溶液中的NVP/HEA共聚物，K值為34.0、水不溶分含有率0.02%、重量平均分子量為1 13685、數量平均分子量69026、分散度1.65。 • (實施例7) . 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水17份、乙醇3.3份，邊攪拌邊導入氮氣作鲁成氮氣環境氣氛。將聚合容器以油浴加熱使内溫為80°C 後，將混合有N-乙烯基吡咯烷酮（NVP) 16.8份、丙烯酸2-經基乙酯（ΗΕΑ)3·8份、2-酼基乙醇0.05份、離子交換水 14.4、乙醇6.2份之單體溶液（Α7)、與混合溶解有二甲基_ 2,2’-偶氮雙異丁酸酯（和光純藥公司製「V601」）0.21份、乙醇4份之起始劑溶液（Α7)，分別以2小時連續地滴下。接著，將於離子交換水2.6份及乙醇1,1份中溶解丙烯酸厶經基乙酯（ΗΕΑ)0.42份之單體溶液（Β7)，以1小時加入後， φ 將内溫升溫至85°C ’並且持續加熱攪拌30分鐘。接著，投入於乙醇0.4份中溶解有二甲基·2,2’-偶氮雙異丁酸酯（和 • 光純藥公司製「V601」）〇.〇2份之起始劑溶液（By)，再持 • 續加熱祝拌分鐘。其次，加入離子交換水2〇份，安裝蒸餾裝置，將油浴升溫至uot開始蒸餾。於餾出量為2〇伤之時點，再加入離子交換水1 〇份，繼續蒸顧。之後，於再餾出10份之時點（合計餾出量為30份之時點）將聚合容器冷卻，製得NVP/HEA共聚物之溶液（無色透明、固體成分30.7%)。In a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer, 17 parts of ion-exchanged water and 3·3 parts of ethanol were added, and nitrogen gas was introduced while stirring to form a nitrogen atmosphere. After the polymerization vessel is heated in an oil bath to have an internal temperature of 80 ° C, 'N-vinylpyrrolidone (NVP) 1 6.8 parts, 2-ethylidene ethyl acrylate (3) 3·8 parts, 2-酼 are mixed. 2 parts of ethanol 〇〇〇、, ion exchange water H4, ethanol 6.2 parts of monomer solution (Α6), mixed with dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Co., Ltd.) The company's "ν6(Η") 〇.2 parts and 4 parts of ethanol starter solution (A6) were respectively dissolved in 2 γ ^ 靖吧, followed by 2.6 parts of ion-exchanged water and 1.1 parts of ethanol. 2-hydroxyethyl acrylate (HEA) 0.42 parts of a monomer solution (B6) was added in 1 hour. Then, 0.4 parts of ethanol was added to dissolve dimethyl 2,2, azobisisobutyrate (and "V601" manufactured by Wako Pure Chemical Industries Co., Ltd.) After 2 parts of the initiator solution (B6), the internal temperature was raised to 85, and the heating was continued for a while. Secondly, 20 parts of ion-exchanged water was added to install the steaming hall. In the apparatus, the oil bath is heated to 125. (: Distillation is started. At the time when the amount of distillation is 2 parts, the ion exchange water is added, and then the steaming is continued. Then, when the distillation is further distilled, (At the time of total distillation amount A 30 parts), the polymerization vessel was cooled to prepare 25 1374896 • A solution of NVP/HEA copolymer (colorless transparent, solid content 30.8%) was obtained. NVP/HEA copolymer in the obtained solution The K value was 34.0, the water insoluble content rate was 0.02%, the weight average molecular weight was 1,13,685, the number average molecular weight was 6,026, and the degree of dispersion was 1.65. (Example 7). In a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer 17 parts of ion-exchanged water and 3.3 parts of ethanol were added, and nitrogen gas was introduced into a nitrogen atmosphere while stirring. The polymerization vessel was heated in an oil bath to have an internal temperature of 80 ° C, and then mixed with N-vinylpyrrolidone ( NVP) 16.8 parts, 3 parts by weight of 2-ethyl benzoate (ΗΕΑ), 0.05 parts of 2-mercaptoethanol, 14.4 of ion-exchanged water, 6.2 parts of ethanol (Α7), mixed with dimethyl 0.21 part of base 2,2'-azobisisobutyrate ("V601" manufactured by Wako Pure Chemical Industries, Ltd.) and 4 parts of an initiator solution (Α7) of ethanol were successively dropped for 2 hours. Dissolving ruthenium acrylate via 2.6 parts of ion-exchanged water and 1,1 part of ethanol The ester solution (0.4) 0.42 parts of the monomer solution (Β7), after adding for 1 hour, φ the internal temperature was raised to 85 ° C ' and heating and stirring for 30 minutes. Then, the dimethyl group was dissolved in 0.4 parts of ethanol. · 2,2'-azobisisobutyrate ("V601" manufactured by Wako Pure Chemical Industries, Ltd.) 〇. 2 parts of the initiator solution (By), and then continue to heat the mixture for a minute. Second, join 2 parts of ion-exchanged water, a distillation apparatus was installed, and the oil bath was heated to uot to start distillation. At the time of the distillate amount of 2 伤, add 1 part of ion-exchanged water and continue to steam. Then, the polymerization vessel was cooled at a point where the residue was further distilled off (the total amount of the distillation was 30 parts) to obtain a solution of NVP/HEA copolymer (colorless transparent, solid content: 30.7%).

26 137489626 1374896

所製得之溶液中的NVP/HEA共聚物，κ值為28.6、水不溶分含有率0 〇1%、重量平均分子量為7686〇、數量平均分子量49837 '分散度丨.54。 (比較例1 ) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水20份，邊攪拌邊導入氮氣作成氮氣環境氣氛。將聚合容器以油浴加熱使内溫為95t：後，將混合有 N-乙稀基咬洛烷酮（NvP)16 8份、丙烯酸2羥基乙酯 (HEA)4.2份、離子交換水16 4份之單體溶液（Acl)、與混合溶解4,4，-偶氮雙-4-氰戊酸（日寶化學公司製rNC：25j ) 0.75伤、二乙醇胺〇 76份離子交換水丨丨1份之起始劑溶液（Ac 1) ’分別以2小時連續地滴下。再者，持續加熱攪拌丨時，製得NVp/HEA共聚物之溶液（無色透明、固體成分33.3%)。所製得之溶液中的NVP/HEA共聚物，κ值為29 7、 X不’合刀3有率0 57〇/〇、重量平均分子量為939㈠數量平均分子量4855 1、分散度194。 (比較例2) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水5〇份’錢拌邊導人減作成氮氣氣氛。將聚合容器以油浴加熱使内溫為贼後，將混合有氺乙土㈣:¾ _(NVP)33.6份、㊅稀酸2_經基乙醋（ΗΕΑ)7 9 離子交換水27.9份之單體溶液（Ac2)、與混合溶解二基2,2 -偶氮雙異丁酸g| (和光純藥公司製「】」）a」The NVP/HEA copolymer in the obtained solution had a K value of 28.6, a water insoluble content of 0 〇 1%, a weight average molecular weight of 7686 〇, and a number average molecular weight of 49837 'dispersion 丨.54. (Comparative Example 1) 20 parts of ion-exchanged water was placed in a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer, and nitrogen gas was introduced while stirring to prepare a nitrogen atmosphere. The polymerization vessel was heated in an oil bath to have an internal temperature of 95 t: after that, 16 parts of N-Ethyl L-alkanone (NvP), 4.2 parts of 2-hydroxyethyl acrylate (HEA), and ion-exchanged water 16 4 were mixed. A monomer solution (Acl), mixed with 4,4,-azobis-4-cyanovaleric acid (RNC:25j, manufactured by Ribao Chemical Co., Ltd.) 0.75 wound, diethanolamine oxime 76 parts ion exchanged water 丨丨1 The portion of the initiator solution (Ac 1)' was continuously dropped over 2 hours. Further, a solution of NVp/HEA copolymer (colorless transparent, solid content 33.3%) was obtained by continuously heating and stirring the crucible. The NVP/HEA copolymer in the obtained solution had a κ value of 297, an X-No knives 3 rate of 0 57 〇/〇, a weight average molecular weight of 939 (a), an average molecular weight of 4855, and a degree of dispersion of 194. (Comparative Example 2) In a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer, 5 parts of ion-exchanged water was added, and the mixture was reduced to a nitrogen atmosphere. After the polymerization vessel is heated in an oil bath to make the internal temperature a thief, the mixture is mixed with bismuth (4): 3⁄4 _ (NVP) 33.6 parts, and hexa-dibasic acid 2 _ base vinegar (ΗΕΑ) 7 9 ion exchange water 27.9 parts Monomer solution (Ac2), mixed with dibasic 2,2-azobisisobutyric acid g| ("Wako Pure Chemical Co., Ltd.")")

27 1374896 份、異丙醇4份、離子交換水4.4份之起始劑溶液（Ac2)，分別以1小時連續地滴下。接著，將於離子交換水9.6份中溶解有丙烯酸2·羥基乙酯（HEA)0.5份之單體溶液（Bc2)，以15分鐘加入。再者，持續加熱攪拌45分鐘，製得NVP/HEA 共聚物之溶液（無色透明、固體成分3 1 .〇% )。所製得之溶液中的NVP/HEA共聚物，K值為31.9、水不溶分含有率0.64%、重量平均分子量為1 10575、數量平均分子量53419、分散度2.07。 (比較例3 ) 於具備冷凝管、氮氣導入管線、溫度計之聚合容器中，加入離子交換水50份，邊攪拌邊導入氮氣作成氮氣氣氛。將聚合容器以油浴加熱使内溫為9(TC後，將混合有N-乙烯基°比略烧酮（NVP)33.6份、丙稀酸2-經基乙酯（HEA)7.9 份、離子交換水32.1份之單體溶液（Ac3)、與混合溶解有二曱基-2,2’-偶氮雙異丁酸酯（和光純藥公司製r ν6〇ι」） 1·26份、異丙醇2_4份、離子交換水2.6份之起始劑溶液 (Ac3) ’分別以1小時連續地滴下。接著，將於離子交換水 9.6份中溶解有丙烯酸2-羥基乙酯（ΗΕΑ)0·5份之單體溶液 (Bc3)，以15分鐘加入。再者，於持續加熱攪拌1〇5分鐘之間’將於離子交換水0.13份、異丙醇0.12份中溶解有二甲基-2,2’-偶氮雙異丁酸酯（和光純藥公司製「v6〇1」） 0.06份之起始劑溶液（Bc3)，分三次投入，製得共聚物之溶液（無色透明、固體成分3 1 .〇% )。所製得之溶液中的NVP/HEA共聚物，κ值為37 3、 28 1374896 水不溶分含有率1.03%、重量平均分子量為158628、數量平均分子量75975、分散度2.09。以上之結果示於表1。【表1】鏈轉移劑:量醇:量水不溶分含有率分散度 (質量％/單體） (質量％/溶劑） (%) 實施例1 次磷酸:0.9 - 0.09 1.99 實施例2 次磷酸:0.9 0.11 1.81 實施例3 次磷酸:0.9 - 0.08 1.82 實施例4 2-巯基乙醇:0.31 異丙醇:0〜3 0.00 1.57 實施例5 - 乙醇:50 0.04 1.62 實施例6 2-酼基乙醇:0.10 乙醇:16〜31 0.02 1.65 實施例7 2-酼基乙醇:0.24 乙醇：16〜31 0.01 1.54 比較例1 0.57 1.94 比較例2 - 0.64 2.07 比較例3 - 異丙醇:0〜3 1.03 2.09 本發明之乙烯基吡咯烷酮系共聚物，例如，可適用於能製得兼備耐水性與親水性之膜之硬化性樹脂組成物的原料聚合物等。【圖式簡單說明】無【主要元件符號說明】無. 2927 1374896 parts, 4 parts of isopropyl alcohol, and 4.4 parts of an initiator solution (Ac2) of ion-exchanged water were successively dropped for 1 hour. Next, a monomer solution (Bc2) of 0.5 part by weight of 2-hydroxyethyl acrylate (HEA) was dissolved in 9.6 parts of ion-exchanged water, and added thereto over 15 minutes. Further, stirring was continued for 45 minutes to obtain a solution of NVP/HEA copolymer (colorless transparent, solid content 31%). The NVP/HEA copolymer in the obtained solution had a K value of 31.9, a water-insoluble content of 0.64%, a weight average molecular weight of 1,10575, a number average molecular weight of 53419, and a degree of dispersion of 2.07. (Comparative Example 3) 50 parts of ion-exchanged water was added to a polymerization vessel equipped with a condenser, a nitrogen gas introduction line, and a thermometer, and nitrogen gas was introduced into a nitrogen atmosphere while stirring. The polymerization vessel was heated in an oil bath to have an internal temperature of 9 (TC, followed by mixing 33.6 parts of N-vinyl group with ketone (NVP), 7.9 parts of 2-ethyl thioacetate (HEA), ion 32.1 parts of the monomer solution (Ac3) was exchanged with water, and dimercapto-2,2'-azobisisobutyrate (r ν6〇ι, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved and dissolved in 1·26 parts. 2 to 4 parts of propanol and 2.6 parts of the initiator solution (Ac3) of ion-exchanged water were continuously dropped in 1 hour. Then, 2-hydroxyethyl acrylate (ΗΕΑ) was dissolved in 9.6 parts of ion-exchanged water. 5 parts of the monomer solution (Bc3) was added in 15 minutes. Further, during continuous heating and stirring for 1 to 5 minutes, '0.12 parts of ion-exchanged water and 0.12 parts of isopropanol were dissolved in dimethyl-2. , 2'-azobisisobutyrate ("V6〇1", manufactured by Wako Pure Chemical Industries, Ltd.) 0.06 parts of the initiator solution (Bc3), which was added in three portions to prepare a solution of the copolymer (colorless transparent, solid content) 3 1 .〇%). NVP/HEA copolymer in the prepared solution, kappa value 37 3, 28 1374896 water insoluble content rate 1.03%, weight average molecular weight 158628, number average molecule The amount is 75975 and the dispersion is 2.09. The above results are shown in Table 1. [Table 1] Chain transfer agent: Amount of alcohol: Water content, insoluble content, dispersion (% by mass/monomer) (% by mass/solvent) (%) Example 1 Hypophosphorous acid: 0.9 - 0.09 1.99 Example 2 Hypophosphorous acid: 0.9 0.11 1.81 Example 3 Phosphoric acid: 0.9 - 0.08 1.82 Example 4 2-mercaptoethanol: 0.31 Isopropanol: 0 to 3 0.00 1.57 Example 5 - Ethanol: 50 0.04 1.62 Example 6 2-Mercaptoethanol: 0.10 Ethanol: 16 to 31 0.02 1.65 Example 7 2-mercaptoethanol: 0.24 Ethanol: 16 to 31 0.01 1.54 Comparative Example 1 0.57 1.94 Comparative Example 2 - 0.64 2.07 Comparative Example 3 - Isopropanol: 0 to 3 1.03 2.09 The vinylpyrrolidone copolymer of the present invention can be suitably used, for example, as a base polymer capable of producing a curable resin composition having both a water resistance and a hydrophilic film. Etc. [Simple description of the diagram] No [Main component symbol description] None. 29

Claims

1374896 101年6月14日替換頁 \ 十、申請專利範圍： 1. 一種乙烯基吡咯烷酮系共聚物，其特徵在於，其來自N·乙烯基吡咯烷酮之構成單位（A)與來自含羥基之（曱基）丙烯酸酯之構成單位（B)以對於兩者合計量之比率來表示時，係含有該（A)50〜95質量％、該（B)50〜5質量％之比例，以菲肯齊爾法所測得之K值為12以上、且水不溶分為〇 5 質量％ (固體成分基準）以下。 2. —種乙烯基吼咯烷酮系共聚物，其特徵在於，其來 • 自N-乙烯基吡咯烷酮之構成單位（A)與來自含羥基之（甲基）丙烯酸酯之構成單位（B)以對於兩者合計量之比率來表示時，係含有該（A)50〜95質量％、該（B)50〜5質量％之比例，以菲肯齊爾法所測得之K值為12以上、水不溶分為〇 5質量％ (固體成分基準）以下、且分散度為丨8以下。 3. 如申請專利範圍第丨或2項之乙烯基吡咯烷酮系共水物，其中，來自Ν-乙烯基吡咯烷酮之構成單位（Α)與來自含羥基之（甲基）丙烯酸酯之構成單位（Β)，佔總構成單位中 • 之8〇質量％以上。 • 種乙烯基。比略烧酮系共聚物之製造方法，用以製造申請專利範a第1項之乙烯基料烧㈣共聚物，其特徵在於’N-乙烯基吼略烧嗣（a)與含經基之（甲基）丙烯酸醋⑻ 。以對於兩者合計量之比率來表示時，在含有該（a)5〇〜95質量 %忒（b)50〜5質量％比例之單體成分進行聚合時，係於對單體成分存在GW質量％以上之鏈轉移劑下進行聚合。 5.如申請專利範圍第4項之乙烯基吼略院酮系共聚物 30 101年6月14曰替換頁之製造方法，其中，該鏈轉移劑係使用巯基- 6· ~種乙烯基吡咯烷鲷系共聚物之製造方法用以製造申請專利範圍第i項之乙烯基料貌綱系共聚物，其特徵在於’N-乙烯基吡咯烷酮⑷與含羥基之(甲基)丙烯酸酯⑻ 。、十於兩者σ汁里之比率來表示時，在含有該（a)5〇〜％質量 =、該（b)50〜5 f量％比例之單體成分進行聚合時，係於含反數1〜5之醇1〇質量％ (對溶劑總量之比例）以上之溶劑中進行聚合。 7. 如申请專利範圍第4至6項中任一項之乙烯基吡咯燒酮系共聚物之製造方法，其中，N乙稀基d比洛烧酮⑷與含搜基之（甲基）丙稀酸酯（b)，係佔供聚合之單體成分中8〇質量％以上。 8. 如申請專利範圍第4或6項之乙烯基吡咯烷酮系共聚物之製造方法，其中，使用偶氮系聚合起始劑。十一、圖式：〇 311374896 Replacement page on June 14, 101. X. Patent application scope: 1. A vinylpyrrolidone-based copolymer characterized by a constituent unit (A) derived from N-vinylpyrrolidone and a hydroxyl group-containing (曱) When the constitutive unit (B) of the acrylate is expressed as a ratio of the total amount of the two, the ratio of 50% to 95% by mass of the (A) and 50% to 5% by mass of the (B) is included. The K value measured by the method is 12 or more, and the water insoluble is classified into 〇5 mass% (solid content basis) or less. 2. A vinyl pyrrolidone-based copolymer characterized by comprising: a constituent unit of N-vinylpyrrolidone (A) and a constituent unit derived from a hydroxyl group-containing (meth) acrylate (B) When expressed as a ratio of the total amount of the two, the ratio of 50% to 95% by mass of the (A) and 50% to 5% by mass of the (B) is included, and the K value measured by the Fiknijker method is 12 The above water insoluble is classified into 〇5 mass% (solid content basis) or less, and the degree of dispersion is 丨8 or less. 3. The vinylpyrrolidone-based hydrophile of claim 2 or 2, wherein the constituent unit (Ν) derived from Ν-vinylpyrrolidone and the constituent unit derived from the hydroxyl group-containing (meth) acrylate (Β) ), accounting for more than 8% by mass of the total constituent units. • Vinyl. A method for producing a ketone-based copolymer, which is used for producing a vinyl-fired (tetra) copolymer of the patent application, a first item, characterized in that 'N-vinyl fluorene (a) and a thiol-containing group (Meth)acrylic acid vinegar (8). When it is represented by the ratio of the total amount of the two, when the monomer component containing the ratio of (a) 5 〇 to 95% by mass 忒 (b) 50 to 5% by mass is polymerized, the GW is present for the monomer component. The polymerization is carried out under a chain transfer agent of a mass % or more. 5. The method for producing a vinyl ketone ketone copolymer according to claim 4 of the fourth aspect of the invention, wherein the chain transfer agent is a thiol-6-vinylpyrrolidine. A method for producing a lanthanide copolymer for producing a vinyl-based copolymer of the invention of claim i, characterized by 'N-vinylpyrrolidone (4) and a hydroxyl group-containing (meth) acrylate (8). When the ratio of the ratio of the two in the σ juice is expressed, when the monomer component containing the ratio of (a) 5 〇 to % by mass = (b) 50 to 5 f % is polymerized, The polymerization is carried out in a solvent of 1 to 5 times by mass of the alcohol (1% by mass of the total amount of the solvent). 7. The method for producing a vinylpyrrolidone-based copolymer according to any one of claims 4 to 6, wherein the N-ethyl d-pyrrolidone (4) and the (meth)-containing C-containing The dilute acid ester (b) is 8% by mass or more of the monomer component to be polymerized. 8. The method for producing a vinylpyrrolidone-based copolymer according to claim 4 or 6, wherein an azo-based polymerization initiator is used. XI. Schema: 〇 31