1283690 玖、發明說明： (一） 發明所屬之技術領域 本發明關於紫外線吸收性樹脂水乳液及含彼之耐光性 和耐藥品性優良的水乳液樹脂組成物。 (二） 先前技術 近年來，因爲考慮環境問題，例如，汽車、電氣、電 子、建築等之廣泛產業領域都在推動使用之合成樹脂乳液 的水乳化。此等之水乳液樹脂（樹脂含於水乳液中，亦稱 爲水系樹脂）若暴露於日光等之含紫外線的光線下時，會 因爲紫外線劣化或變色，有分子量降低及強度降低之缺 點。 爲提高由水乳液樹脂對於紫外線之耐久性（耐光性）， 通常添加紫外線吸收劑。該紫外線吸收劑例如有已知的2-(2’-羥基-5’-甲基苯基）苯並三唑、5·氯-2-(2’-羥基-3’，5’-二-第三丁基苯基）苯並三唑等之苯並三唑類或2,4-二羥基 二苯甲酮、2-羥基-4-辛氧基二苯甲酮等之二苯甲酮類等。 然而，這些習知紫外線吸收劑由於是低分子量之低沸 點化合物，故將這些添加於水系樹脂中時會產生各種不良 情況。例如大量添加紫外線吸收劑時，會引起相分離，使 樹脂透明性及機械強度降低。因此，使紫外線吸收劑之添 加量在極少量，然而這樣子卻無法將水乳液樹脂之耐光性 提高至令人滿意的程度。而且，紫外線吸收劑於水乳液樹 脂之塗覆、成膜時’會發生揮散或熱分解，或滲出塗膜表 面，故經過長時間後仍無法賦予樹脂具有安定的耐光性。 1283690 爲解決上述缺點，嘗試使上述紫外線吸收劑中具有乙 烯基等的聚合性雙鍵之基，使該物聚合以便高分子量化， 改善與樹脂之相溶性，而防止紫外線吸收劑之揮散、熱分 解、滲出等情形（日本特開昭6 0 - 3 8 4 1 1號公報、特開昭 62-181360號公報、特開平3-281685號公報等）。 然而’此等紫外線吸收性聚合物亦有下述之缺點，而 尙有改善的餘地。換言之，此等紫外線吸收性聚合物由於 不具親水性，故於配合水乳液樹脂時無法安定且均勻地混 合。而且，視水乳液樹脂之種類而定，相溶性不充分，且 樹脂之機械強度降低。該傾向尤其在熱塑性樹脂由聚烯 烴、聚偏二氯乙烯水乳液等得到時係特別顯著的。此外， 就長期耐光性而固亦尙未令人滿足的。 ’ 另外，由聚偏二氯乙烯水乳液、聚酯水乳液、聚胺甲 酸酯樹脂水乳液等所得到的樹脂係有極高的機械強度，而 可廣泛地使用於各種塗覆用材料或黏合用材料，惟聚偏二 氯乙烯、聚碳酸酯、聚酯及聚胺甲酸酯樹脂會有複鹼成分 所分解，而有降低其機械強度之缺點，因此希望改善耐驗 性或耐溶劑性等之耐藥品性。 本發明之目的爲提供紫外線吸收性樹脂水乳液及使用 彼之乳液樹脂組成物，其與廣範圍的合成樹脂之相溶性優 良，賦予優良的耐光性而不會損害合成樹脂的優良特性， 紫外線吸收性樹脂滲出由乳液所得到的塗膜表面之現象 少’再者能將優良的耐鹼性和耐溶劑性給予缺乏耐鹼性和 耐溶劑性的合成樹脂。 1283690 (三）發明內容 本案發明人經過專心致力地再三硏究，發現以已知的 紫外線吸收劑當作原料，對其作胺甲酸酯化反應以得到紫 外線吸收性樹脂的水系乳液，使用此水系乳液則能解決上 述問題，而終於完成本發明。 即’本發明之第1目的係提供一種紫外線吸收性樹脂 之水乳液’其之獲得係藉由使含有紫外線吸收基之多元醇 成分（A)、任意可添加之多元醇（B)、烷基或芳基二烷醇胺 化合物（C)以及有機聚異氰酸脂（D)在有機溶劑（£)中進行胺 甲酸酯化反應’再經沸點低於l〇〇t：的有機溶劑（F)所稀釋 而得到樹脂溶液，用中和劑（G)將其中和後，藉分散於水 中而獲得。 本發明之第2目的係提供如本發明申請專利範圍第i 項之紫外線吸收性樹脂之水乳液，其中該含有紫外線吸收 基之多元醇成分（A)係爲下式所表示的化合物。[Technical Field] The present invention relates to an ultraviolet emulsion resin aqueous emulsion and an aqueous emulsion resin composition excellent in light resistance and chemical resistance. (II) Prior Art In recent years, water emulsification of synthetic resin emulsions has been promoted in consideration of environmental issues, for example, in a wide range of industries such as automobiles, electrics, electronics, and construction. When such an aqueous emulsion resin (a resin is contained in an aqueous emulsion, also referred to as a water-based resin), when exposed to ultraviolet light such as sunlight, there is a disadvantage that the molecular weight is lowered and the strength is lowered due to deterioration or discoloration of ultraviolet rays. In order to improve the durability (light resistance) of the aqueous emulsion resin against ultraviolet rays, an ultraviolet absorber is usually added. The ultraviolet absorber is, for example, known 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 5·chloro-2-(2'-hydroxy-3', 5'-di- Benzotriazoles such as tributylphenyl)benzotriazole or benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone Wait. However, since these conventional ultraviolet absorbers are low-molecular-weight low-boiling compounds, various disadvantages occur when these are added to aqueous resins. For example, when a large amount of the ultraviolet absorber is added, phase separation is caused, and the transparency and mechanical strength of the resin are lowered. Therefore, the amount of the ultraviolet absorber added is extremely small, but in this case, the light resistance of the aqueous emulsion resin cannot be improved to a satisfactory level. Further, when the ultraviolet absorber is applied to the aqueous emulsion resin and formed into a film, it may be volatilized or thermally decomposed or bleed out of the surface of the coating film, so that the resin cannot be imparted with stable light resistance after a long period of time. 1283690 In order to solve the above-mentioned drawbacks, it is attempted to have a polymerizable double bond group such as a vinyl group in the above ultraviolet absorber, to polymerize the material for high molecular weight, to improve compatibility with a resin, and to prevent volatilization and heat of the ultraviolet absorber. In the case of the decomposition, the exudation, and the like, etc. (Japanese Unexamined-Japanese-Patent No. Publication No. JP-A------------ However, such ultraviolet absorbing polymers also have the following disadvantages, and there is room for improvement. In other words, since these ultraviolet absorbing polymers are not hydrophilic, they cannot be stably and uniformly mixed when the aqueous emulsion resin is blended. Further, depending on the type of the aqueous emulsion resin, the compatibility is insufficient and the mechanical strength of the resin is lowered. This tendency is particularly remarkable when the thermoplastic resin is obtained from a polyene olefin, a polyvinylidene chloride aqueous emulsion or the like. In addition, it is unsatisfactory for long-term lightfastness. In addition, the resin obtained from a polyvinylidene chloride aqueous emulsion, a polyester aqueous emulsion, a polyurethane aqueous emulsion or the like has extremely high mechanical strength and can be widely used for various coating materials or Adhesive materials, but polyvinylidene chloride, polycarbonate, polyester and polyurethane resin have decomposition of the alkali component, but have the disadvantage of reducing the mechanical strength, so it is desired to improve the testability or solvent resistance. Chemical resistance to sex. An object of the present invention is to provide an ultraviolet emulsion resin aqueous emulsion and an emulsion resin composition using the same, which is excellent in compatibility with a wide range of synthetic resins, imparts excellent light resistance without impairing the excellent properties of the synthetic resin, and ultraviolet absorption. The resin bleeds out from the surface of the coating film obtained by the emulsion. In addition, excellent alkali resistance and solvent resistance can be imparted to the synthetic resin lacking alkali resistance and solvent resistance. 1283690 (III) SUMMARY OF THE INVENTION The inventors of the present invention have repeatedly studied and found that an aqueous emulsion of a UV-absorbing resin is obtained by using a known ultraviolet absorber as a raw material to obtain a urethane reaction. The aqueous emulsion can solve the above problems, and finally the present invention has been completed. That is, the first object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin obtained by using a polyol component (A) containing an ultraviolet absorbing group, any optional polyol (B), and an alkyl group. Or an aryl dialkanolamine compound (C) and an organic polyisocyanate (D) are subjected to a urethanization reaction in an organic solvent (£) and then passed through an organic solvent having a boiling point lower than 1 〇〇t: F) A resin solution is obtained by dilution, neutralized with a neutralizing agent (G), and obtained by dispersing in water. A second aspect of the present invention provides an aqueous emulsion of an ultraviolet absorbing resin according to the invention of claim 1, wherein the ultraviolet absorbing group-containing polyol component (A) is a compound represented by the following formula.
本發明之第3目的係提供如本發明申請專利範圍第1 項之糸外線吸收性樹脂之水乳液’其中在去除1〜1 0 0 %的 1283690 該有機溶劑（E)後，用有機溶劑（F)稀釋而獲得。 本發明之第4目的係提供如本發明申請專利範圍第2 項之紫外線吸收性樹脂之水乳液，其中在去除1〜丨〇〇%的 該有機溶劑（E)後，用有機溶劑（F)稀釋而獲得。 本發明之第5目的係提供如本發明申請專利範圍第i 項之紫外線吸收性樹脂之水乳液，其中去餘有機溶劑（F) 而獲得。 本發明之第6目的係提供如本發明申請專利範圍第2 項之紫外線吸收性樹脂之水乳液，其中去除有機溶劑（F) 而獲得。 本發明之第7目的係提供如本發明申請專利範圍第3 項之紫外線吸收性樹脂之水乳液，其中去除有機溶劑（F) 而獲得。 本發明之第8目的係提供如本發明申請專利範圍第4 項之紫外線吸收性樹脂之水乳液，其中去除有機溶劑（F) 而獲得。 本發明之第9目的.係提供如本發明申請專利範圍第1 至8項中任一項之紫外線吸收性樹脂之水乳液，其中在紫 外線吸收性樹脂中含有1 0重量％以上的該含有紫外線吸 收基之多元醇成分（A)。 本發明之第1 〇目的係提供一種水乳液樹脂組成物， 其由如本發明申請專利範圍第1至8項中任一項之紫外線 吸收性樹脂之水乳液（I)與其它樹脂之水乳液（II)所構成。 本發明之第 U目的係提供一種水乳液樹脂組成物， 1283690 其由如本發明申請專利範圍第9項之紫外線吸收性樹脂之 水乳液（I)與其它樹脂之水乳液（II)所構成。 (四）實施方式 1明的最佳實施形熊 以下詳細說明本發明。 [水乳液] 本發明的紫外線吸收性樹脂之水乳液（I)的獲得係藉由 含有紫外線吸收基之多元醇成分（A)、任意可添加之多元 醇（B)、烷基或芳基二烷醇胺化合物（C)以及有機聚異氰酸 脂（D)在有機溶劑（E)中進行胺甲酸酯化反應，再經沸點低 於1 〇〇°C的有機溶劑（F)所稀釋而得到樹脂溶液，用中和劑 (G)將其中和後，藉分散於水中而獲得。 [含有紫外線吸收基之多元醇成分（A)] 上述含有紫外線吸收基之多元醇成分（A)較佳係爲含有 三唑環的多元醇，例如上述式（1)所示的1，1_雙[3_(2H-苯 並三唑_2_基）-心羥基苯乙醇]甲烷。多元醇成分（A)較佳爲 使用以式（1)化合物當作有效成分的紫外線吸攸劑，可以 使用合成物或市售品。 而且，紫外線吸收性樹脂中較佳爲含有1 〇重量％以上 的多元醇成分（A)，更佳爲40〜70重量％。 [多元醇（B)] 上述多元醇（B)係爲可任意添加的成分。該多元醇（B) 例如爲聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚（甲 基）丙烯基多元醇、聚烷基多元醇及聚伸烷基多元醇等。 -10 - 1283690 這些多元醇可被單獨使用或可2種以上倂用。 相對於100重量份的成分（A)，多元醇（B)的添加量係 0〜200重量份，較好〇〜100重量份。 [烷基或芳基二烷醇胺化合物（C)] 上述烷基或芳基二烷醇胺化合物（C)例如爲以N-甲基 二乙醇胺、N-乙基二乙醇胺、N-苯基二乙醇胺或N-乙基 二乙醇胺等當作起始劑的內酯加成物。 內酯例如爲ε -己內酯、三甲基-ε -己內酯、單甲基-ε -己內酯、r -丁內酯、5 -戊內酯等。相對於1莫耳的上述 起始劑，內酯的加成莫耳數係1〜10莫耳，較佳1〜6莫耳。 成分（C)就相對於100重量份成分（A)而言係4〜25重量 份，較佳8〜1 5重量份。 [有機聚異氰酸脂（D)] 上述有機聚異氰酸酯（D)例如爲2,4-甲苯二異氰酸酯、 2，6-甲苯二異氰酸酯、2,2’·二苯基甲烷二異氰酸酯、2,4，-二苯基甲烷二異氰酸酯4，4，-二苯基甲烷二異氰酸酯、二 苯基土甲基甲烷二異氰酸酯…、二苯甲基二異氰酸酯、伸萘 基二異氰酸酯、伸苯基二異氰酸酯、伸二甲苯基二異氰酸 酯、四甲基伸二甲苯基二異氰酸酯等之芳香族二異氰酸酯 •’四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、賴胺酸二 異氰酸酯、2-甲基戊烷-i，5_二異氰酸酯、3_甲基戊烷-U — 二異氰酸酯、2,2,4-三甲基六亞甲基-i，6-二異氰酸酯等之 脂肪族二異氰酸酯；異佛爾酮二異氰酸酯、環己烷二異氰 酸酯、加氫伸二甲苯基二異氰酸酯、加氫二苯基甲烷二異 -11 - 1283690 氰酸酯、加氫三甲基伸二甲苯基二異氰酸酯等之脂環族二 異氰酸酯。A third object of the present invention is to provide an aqueous emulsion of an external absorbent resin according to the first aspect of the present invention, wherein an organic solvent (after removing 1 to 100% of 1,283,690 of the organic solvent (E) is used. F) Obtained by dilution. A fourth object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin according to the second aspect of the present invention, wherein an organic solvent (F) is used after removing 1 to 丨〇〇% of the organic solvent (E). Obtained by dilution. A fifth object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin according to the invention of claim i, wherein the organic solvent (F) is obtained. A sixth object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin according to the second aspect of the present invention, which is obtained by removing an organic solvent (F). A seventh object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin according to the third aspect of the present invention, which is obtained by removing an organic solvent (F). An eighth object of the present invention is to provide an aqueous emulsion of an ultraviolet absorbing resin according to item 4 of the present invention, which is obtained by removing an organic solvent (F). The ninth aspect of the present invention provides an aqueous emulsion of an ultraviolet absorbing resin according to any one of the first to eighth aspects of the present invention, wherein the ultraviolet absorbing resin contains 10% by weight or more of the ultraviolet ray. The polyol component (A) of the absorption group. A first aspect of the present invention provides an aqueous emulsion resin composition comprising an aqueous emulsion (I) of an ultraviolet absorbing resin according to any one of claims 1 to 8 of the present invention and an aqueous emulsion of another resin. (II) constitutes. A second object of the present invention is to provide an aqueous emulsion resin composition, which is composed of an aqueous emulsion (I) of an ultraviolet absorbing resin according to claim 9 of the present invention and an aqueous emulsion (II) of another resin. (IV) Embodiment 1 The best embodiment of the present invention The present invention will be described in detail below. [Aqueous Emulsion] The aqueous emulsion (I) of the ultraviolet absorbing resin of the present invention is obtained by a polyol component (A) containing an ultraviolet absorbing group, any optional polyol (B), an alkyl group or an aryl group The alkanolamine compound (C) and the organic polyisocyanate (D) are subjected to a urethanization reaction in an organic solvent (E) and then diluted with an organic solvent (F) having a boiling point of less than 1 〇〇 ° C. The resin solution was obtained, and after neutralizing with a neutralizing agent (G), it was obtained by dispersing in water. [Polyol Absorbing Group-Containing Polyol Component (A)] The above-mentioned ultraviolet absorbing group-containing polyol component (A) is preferably a triazole ring-containing polyol, for example, 1,1_ represented by the above formula (1). Bis[3_(2H-benzotriazol-2-yl)-cardohydroxyphenylethanol]methane. The polyol component (A) is preferably an ultraviolet absorbing agent using the compound of the formula (1) as an active ingredient, and a synthetic or commercial product can be used. Further, the ultraviolet absorbing resin preferably contains 1 〇 by weight or more of the polyol component (A), more preferably 40 to 70% by weight. [Polyol (B)] The above polyol (B) is a component which can be arbitrarily added. The polyol (B) is, for example, a polyester polyol, a polyether polyol, a polycarbonate polyol, a poly(meth)acryl polyol, a polyalkyl polyol, a polyalkylene polyol, or the like. -10 - 1283690 These polyols may be used singly or in combination of two or more. The amount of the polyol (B) to be added is 0 to 200 parts by weight, preferably 〇 to 100 parts by weight, per 100 parts by weight of the component (A). [Alkyl or aryl dialkanolamine compound (C)] The above alkyl or aryl dialkanolamine compound (C) is, for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyl A lactone adduct as a starter such as diethanolamine or N-ethyldiethanolamine. The lactone is, for example, ε-caprolactone, trimethyl-ε-caprolactone, monomethyl-ε-caprolactone, r-butyrolactone, 5-valerolactone or the like. The lactone addition molar number is from 1 to 10 moles, preferably from 1 to 6 moles, per mole of the above initiator. The component (C) is 4 to 25 parts by weight, preferably 8 to 15 parts by weight, per 100 parts by weight of the component (A). [Organic Polyisocyanate (D)] The above organic polyisocyanate (D) is, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2, 4,-diphenylmethane diisocyanate 4,4,-diphenylmethane diisocyanate, diphenyl chloromethane diisocyanate..., benzhydryl diisocyanate, stilbene diisocyanate, phenyl diisocyanate , an aromatic diisocyanate such as xylylene diisocyanate or tetramethylxylylene diisocyanate, 'tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane- Aliphatic diisocyanate of i,5-diisocyanate, 3-methylpentane-U-diisocyanate, 2,2,4-trimethylhexamethylene-i,6-diisocyanate; isophorone Alicyclic diisocyanate of diisocyanate, cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diiso-11 - 1283690 cyanate, hydrogenated trimethyl xylylene diisocyanate, etc. .
It匕等之有機聚異氰酸酯可單獨使用或2種以上倂用。 另外’此等之加成改質體、羰基二醯亞胺改質體、脲基甲 酸酯質體、縮二脤質體、脲二酮質體、脲亞胺質體、異氰 酸酯質體等之質體。The organic polyisocyanate of It匕 or the like may be used singly or in combination of two or more. In addition, such addition modifiers, carbonyl diquinone imines, allophanate bodies, diterpenoids, uretdiones, ureaimines, isocyanates, etc. The plastid.
It匕等之聚異氰酸酯就考慮耐光性而言以六亞甲基二異 氰酸酯、異佛爾酮二異氰酸酯、加氫伸二甲苯基二異氰酸 酯、加氫二苯基甲烷二異氰酸酯較佳。 有機聚異氰酸脂（D)之使用量方面，就相對於成分（A) 和成分（B)和成分（C)的活性氫之合計量而圍，成分（D)的異 氰酸脂係0.7〜1.4當量倍，較佳0.8〜1.2當量倍。 [有*機溶劑（E)及有機溶劑（F)] 上述反應中所使用的有機溶劑（E)例如爲甲醯胺、Ν，Ν· 二甲基甲醯胺、二甲亞碾、二甲碾、環丁楓、2,4-二甲基 環丁碾、Ν-甲基吡咯啶酮等。這些有機溶劑（Ε)可單獨使 用或2種以上倂用。 有機溶劑（Ε)的使用量就相對於1〇〇重量份所得到的紫 外線吸收性樹脂（不揮發份）而言係0.4〜2倍，較佳0.7〜1 倍。 上述稀釋用有機溶劑（F)例如爲丙酮、丁酮、四氫呋喃 等。這些有機溶劑（F)可單獨使用或2種以上倂用。 有機溶劑（F)的使用量就相對於1 〇〇重量份所得到的紫 外線吸收性樹脂（不揮發份）而言係〇·7〜2.3倍’較佳0.9〜1.5 -12- 1283690 倍。 [中和劑（G)] 上述中和劑（G)例如爲鹽酸、硫酸、硝酸等的無機酸、 甲酸、醋酸、丙酸、丁酸等之有機酸、氯甲烷、溴甲烷、 二甲基硫酸、二乙基硫酸、氯苯、對硝基苯甲基氯、苯甲 基溴、氯乙醇、溴乙醇、環氧氯丙烷、溴丁烷等的四級化 劑。這些中和劑可單獨或2種以上倂用。 上述成分（A)、成分（B)、成分（C)及有機聚異氰酸酯（D) 的胺甲酸酯化反應係在有機溶劑（E)中，例如在反應溫度6 5 °C及反應時間1 2小時的條件下進行。 所得到之含有反應生成物的胺甲酸酯樹脂溶液，若必 要時可藉由例如蒸發器、真空蒸餾等來去除1〜100%的有 機溶劑（E)後，更用沸點低於l〇〇°C的有機溶劑（F)來稀釋 而得到樹脂溶液，用上述中和劑（G)來中和，必要時用十 二烷基苯磺酸，聚環氧乙烷壬基苯醚等之乳化劑使其分散 於水中，以成爲紫外線吸收性樹脂之水乳液（I)。 如此.，藉由有機溶劑（F)來稀釋，在水分散時可容易有 分散安定性。 紫外線吸收性樹脂之水乳液（I)可使用不揮發份濃度 5〜60重量％者。 必要時可去除有機溶劑（F)以成爲不含有機溶劑的水乳 液’而且可經其使樹脂乾燥而得到紫外線吸收性樹脂。 因此，本發明亦揭示一種由成分（A)、成分（C)、任意 成分（B)及有機聚異氰酸酯（D)之胺甲酸酯化反應而得到的 -13 - 1283690 紫外線吸收性樹脂。 於本發明中，爲了使上述胺甲酸酯化之樹脂具有水分 散能力，將第四級銨鹽導入分子中當做親水基，必要時， 亦可導入羧酸鹽、磺酸鹽、磷酸鹽及膦酸鹽等陰離子性極 性基、第四級銨鹽以外之陽離子性極性基、醚基等之非離 子性極性基。 [水乳液樹脂組成物] 本發明的水乳液樹脂組成物係由上述紫外線吸收性樹 脂之水乳液⑴與後述的其它樹脂之水乳液（II)所構成。 (I)與（II)的配合比並沒有特別的限制，而可由寬廣的 範圍中適當地選出，但通常（I) : (II)的重量比（不揮發份換 算）係 20 〜0.005 : 80 〜99.995，較佳 1 0〜0 · 1 : 9 0〜9 9 · 9 (兩者 合計成爲1 〇 〇)。 [其它樹脂之水乳液（II)] 上述其它樹脂之水乳液（II)並沒有特別的限制，可廣爲 使用習知物，惟就考慮上述紫外線吸收性樹脂之水乳液（I) 的容易添加性時，以使用熱塑性樹脂之水乳液較佳。 上述熱塑性樹脂例如爲聚氯乙烯、聚偏二氯乙烯、聚 烯烴、聚碳酸酯、聚苯乙烯、（甲基）丙烯酸樹脂、聚醯胺 、聚酯、丙烯腈-丁二烯-苯乙烯（ABS)樹脂、（I)所使用者 以外的聚胺甲酸酯樹脂、氯乙烯-偏二氯乙烯-丙烯腈共聚 物、丙烯腈-苯乙烯（AS)樹脂、醋酸乙烯酯樹脂、聚苯醚 、聚碾、聚醚碾、聚醚醚酮、液晶塑膠等。其中例如以使 用聚氯乙烯、聚偏二氯乙烯、聚烯烴、聚碳酸酯、聚苯乙 -14- 1283690 烯、（甲基）丙烯酸樹脂、聚醯胺、聚酯、ABS樹脂、聚胺 甲酸酯樹脂等較佳。另外，於此等之中以使用聚氯乙烯、 聚偏二氯乙烯、聚碳酸酯、聚酯、聚胺甲酸酯樹脂等之缺 乏耐鹼性的熱塑性樹脂或聚醯胺等之缺乏耐溶劑性的熱塑 性樹脂爲特佳。 本發明中可單獨使用或混合2種以上使用該些其它樹 脂之水乳液。 在本發明之水乳液樹脂組成物或上述紫外線吸收性樹 脂之水乳液（I)中，視需要可配合至少一種抗氧化劑、光安 定劑、加工安定劑、抗老化劑、相溶化劑等之習知添加劑 〇 抗氧化劑例如爲1，6-己二醇-雙[3-(3，5-二-第三丁基- 4-羥基苯基）丙酸酯]、3,5-二-第三丁基-4-羥基苯甲基磷酸二 乙酯等之受阻酚系抗氧化劑、二月桂基-3，3，-二硫二丙酸 酯等之有機硫系抗氧化劑、三烷基苯基磷酸酯等磷系抗氧 化劑等。 光安定劑例如爲雙<2,2,6,6-四甲基-4-吡喃基）癸酸醋等 之受阻胺系光安定劑、二丁基二硫化胺基甲酸鎳等之鎳鹽 系光安定劑等。 加工安定劑例如爲參（2，4-二-第三丁基苯基）磷酸醋等 之磷系加工安定劑等。 抗老化劑例如爲1，1-雙（4-羥基苯基）環己烯、N，N，-二 苯基-對苯二胺等。 此等添加劑之配合量並沒有特別的限制，通常對水乳 -15 - 1283690 液樹脂組成物或上述紫外線吸收性樹脂之水乳液（I)的不揮 發份樹脂而言較宜使用0.0 1〜20重量％。 本發明之水乳液樹脂組成物可使用於使用樹脂的水乳 液之全部用途，特別是日光或含紫外線之光所曝曬的可能 用途。具體例子爲玻璃代用品和其表面之塗覆材、住家、 . 設施、輸送機器等之玻璃窗、採光玻璃及光源保護玻璃用 · 塗覆材、住家、設施、輸送機器等之內外裝材及內外裝用 塗料、螢光燈、水銀燈等產生紫外線之光源用零件、精密 0 機器、電子電器機器用品零件、各種顯示器所產生的電磁 波等之遮蔽用材、食品、化學品、藥品等之容器或包裝材 、農工業用片或薄膜材、印刷物、染色物、染料顏料等之 防退色劑、防日曬之乳液、/洗髮精、潤濕精、整髮料等之 化妝品成分、運動服、襪子、帽子等之衣料用纖維製品及 纖維、窗簾、毛毯、壁紙等之家庭用內裝品、塑膠鏡片、 隱形眼鏡、義眼等醫療用器具、光學過濾器、三菱鏡、鏡 、照片材料等之光學用品、膠帶、油墨等之文房用具、標 q 示板、標示器等與其表面塗覆材等。 .......„ 實施^ 於下述中藉由實施例來具體地說明本發明，惟本發明 不受此等所限制。 而且，若沒有特別限定時，％和份係表示重量％和重量 份。 (實施例1) 於具有冷卻管、氮氣導入管、滴液下漏斗、溫度計及 -16- 1283690 攪拌器之玻璃製燒瓶內，加入240重量份N，N-二甲基甲 醯胺（DMF)和136.4重量份1，1-雙[3-(2H-苯並三唑-2-基）-4-羥基苯乙醇]甲烷（商品名稱「MB EP」，大塚化學（股）製）， 於80°C溶解。接著於氮氣氣氛下邊攪拌邊滴下80.7重量 份異佛爾酮二異氰酸酯（IPDI)，進行2小時的反應。然後， 滴下22.9重量份N-甲基二乙醇胺，繼續4小時的反應。The polyisocyanate of It匕 or the like is preferably hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate or hydrogenated diphenylmethane diisocyanate in view of light resistance. The amount of the organic polyisocyanate (D) used is in the range of the total amount of active hydrogen of the component (A) and the component (B) and the component (C), and the isocyanate of the component (D) 0.7 to 1.4 equivalent times, preferably 0.8 to 1.2 equivalent times. [The organic solvent (E) and the organic solvent (F)] The organic solvent (E) used in the above reaction is, for example, formamide, hydrazine, hydrazine dimethylformamide, dimethyl amide, dimethyl Milled, ring Dingfeng, 2,4-dimethylcyclobutyl milling, Ν-methylpyrrolidone and the like. These organic solvents (Ε) may be used singly or in combination of two or more. The amount of the organic solvent (Ε) used is 0.4 to 2 times, preferably 0.7 to 1 times, based on 1 part by weight of the ultraviolet ray absorbing resin (nonvolatile matter) obtained. The organic solvent (F) for dilution is, for example, acetone, methyl ethyl ketone or tetrahydrofuran. These organic solvents (F) may be used singly or in combination of two or more. The amount of the organic solvent (F) to be used is 7 to 2.3 times, preferably 0.9 to 1.5 to 12,836,590 times, relative to the ultraviolet absorbent resin (nonvolatile matter) obtained per part by weight. [Neutralizer (G)] The neutralizing agent (G) is, for example, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, an organic acid such as formic acid, acetic acid, propionic acid or butyric acid, methyl chloride, methyl bromide or dimethyl sulfate. A quaternizing agent such as diethylsulfuric acid, chlorobenzene, p-nitrobenzyl chloride, benzyl bromide, chlorohydrin, bromoethanol, epichlorohydrin or bromobutane. These neutralizing agents may be used alone or in combination of two or more. The urethanization reaction of the above component (A), component (B), component (C) and organic polyisocyanate (D) is carried out in an organic solvent (E), for example, at a reaction temperature of 65 ° C and a reaction time of 1 It was carried out under 2 hours. The obtained urethane resin solution containing the reaction product can be removed by using, for example, an evaporator, vacuum distillation or the like to remove 1 to 100% of the organic solvent (E), and further has a boiling point of less than 10 Å. The organic solvent (F) of °C is diluted to obtain a resin solution, which is neutralized with the above neutralizing agent (G), and if necessary, emulsified with dodecylbenzenesulfonic acid, polyethylene oxide nonylphenyl ether or the like. The agent is dispersed in water to become an aqueous emulsion (I) of the ultraviolet absorbing resin. Thus, by the organic solvent (F), it is easy to have dispersion stability when the water is dispersed. The aqueous emulsion (I) of the ultraviolet absorbing resin can be used in a concentration of 5 to 60% by weight of the nonvolatile matter. The organic solvent (F) can be removed as necessary to become an aqueous emulsion containing no organic solvent, and the resin can be dried to obtain an ultraviolet absorbing resin. Accordingly, the present invention also discloses a -13 - 1383690 ultraviolet absorbing resin obtained by the urethanization reaction of the component (A), the component (C), the optional component (B) and the organic polyisocyanate (D). In the present invention, in order to impart water dispersibility to the above urethane-modified resin, a fourth-order ammonium salt is introduced into the molecule as a hydrophilic group, and if necessary, a carboxylate, a sulfonate, a phosphate, and the like may be introduced. a nonionic polar group such as an anionic polar group such as a phosphonate or a cationic polar group other than the fourth-order ammonium salt or an ether group. [Aqueous Emulsion Resin Composition] The aqueous emulsion resin composition of the present invention comprises an aqueous emulsion (1) of the above ultraviolet absorbing resin and an aqueous emulsion (II) of another resin to be described later. The compounding ratio of (I) to (II) is not particularly limited, and may be appropriately selected from a wide range, but usually (I): (II) by weight ratio (non-volatile conversion) is 20 to 0.005 : 80 ~99.995, preferably 1 0~0 · 1 : 9 0~9 9 · 9 (the two become 1 合 in total). [Aqueous emulsion (II) of other resin] The aqueous emulsion (II) of the above other resin is not particularly limited, and a conventional one can be widely used, but the easy addition of the aqueous emulsion (I) of the above ultraviolet absorbent resin is considered. In the case of sex, it is preferred to use an aqueous emulsion of a thermoplastic resin. The above thermoplastic resin is, for example, polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene, (meth)acrylic resin, polyamine, polyester, acrylonitrile-butadiene-styrene ( ABS) resin, polyurethane resin other than the user of (I), vinyl chloride-vinylidene chloride-acrylonitrile copolymer, acrylonitrile-styrene (AS) resin, vinyl acetate resin, polyphenylene ether , poly milling, polyether milling, polyether ether ketone, liquid crystal plastic and so on. Among them, for example, polyvinyl chloride, polyvinylidene chloride, polyolefin, polycarbonate, polystyrene-14-1283690 olefin, (meth)acrylic resin, polyamide, polyester, ABS resin, polyamine An acid ester resin or the like is preferred. Further, among these, a lack of alkali-resistant thermoplastic resin such as polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyester, or polyurethane resin, or a lack of solvent resistance such as polyamide or the like is used. Sexual thermoplastic resins are particularly preferred. In the present invention, two or more kinds of aqueous emulsions using these other resins may be used alone or in combination. In the aqueous emulsion resin composition of the present invention or the aqueous emulsion (I) of the above ultraviolet absorbing resin, if necessary, at least one of an antioxidant, a light stabilizer, a processing stabilizer, an anti-aging agent, a compatibilizing agent, etc. may be blended. The additive antimony antioxidant is, for example, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-third A hindered phenol-based antioxidant such as butyl-4-hydroxybenzylphosphonate or an organic sulfur-based antioxidant such as dilauryl-3,3,-dithiodipropionate or a trialkylphenylphosphoric acid Phosphorus-based antioxidants such as esters. The photostabilizer is, for example, a hindered amine light stabilizer such as bis(2,2,6,6-tetramethyl-4-pyranyl) phthalic acid vinegar or the like, or nickel such as nickel dibutyl disulfide Salt light stabilizer and the like. The processing stabilizer is, for example, a phosphorus-based processing stabilizer such as ginseng (2,4-di-t-butylphenyl)phosphoric acid or the like. The anti-aging agent is, for example, 1,1-bis(4-hydroxyphenyl)cyclohexene, N,N,-diphenyl-p-phenylenediamine or the like. The amount of the additives is not particularly limited, and it is usually preferably used for the non-volatile resin of the water emulsion -15 - 1283690 liquid resin composition or the above aqueous emulsion (I) of the ultraviolet absorbing resin. weight%. The aqueous emulsion resin composition of the present invention can be used for all uses of aqueous emulsions using resins, particularly sunlight or ultraviolet light. Specific examples are glass substitutes and coated materials on the surface, homes, glass windows for facilities, conveyors, etc., interior and exterior materials for lighting glass and light source protective glass, coated materials, homes, facilities, conveyors, etc. Containers for light sources such as paints, fluorescent lamps, and mercury lamps that generate ultraviolet light, precision 0 devices, electronic and electrical equipment parts, shielding materials for electromagnetic waves generated by various displays, containers or packaging for foods, chemicals, pharmaceuticals, etc. Cosmetics, sportswear, socks, etc., anti-fading agents, anti-sunning lotions, shampoos, moisturizing essences, hair styling materials, etc. for materials, agricultural products or films, printing materials, dyes, dyes and pigments , such as fiber products for hats, hats, fabrics, curtains, blankets, wallpapers, etc., household interiors, plastic lenses, contact lenses, medical equipment such as artificial lenses, optical filters, Mitsubishi mirrors, mirrors, photo materials, etc. Supplies, tapes, inks, etc., such as stationery, labeling, signage, etc. The invention is specifically described below by way of examples, but the invention is not limited thereto. Moreover, unless otherwise specified, % and parts represent % by weight. And parts by weight. (Example 1) 240 parts by weight of N,N-dimethylformamidine was placed in a glass flask equipped with a cooling tube, a nitrogen introduction tube, a dropping funnel, a thermometer, and a -16-12836 90 stirrer. Amine (DMF) and 136.4 parts by weight of 1,1-bis[3-(2H-benzotriazol-2-yl)-4-hydroxyphenylethanol]methane (trade name "MB EP", manufactured by Otsuka Chemical Co., Ltd.) ), dissolved at 80 ° C. Then, 80.7 parts by weight of isophorone diisocyanate (IPDI) was added dropwise with stirring under a nitrogen atmosphere, and the reaction was carried out for 2 hours. Then, 22.9 parts by weight of N-methyldiethanolamine was added dropwise, and the reaction was continued for 4 hours.
接著，於40〜50mmHg的減壓下加熱到95°C爲止，以 去除190重量份DMF，用240重量份丁酮（ME K)來稀釋溶 解。然後，添加1 4.1重量份醋酸，將胺部分四級化，滴 下5 60重量份水，以使乳化。之後，於減壓下去除溶劑的 MEK，而得到目標的紫外線吸收性樹脂水乳液（I-1)。 該紫外線吸收性樹脂水乳液的不揮發份濃度係3 7 %， 平均粒徑（以下，藉由光散射粒徑測量裝置（大塚電子製， ELS-800)係 160nm。 (實施例2) 在與實施例1同樣的裝置中，加入24〇重量份N-甲基 Ο· 吡咯啶酮（NMP)和136.4重量份實施例所使用的紫外線吸 收劑Μ B E P，於8 0 °C溶解。接著於氮氣氣氛下邊攪拌邊滴 下8 0.7重量份異佛爾酮二異氰酸酯（IPDI)，進行2小時的 反應。然後，滴下22.9重量份N-甲基二乙醇胺，繼續4 小時的反應。接著，於40〜50mmHg的減壓下加熱到95°C 爲止，以去除190重量份DMF，用240重量份丁酮（meK) 來稀釋溶解。然後，添加1 4.1重量份醋酸，將胺部分四 級化，滴下5 60重量份水，以使乳化。之後’於減壓下去 17 1283690 除溶劑的ΜΕΚ，而得到目標的紫外線吸收性樹脂水乳液 (1-2)。該紫外線吸收性樹脂水乳液的不揮發份濃度係 3 2 %，平均粒徑係2 5 6nm。 (實施例3及比較例1) 對100重量份陽離子性水系聚胺甲酸酯乳液F_ 85 5 9D( 第一工業製藥股份有限公司製）而言，以下述表1中所示 重量份來混合上述實施例1及實施例2所得到的紫外線吸 收性樹脂水乳液（I-1 )、（1-2)和紫外線吸收劑MBEP本身， 將它流延於鐵弗龍塗覆的玻璃板上，使乾燥後之薄膜厚度 成爲10 0 μηι，在室溫下硬化乾燥14天，得到薄膜。 將薄膜供應給下述（1)的暴露試驗，在1 000小時暴露 後進行如下述（2 )的拉伸強度試驗，以測量各拉伸破壞伸 長率。又，供應給至2000小時爲止的暴露試驗，以調查 薄膜的著色。 (1) 曝光試驗裝置及條件： 雙循環陽光氣候測定器WEL-SUN-DC(史卡試驗機（股） 製，光源：碳弧），降雨循環：每1 20分鐘降雨1 8分鐘， 溫度：黑色面板8 0 °C。 (2) 抗強度試驗： 島津自動繪圖 DSC(島津製作所製（股），條件： 200kg/FS(滿刻度）、十字頭速度50mm/分，GL(標線間距 離=3 0 m m。 試驗結果如表1中所示。由表1可知，本發明者的耐 光性係比習用品優良。 -18 - l28369〇 袠1 紫外線吸收 重量 拉伸破壞伸長率 暴露試驗 1生樹脂水乳 液 份 初期 1 00 0 小 時後 實施例 (1-1) 1.5 118 119 2〇〇〇小時沒 有變化 3 (1-2) 1.5 115 114 2000小時沒 有變化 比較例 紫外線吸收 劑 MBEP 1.5 106 3 1 1 000小時後 著色 1 無 一 108 17 600小時後著 色 (實施例4及比較例2) 使以上述實施例1所得的紫外線吸收性樹脂水乳液（ΙΟ或習 知的紫 外線吸 收劑， 與聚苯 乙烯水 乳液以 下述表 2 所示配合量（不揮發份）混合，使用旋塗器使流延於直徑 3〇mm、厚度1mm之石英玻璃製碟片上並乾燥，作成厚度 〇·9〜1·〇μηι之均勻薄膜。將該碟片置於70°C之溫水中， 每2小時測量該薄膜在340nm的吸光度。表2中顯示初期 吸光度（A0)、10小時後之吸光度（A10)及吸光度保持率（％ 、A1 0/A0) ° 就使用習知的紫外線吸收劑（比較例2)者而言，由於所 用的紫外線吸收劑之溶出而使得吸光度呈現大約直線地減 少。與其相對地，使用實施例1之紫外線吸收性樹脂水乳 液（1-1)者，不會有溶出或滲出），而吸光度保持與初期同 等水準。 另外，使1 〇小時後的碟片進行與實施例1同樣的暴露 ，結果目視確認實施例4所得到的碟片在經過5 00小時後 也沒有看到變化，但是比較例2所得到的碟片在200小時 -19- 1283690 就變黃。因此，可知本發明之組成物具有安定的耐光性。 (實施例5及比較例3 ) 使以上述實施例2所得到的紫外線吸收性樹脂水乳液（I-2)或習知紫外線吸收劑與陽離子性水性聚胺甲酸酯乳液F-85 5 9D(第一工業製藥股份有限公司製，不揮發份濃度40%) 依表2中所示的配合量（不揮發份）混合，以形成水乳液樹 脂組成物。用於實例4同樣的方法來調製厚度約1 μπι之 均勻薄膜，求得吸光度和吸光度保持率，如表2所示。 表2 水乳液樹脂組成物 重量 份 上段：A 0 吸光度保 持率（％) 下段：A 1 0 實施例 4 (I-D 75 0.320 97.0 聚苯乙烯水乳液 925 0.3 10 比較例 2 紫外線吸收劑 ΜΒΕΡ 75 0.325 74.8 聚苯乙烯水乳液 925 0.243 實施例 5 (1-2) 87.5 0.469 97.0 F-8559D 912.5 0.455 比較例 3 紫外線吸收劑 ΜΒΕΡ 50 0.415 13.5 F-8559D 950 0.056 結果，可知當使用本發明的水乳液樹脂組成物時，紫 外線吸收性樹脂係幾乎完全保持於其它樹脂的基體中，溶 出或滲出現象係幾乎沒有。 產業上的利用可能性 依本發明，可得到一種水乳液樹脂組成物，其含有紫 外線吸收性樹脂的水乳液及其它樹脂的水乳液，與廣範圍 的合成樹脂之相溶性優良，賦予優良的耐光性而不會損害 合成樹脂的優良特性，紫外線吸收性樹脂滲出由乳液所得 -20- 1283690 到的塗膜表面之現象少’再者能將優良的耐鹼性和耐溶劑 性給予缺乏耐鹼性和耐溶劑性的合成樹脂。 本發明的水乳液和水乳液組成物係不會對環境增加負 荷，而且可形成且有耐久性（尤其耐光性）的塗膜，故期待 可利用於汽車、電氣、電子、建築等之廣泛產業領域中。 (五）圖式簡單說明 〇 -21 -Subsequently, the mixture was heated to 95 ° C under reduced pressure of 40 to 50 mmHg to remove 190 parts by weight of DMF, and diluted with 240 parts by weight of methyl ethyl ketone (ME K) to dissolve. Then, 14.1 parts by weight of acetic acid was added, the amine portion was quaternized, and 5 60 parts by weight of water was dropped to effect emulsification. Thereafter, the MEK of the solvent was removed under reduced pressure to obtain the desired ultraviolet absorbent resin aqueous emulsion (I-1). The non-volatile content of the ultraviolet-ray absorbing resin aqueous emulsion was 37%, and the average particle diameter (hereinafter, by a light scattering particle diameter measuring device (ELS-800, manufactured by Otsuka Electronics Co., Ltd.) was 160 nm. (Example 2) In the same apparatus as in Example 1, 24 parts by weight of N-methyloximepyrrolidinone (NMP) and 136.4 parts by weight of the ultraviolet absorber ΜBEP used in the examples were dissolved and dissolved at 80 ° C. followed by nitrogen. 8 0.7 parts by weight of isophorone diisocyanate (IPDI) was added dropwise under stirring in an atmosphere for 2 hours. Then, 22.9 parts by weight of N-methyldiethanolamine was added dropwise, and the reaction was continued for 4 hours. Next, at 40 to 50 mmHg. The mixture was heated to 95 ° C under reduced pressure to remove 190 parts by weight of DMF, and diluted and dissolved with 240 parts by weight of methyl ethyl ketone (meK). Then, 14.1 parts by weight of acetic acid was added, the amine portion was quaternized, and 5 60 was dropped. The water is added in parts by weight to emulsify. After that, the solvent is dehydrated to remove the enthalpy of the solvent to obtain the target ultraviolet absorbing resin aqueous emulsion (1-2). The non-volatile concentration of the ultraviolet absorbing resin aqueous emulsion is 3 2 %, average particle size 2 5 6n m. (Example 3 and Comparative Example 1) For 100 parts by weight of the cationic water-based polyurethane emulsion F_85 5 9D (manufactured by Dai-Il Pharmaceutical Co., Ltd.), the parts shown in Table 1 below were used. The ultraviolet absorbent resin aqueous emulsions (I-1), (1-2) and the ultraviolet absorbent MBEP itself obtained in the above Examples 1 and 2 were mixed and cast on a Teflon-coated glass plate. The film thickness after drying was changed to 100 μm, and it was hardened and dried at room temperature for 14 days to obtain a film. The film was supplied to the exposure test of the following (1), and after 1000 hours of exposure, the following (2) was carried out. Tensile strength test to measure each tensile elongation at break. Also, an exposure test up to 2000 hours was supplied to investigate the color of the film. (1) Exposure test device and conditions: Double cycle solar climate analyzer WEL- SUN-DC (Ska test machine (share) system, light source: carbon arc), rainfall cycle: every 18 minutes rainfall for 18 minutes, temperature: black panel 80 ° C. (2) Strength test: Shimadzu automatic drawing DSC (Shimadzu Manufacturing Co., Ltd., condition: 200kg/FS (full) GT), crosshead speed 50 mm/min, GL (distance between the marking lines = 30 mm. The test results are shown in Table 1. As is clear from Table 1, the light resistance of the present inventors is superior to that of the conventional products. L28369〇袠1 UV Absorbing Weight Tensile Destruction Elongation Exposure Test 1 Raw Resin Water Emulsion Part 1 00 0 hours later Example (1-1) 1.5 118 119 2 〇〇〇 hours no change 3 (1-2) 1.5 115 114 No change in 2000 hours Comparative Example UV absorber MBEP 1.5 106 3 1 Coloring after 1 000 hours No one 108 17 600 hours after coloring (Example 4 and Comparative Example 2) The ultraviolet absorbing property obtained in the above Example 1 was obtained. An aqueous resin emulsion (ΙΟ or a known ultraviolet absorber, mixed with a polystyrene aqueous emulsion in the amount shown in Table 2 below (non-volatile), cast using a spinner to a diameter of 3 mm and a thickness of 1 mm. The quartz glass disc was dried and dried to form a uniform film having a thickness of 〇·9~1·〇μηι. The disc was placed in warm water at 70 ° C, and the absorbance of the film at 340 nm was measured every 2 hours. Table 2 shows the initial absorbance (A0), the absorbance after 10 hours (A10), and the absorbance retention (%, A1 0/A0) °. For the use of the conventional ultraviolet absorber (Comparative Example 2), The dissolution of the ultraviolet absorber causes the absorbance to decrease approximately linearly. On the other hand, in the case of using the ultraviolet absorbent resin aqueous emulsion (1-1) of Example 1, there was no elution or bleeding, and the absorbance was maintained at the same level as the initial stage. Further, the same exposure as in Example 1 was carried out for the disc after 1 hour, and it was visually confirmed that the disc obtained in Example 4 did not show a change even after 500 hours passed, but the disc obtained in Comparative Example 2 was observed. The film turns yellow in 200 hours -19 - 1283690. Therefore, it is understood that the composition of the present invention has stable light resistance. (Example 5 and Comparative Example 3) The ultraviolet absorbing resin aqueous emulsion (I-2) obtained in the above Example 2 or a conventional ultraviolet absorbing agent and a cationic aqueous polyurethane emulsion F-85 5 9D were used. (manufactured by Daiichi Kogyo Co., Ltd., non-volatile content: 40%) The blending amount (nonvolatile matter) shown in Table 2 was mixed to form an aqueous emulsion resin composition. The same method as in Example 4 was used to prepare a uniform film having a thickness of about 1 μm, and the absorbance and absorbance retention were determined as shown in Table 2. Table 2 Amount of the water emulsion resin composition Upper part: A 0 Absorbance retention rate (%) Lower stage: A 1 0 Example 4 (ID 75 0.320 97.0 Polystyrene aqueous emulsion 925 0.3 10 Comparative Example 2 Ultraviolet absorbent ΜΒΕΡ 75 0.325 74.8 Polystyrene aqueous emulsion 925 0.243 Example 5 (1-2) 87.5 0.469 97.0 F-8559D 912.5 0.455 Comparative Example 3 Ultraviolet absorbent ΜΒΕΡ 50 0.415 13.5 F-8559D 950 0.056 As a result, it was found that when the aqueous emulsion resin of the present invention was used In the case of the material, the ultraviolet absorbing resin is almost completely retained in the matrix of the other resin, and there is almost no elution or oozing. Industrial Applicability According to the present invention, an aqueous emulsion resin composition containing ultraviolet absorbing property can be obtained. The aqueous emulsion of the resin and the aqueous emulsion of other resins are excellent in compatibility with a wide range of synthetic resins, impart excellent light resistance without impairing the excellent properties of the synthetic resin, and the ultraviolet absorbing resin oozes from the emulsion to -20-1263890 to There is less phenomenon on the surface of the coating film. In addition, it can give excellent alkali resistance and solvent resistance to the lack of alkali resistance. Synthetic resin and solvent-resistant synthetic resin. The aqueous emulsion and the aqueous emulsion composition of the present invention are designed to be used in automobiles without causing an increase in load on the environment and having a coating film having durability (especially light resistance). In the broad industrial fields of electricity, electronics, construction, etc. (5) Simple description of the model 〇-21 -