201200529 六、發明說明： 【發明所屬之技術領域】201200529 VI. Description of the invention: [Technical field to which the invention pertains]
本發明涉及-種對水溶液具有吸收良好的吸水物，稱謂為古 吸水性樹脂’此高吸水性樹脂具有強大的保水力，可吸收百倍: 至於千倍於本身重量的水，且於吸水後膨潤具有保持不流動的狀 態，即使杨壓力也不會相，其敎收的林可魏地在大氣 中釋出。此種高吸水性樹脂’目前已廣泛地被運用於農業，或園 藝方面的水鑛劑、建㈣料巾的抗露珠凝結敝及移除石油中 水份的除水劑，或魏線中的外層防水包覆_及衛朗品如尿 布、婦女衛生用品、拋棄式的擦巾等。 在日常的生活，由於高吸水性樹脂會直接與人體接觸，所以 一及水性旨的制安全性㈣十分重要。—般而言，高吸水性 樹脂所須具備的物理性質包括吸收速率、吸收力、壓力下吸收倍 φ率、低單體殘留量以及吸收後的凝膠力。優良的高吸水性樹料 僅要滿;I上義物理性質，具備了良好的安全性，更重要的是必 須為低汙染以及省能的物品。 【先前技術】 目前已知作為高吸水性樹脂成分材料的，有遇水分解型的澱 私'•丙烯腈(hydrolyzed starchacrylonitrile)接枝聚合物（曰本專利公 開公報昭49(1974)-43,395)，中和之;殿粉_丙稀酸接枝聚合物（曰 ^專利公開公報昭51 (1976>125,468)，皂化乙_酸—丙稀醋共 聚物（日本專利公開公報日召52(1977)娜的），水解丙稀猜共聚物 3 201200529 或丙稀醯胺共聚物（日本專利公報昭53 (1978)七綱，及部份 中和聚丙稀酸（日本專利公開公告日召MM叫Μ%4)等。其中， 澱粉-丙烯腈接枝聚合物的原料，因為含有殿粉而容易引起分解， 所以無法長時間保存’再者其製造方法亦十分複雜，所以現今高 吸水性樹脂之製備都以使用㈣酸及輯㈣進行交聯聚合反應 製得向吸水性樹齡最大部份。其主因為製造丙稀酸鹽共聚物的 原料-丙稀酸可迅速便宜地由工業化大量生產，且製得的高吸水性 樹脂具有很高的吸水能力，及具㈣造成本低廉之輯效益，以 及較不會引起腐爛性的分解’故成為最普遍化的高吸水性樹脂製 造用料^ 【發明擬解決的課題】 但上述所舉的尚吸水性樹脂尚存在著一個嚴重的問題，當它 儲藏於長時間之保存(數個月）’即便是處於常溫之下，其高吸水性 樹脂是容易造成自身著色的問題，也就是吸水性樹脂容易變黃甚 至是棕色，這種向吸水性樹脂於長時間保存所引起之黃化影響其 本身所具有之商業價值甚鉅。對於此問題已有日本專利 JP-A-05-086251及中國專利CN 1137159C等公開提及解決之道。 曰本專利JP-A-05-086251提及影響此黃化問題之主因為高吸水性 樹脂中之微量過渡金屬產生游離基，進而造成高吸水性樹脂分解 以及聚合物鏈之斷裂所致，因此建議使用有機磷酸化合物或是其 鹽類，以清除微量過渡金屬而減低黃化之問題。此外，CN 1137159C 也公開有關此一黃化問題之緣由，該案發明人認為引發黃化之機 201200529 轉與日本專利ΙΡ·Α·05·驗51有所不同，因此研究、試驗出不同 方法以減低黃化問題，也引發本轉明人進行降低高吸水性樹脂 黃化問題之研究與試驗。 【解決課題之技術手段】 經由研究及長期多次之試，驗以及參考CN nmwc號專利 毛現其引發g化可此原因為以1¾稀酸製造吸水性樹脂過程所使用 之阻聚劑舰所胁，其可能之機轉如式⑴及式(2)所示，The invention relates to a water-absorbing material with good absorption to an aqueous solution, and is called an ancient water-absorbent resin. The super-absorbent resin has strong water-retaining power and can absorb a hundred times: as for a thousand times its own weight of water, and swells after absorbing water. It has a state of not flowing, even if the pressure of Yang is not the same, and the forest that it collects can be released in the atmosphere. Such superabsorbent resins have been widely used in agriculture, or horticultural water mineralizers, construction (four) wipes for dew condensation, and water removal agents for removing oil from oil, or in the Wei line. The outer layer is covered with water _ and Wei Lang products such as diapers, feminine hygiene products, disposable wipes, etc. In daily life, since the super absorbent resin will directly contact the human body, the safety of the water-based system (4) is very important. In general, the physical properties of the superabsorbent resin include absorption rate, absorption, absorption ratio under pressure, low monomer residual amount, and gel strength after absorption. Excellent superabsorbent tree material only needs to be full; I have physical properties, good safety and, more importantly, must be low pollution and energy-saving items. [Prior Art] Hydrolyzed starch acrylonitrile graft polymer which is known as a water-absorbent resin component material is known as a water-absorbent resin component material (Japanese Patent Laid-Open Publication No. Sho 49 (1974)-43,395) , Neutralization; Dian powder_Acrylic acid graft polymer (曰^ Patent Publication No. 51 (1976) 125,468, saponified ethyl-acid-propylene vinegar copolymer (Japanese Patent Publication No. 52 (1977) Na's), hydrolyzed propylene guess copolymer 3 201200529 or acrylamide copolymer (Japanese Patent Gazette Sho 53 (1978) VII, and partially neutralized polyacrylic acid (Japanese Patent Publication Announcement MM Μ Μ% 4) Etc. Among them, the raw material of the starch-acrylonitrile graft polymer is easy to cause decomposition because it contains the temple powder, so it cannot be stored for a long time. Moreover, the manufacturing method is also very complicated, so the preparation of the high water absorbent resin is nowadays. The use of (4) acid and series (4) for cross-linking polymerization to obtain the largest part of the water absorption age. The main reason for the manufacture of the acrylic acid copolymer-acrylic acid can be quickly and inexpensively produced in large quantities by industrial production. High water absorption tree The fat has a high water absorption capacity, and (4) the low-cost benefits and the decomposition that does not cause rot, so it is the most common superabsorbent resin manufacturing material ^ [The problem to be solved by the invention] The above-mentioned water-absorbent resin still has a serious problem. When it is stored for a long time (several months), even if it is at normal temperature, its super absorbent resin is liable to cause self-coloring. That is, the water-absorbent resin is liable to turn yellow or even brown, and the yellowing effect caused by the long-term storage of the water-absorbent resin has a great commercial value. For this problem, there has been a Japanese patent JP-A-05. -086251 and Chinese patent CN 1137159C, etc., publicly mention the solution. 曰 JP-A-05-086251 mentions that the main factor affecting this yellowing problem is that the radicals in the superabsorbent resin generate free radicals, which in turn Decomposition of superabsorbent resin and breakage of polymer chains, it is recommended to use organic phosphoric acid compounds or their salts to remove trace transition metals and reduce the problem of yellowing. CN 1137159C also disclosed the reason for this yellowing problem. The inventor of the case believed that the machine for inducing yellowing 201200529 was different from the Japanese patent ΙΡ·Α·05·51, so different methods were studied and tested to reduce The problem of yellowing has also led to the research and experimentation of this illuminating person to reduce the yellowing of superabsorbent resin. [Technical means to solve the problem] Through research and long-term trials, and the reference CN nmwc patent The reason for the initiation of g-growth is that the polymerization inhibitor used in the process of manufacturing the water-absorbent resin with 13⁄4 dilute acid is threatened, and the possible mechanism is as shown in formula (1) and formula (2).
本案發明人等認為當氫醌與笨醌轉換成為中間體半醌時，可 月會幵>成一酿氫g昆之物質⑷或(B)，進而引發高吸水性樹脂變色， 此—變色我們即繼續不斷地研究抑制此一醌氫醌物質出現之機 U. | ’’終於成功地完成一個可抑制高吸水性樹脂黃化之方法，該方 法解決之道是透過加入一定比例之醌氫醌抑制劑於高吸水性樹脂 而達成’所述加入之醌氫醌抑制劑如式(3)所示； 201200529The inventors of the present invention thought that when hydroquinone and alum were converted into intermediate hafnium, it was possible to form a substance (4) or (B) which is a hydrogen-absorbing substance, thereby causing discoloration of the superabsorbent resin. That is to continue to study the inhibition of the occurrence of this hydrazine hydrazine material U. | '' finally successfully completed a method to inhibit the yellowing of superabsorbent resin, the solution is to add a certain proportion of hydrazine Inhibiting the superabsorbent resin to achieve the said addition of the hydrazine hydroquinone inhibitor as shown in formula (3); 201200529
GrYrX-Y2_G2 …….(3) 其中： Χ’ΥΑΥ2可為乙或乙快基；GrYrX-Y2_G2 . . . (3) where: Χ’ΥΑΥ2 can be B or B fast;
Gi及可為 (a) 線性、分支或環狀之Ci〜Ci。烧； (b) 具有單元的醇、胺、酸基、酯基、醯胺基、醛、酮， 或3 -元的醇、胺、酸基、醋基、醯胺基、路、酮取代基之線 性、分支或環狀之Cl〜Ci〇烧； (C)具有單元的醇、胺、酸基、酯基、醯胺基、醛、酮、 曱氧土乙氧基、氟、氣、漠、碰、腈基’或含二元的醇、胺、 酸基、酿基、酸胺基、搭、_、甲氧基、乙氧基、m 碘、腈基取代基之苯。 上述化合物可依下列期刊所記載之方法製備而得婉 Chem., 2008, 51 (9), 2682-2688 Chem., 2002, 67 (ΐ7χ 5907-5912 ^ J. 〇rg. Chem., 2004, 69 (6), 2106-2110 ^ J. 〇rg_ Chem^ 1997, 62 (13), 4546-4548 ^ 〇rg. Lett, 1999, 1 (5), 767-768 »m〇 2-(6-Γ基-3(Z)-己稀-l，5-雙块基苯胺、2-(6_ 丁基_3(z)_己缔],5·雙快基笨 腈、2-(6-丁基-3(Z)-己稀]，5-雙炔基苯、2_(6_丁基部)己稀; 雙丙块基料。其添加於高吸水性樹脂之缝可為高吸水性樹月旨 總量之O.lwt%〜lwt%，最佳添加量為〇Kswt%。添加方式是將 黃化抑制劑溶於水或溶於含50%〜10%有機溶劑較佳為含1〇%有機 201200529 〜j之水*液中’此所述有機溶劑可為甲醇、乙醇、異丙醇、丙 户丙酮了闕、甲基異丁闕。然後再將此含有黃化抑制劑之水 溶液與高吸水性樹脂進行混合。 此八有稀雙快骨架的黃化抑制劑化合物，其所具有之抑制黃 化此力’可此使半職較易進行加成反應至具稀雙炔骨架化合物， 而進行抑制形成式(2)至式⑶之結構所致。 本發明之南吸水性樹脂可在長期保存下，具有極佳之減少著 鲁色或抗只化此力。具體而言，可於相對濕度7〇%，溫度為9〇度之 城下存放二週後，高吸水性樹脂之著色度(γι)最多為Μ，色度 文化最夕為2.7’與則述jp_A_〇5_〇8625bCN um發明對比， 本發明之高吸水性獅於長時·更嚴苛環糊試下仍可保持較 佳色態，為本發明之一大特點。 【發明内容】 丙稀酸聚合物的代表性例子是包含有親水性樹脂，該親水性 _樹脂在聚合麟上都具有親水性官能基團如酸基、醯胺基、氨基 和石頁酸基等之聚合物’而本發明之親水性樹脂是聚丙烯酸及其經 中和後之鹽類’此鹽類包含链、納、鉀等驗金屬陽離子鹽類或銨 鹽、及前述兩者之聚合物，前述經中和後之丙烯酸鹽中和率可為 30〜mnol% ’此外，本發明亦可由前述兩者與水溶性或水不溶性 之單體共聚而成。其中之單體可選自甲基丙稀酸、馬來酸、富馬 酸、巴豆酸、衣康酸、乙稀基確駿、2_(甲）丙婦酿胺氣基_2_甲基丙 烧石頁酸、（曱基)丙烯酿氧基鏈烧fe磺g楚、以及單體所有的鹼金屬陽 201200529 離子鹽類或銨鹽等，此外尚包括N-乙烯基乙醢胺、（曱基)丙烯醯 胺、N，N-二曱基丙烯醯胺等單體。 以丙烯酸為原料製造吸水性樹脂同時使用丙烯酸以外之單 體時，其使用劑量應為全部丙烯酸之5〇wt%或更少，較佳為 30wt%以下，而最佳之使用量為不超過丙烯酸之l〇wt%。 本發明高吸水性樹脂，主要為丙烯酸或其鹽類之一種或兩種 所組成，但基於機能及物理性質上之考量，製程上之丙烯酸中和 率較佳以50〜95 mol%，而最佳範圍為6〇〜8〇 m〇1%之間，而形成 丙烯酸鹽之鹽類，可為鹼金屬鹽或銨鹽，其中較佳者為鋰或鈉鹽。 此外’較易引起著色問題之鋰鹽，可有限度的使用於本發明中， 前述之中和，可於聚合前或聚和後為之。 一般習知製備吸水性樹脂的過程，都在進行自減聚合反應 前，先添加自由基聚合反應交聯劑於未反應單體溶射，此自由Gi and can be (a) Ci~Ci linear, branched or cyclic. (b) an alcohol, an amine, an acid group, an ester group, a guanamine group, an aldehyde, a ketone, or a 3-membered alcohol, an amine, an acid group, a vine group, a guanamine group, a ketone substituent, or a ketone substituent Linear, branched or cyclic Cl~Ci〇; (C) alcohol, amine, acid, ester, guanamine, aldehyde, ketone, ethoxylate, fluorine, gas, desert Benzene, a nitrile group or a diol containing a dibasic alcohol, an amine, an acid group, a stilbene group, an acid amine group, a hydrazine, a methoxy group, an ethoxy group, a m iodine group, and a nitrile group. The above compounds can be prepared according to the methods described in the following journals. Chem., 2008, 51 (9), 2682-2688 Chem., 2002, 67 (ΐ7χ 5907-5912 ^ J. 〇rg. Chem., 2004, 69 (6), 2106-2110 ^ J. 〇rg_ Chem^ 1997, 62 (13), 4546-4548 ^ 〇rg. Lett, 1999, 1 (5), 767-768 »m〇2-(6-Γ基-3(Z)-hexa-l,5-diphenylaniline, 2-(6-butyl_3(z)_hexan],5·bis-fast-form nitrile, 2-(6-butyl- 3(Z)-diluted], 5-bisynylbenzene, 2-(6-butyl) hexene; double-propyl block base. It can be added to the high water-absorbent resin to be highly absorbent. The amount of O.lwt%~lwt%, the optimum addition amount is 〇Kswt%. The method of adding is to dissolve the yellowing inhibitor in water or dissolve in 50%~10% organic solvent, preferably containing 1% organic 201200529 ~ j water * liquid 'this organic solvent can be methanol, ethanol, isopropanol, propyl acetonide, methyl isobutyl hydrazine. Then this aqueous solution containing yellowing inhibitor and high water absorption The resin is mixed. The eight yellowing inhibitor compound with a rare double fast skeleton, which has the ability to inhibit yellowing, can make the half job easier to add. The structure of the formula (2) to the formula (3) is inhibited by the compound having a diacetyl acetylene skeleton. The south water-absorbent resin of the present invention can be excellently reduced in color or long-term preservation. Specifically, after storing for 2 weeks at a relative humidity of 7〇% and a temperature of 9〇, the color of the superabsorbent resin (γι) is at most Μ, and the chromaticity culture is 2.7′ Compared with the invention of jp_A_〇5_〇8625bCN um, the super absorbent lion of the present invention can maintain a better color state under the long-term and more severe cyclodext test, which is one of the major features of the invention. A representative example of the acrylic polymer is a polymer comprising a hydrophilic resin having hydrophilic functional groups such as an acid group, a guanamine group, an amino group, and a sulphate group on the polymerization lining. 'The hydrophilic resin of the present invention is a polyacrylic acid and a neutralized salt thereof. The salt comprises a metal cation salt or an ammonium salt such as a chain, a nano or a potassium salt, and a polymer of the foregoing, The neutralization rate of the acrylate after neutralization may be 30 to mnol% ' In addition, the present invention also The above two are copolymerized with a water-soluble or water-insoluble monomer, wherein the monomer may be selected from the group consisting of methyl acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and ethylene. , 2_(A) propylene, aryl alcohol, 2, methyl propyl sulphate, (fluorenyl) propylene, oxy chain, sulphonic acid, and all alkali metal cations 201200529 ionic salts or The ammonium salt or the like further includes a monomer such as N-vinylacetamide, (mercapto) acrylamide, and N,N-dimercaptopropenylamine. When a water-absorbent resin is used as a raw material for acrylic acid and a monomer other than acrylic acid is used, it should be used in an amount of 5% by weight or less, preferably 30% by weight or less, based on the total amount of acrylic acid, and the optimum amount is not more than acrylic acid. L〇wt%. The super absorbent resin of the present invention is mainly composed of one or two kinds of acrylic acid or a salt thereof, but based on functional and physical properties, the neutralization ratio of acrylic acid in the process is preferably 50 to 95 mol%, and most Preferably, the range is from 6 〇 to 8 〇 m 〇 1%, and the salt of the acrylate is formed, which may be an alkali metal salt or an ammonium salt, of which lithium or sodium salt is preferred. Further, the lithium salt which is more likely to cause coloring problems can be used in the present invention in a limited manner, and the aforementioned neutralization can be carried out before or after the polymerization. It is generally known that the process of preparing a water-absorbent resin is carried out by adding a radical polymerization crosslinking agent to the unreacted monomer before the self-reduction polymerization reaction.
酯、三丙烯酸聚氧乙烯甘油酯、三 、三甲醇丙烷三甲基丙烯酸酯、 •二(2-丙烯基)胺、二丙烯酸乙二醇 二丙締酸二乙基聚氧乙烯甘油酯、 201200529 一丙稀二甘醇醋等’亦可選用具有兩個或兩個以上環氧基的化合 物，如山梨醇聚縮水甘油醚、聚丙三醇聚縮水甘油醚、乙二醇二 縮水甘油趟、二乙二醇二縮水甘油_、聚乙二醇二縮水甘油驗、 雙丙二醇聚縮水甘油趟等。在進行自由基反應後高吸水性樹脂就 具有適當交聯度而使高吸水性樹脂膠體有適當的加工性。 自由基聚合反應交聯劑可單獨使用或兩種以上混合使用。其 適當的添加劑量在重量百分比o.ooiwt%至5wt%之間(以反應物總 鲁固形份為基準），更適當的用量重量百分比為〇〇lwt%至 3wt% 之 間。添加劑量在重量百分比o.ooiwt%以下，聚合後之水合體太軟 且有黏性不利機械加工；添加劑量在重量百分比5wt%以上，吸水 性太低，降低高吸水性樹脂之性能。 ΛΚ合反應，由自由基聚合反應起始劑的分解產生自由基開 始自由基起始劑可選用熱分解型起始劑，適合的熱分解型起始 Μ有過氧化物，如：過氧化氫、二-第三丁基過氧化物、過氧化醯 胺2過硫酸鹽(_、驗金難)等，及偶I化合物如：22, _偶氮 基雙(2-脉基丙烧)二鹽酸鹽、2 2’ _偶氮基雙(Ν,Ν_二伸甲基異丁脉) :鹽酸鹽；亦可使用還原劑，使其成為氧化還原型起始劑，如： 丨亞成鹽、硫代硫酸鹽、抗壞血酸或亞鐵鹽；或將氧化還原 型起始劑和熱分解型起始劑合併使S。首先氧化還原起始劑是先 進仃反應產生自由基，t其自由基轉移至單體上即引發聚合反應 =進:纟於進仃聚合反應時會釋放出大量的熱量而使溫度升 田/i度到達熱分解型起始劑的分解溫度時，又會引發第二段 201200529 熱分解型起始劑的分解，使整個聚合反應更臻於完全。一般自由 基聚合反應起始劑的適當用量為重量百分比〇 〇〇lwt%至 10wt%(以中和丙烯酸鹽重量為基準）’更適當用量則在〇lwt%至 5wt%之間’使用重量百分比在〇.〇〇lwt%以下時，反應太慢不利經 濟效益’使用重#百分tb為lGwt%以上時’反應太快反應熱不易 控制。 t合反應可於傳統批次反應容器中，或於輸送帶式反應器上 進行反應，反應所得之高吸水性樹脂，先利用絞碎機切成體積 10mm3以下小凝膠體，再進行筛選。筛選固定粒徑之凝膠體直徑 以2.00 mm以下為宜，以005咖至！ 5〇贿間較佳。由於粒徑 0.05mm以下之凝膠體進行烘乾、粉碎處理後，易產生成品細粉量 之提高，粒徑2.0〇mm以上之凝膠體進行烘乾，容易因為熱傳導效 果不佳，導致成品在殘存單體偏高，有物性表現不佳之缺點。而 丙烯酸鹽凝賴的齡大小分佈越針，不僅可使凝膠體在供乾 後的物性表現達到最佳狀態，且有利於控制烘乾的時間及溫度。 是故，粒徑大於2.00 mm以上及小於〇 〇5mm以下之凝膠體則重 新送回絞碎機進行再次反應、絞碎。 供乾溫度即以攝氏100。^ 18(rc進行烘乾，若供乾溫度在 i〇o°c以下，烘乾時間太久不具經濟效益；若烘乾以⑽。c以上洪 乾將使交聯纖早進行交聯反應’使得後續的乾燥過程，因交聯 度過高而無法有朗去除赫單體，賴降低殘存單體之效果。 201200529 【實施方式】 冋吸水性樹脂林溶解化之親水性聚合體，義内部具有均 勻!·生的架橋、，Ό構般為了改善品質如提高吸收速率、膠體強度、 抗結塊性、液體渗透性，都會在樹脂的表面再作進—步架橋。此 表面交聯處理之架橋’即利用具有能與酸基反應之多官能基交聯 劑’在本案申請專利之前已有許多專利被提出公開，如：分散高 吸水性樹脂與交聯劑於有機溶劑中進行表面交聯處理 • ( JP'A-56-1316〇8 ' JP-A-57-44627 . JP-A-58-42602 . 58 117222 )’使用無機粉直接將交聯劑與交聯劑;容液混入高吸 水性樹脂處理（JP_A60_163956、爪A_60 255814)，添加交聯劑後 以蒸氣處理（JP.A小113傷），使时機溶劑、水及多元醇進行表 面處理（JP-A-1-292004、美國專利6346569號）使用有機溶液、 水、趟（ether)化合物（JP_A_2_1539〇3)等這些表面處理的方法 ^能提高吸收速率，提紐力下吸水倍率，但造成鋪力下降過 #多的不良後果’降低了實際應用之性能。 根據本發明於實施表面處理時亦能同時進行交聯反應的交 聯劑可為多it醇如：丙三醇、乙二醇、二乙二醇、三乙二醇、聚 乙酉子丙一醇、1，4 丁二醇、三胺基甲基丙院、山梨醇等；或可 使用多元胺如：乙二胺、二乙二胺、三乙二胺、聚乙二胺；或具 有兩個或兩個以上環氧基的化合物如：山_聚縮水甘油越、聚 丙三醇聚縮水甘油趟、乙二醇二縮水甘⑽、二乙二醇二縮水甘 油麵、聚乙二醇二縮水甘油_、雙丙三醇聚縮水甘細等，·亦可 201200529 酮、4,5-二曱基-l，3-二氧雜環戍烧_2_嗣、4,4_二甲基Μ.:氧雜環 戍烷-2-酮、4-乙基-1，3·二氧雜環戊烷_2_酮、u_二氧雜環己烷_2_ 酉同、4,6-二曱基_1，3·二氧雜環己院_2__或u_二氧雜環庚烧_2-酮 等。 上述交聯劑的用法可單獨使用或兩種以上混合使用。其適當 添加劑量在重量百分比_lwt%至腕％之間(以反應物總固形 Ϊ刀為基準）’更適當的用量在〇.QQ5wt%S 5加％之間。交聯劑添加 劑里在重1：百分比G.GGlwt%以下時無法顯出功效，在重量百分比 l〇wt%以上時，吸水性太低，降低樹脂御卜於此階段同時亦可添 加本發明之黃化抑·於交聯反應巾以增進高吸水細旨之抗黃化 此力而其添加方式是將黃化抑制劑溶於水或溶於含 50wt%〜l〇wt〇/0 ’較佳為含1〇对％有機溶劑之水溶液中，而所述之 有機岭劑可為甲醇、乙醇、異丙醇、丙醇、_、丁酮、甲基異 丁酮’再财聯齡加於吸魏樹顧液混合，其黃化抑制劑的 添加量為高吸水性樹脂總量之編％〜祕，最佳添加量為 ().l_0.5wt%。 ,待添加θ化抑制劑於高吸水性樹脂進行表面交聯劑塗 後丄再以9GC至23〇。(：範_進行加熱處理，使表面交聯劑及 I交聯舰均勻而且快速地進行㈣反應而達成本發明的目的 果。若熱處理溫度9(Τγ^τ ^ 下’父聯反應時間太久不具經濟效羞 ‘、、、處理溫度23〇hx上，樹脂易劣化影響品質。 201200529 依照欲獲得的表面處理效果可做熱處理溫度調節原則，熱處 理溫度高則其熱處理時間短，熱處理溫度低，則其熱處理溫度時 間較長’其熱處理時間即以30分鐘至15〇分鐘為宜。而經此處理 原則處理後之高吸水性樹脂具有抗黃化能力。適用於本發明的熱 處理裝置包括·隨道式混合乾燥器、轉鼓式乾燥器、臺式乾燥芎、 流化床乾燥器、氣流式乾燥器以及紅外線乾燥器等。 此外，僅只進行表面交聯塗覆處理之高吸水性樹脂，再與含 有黃化抑制劑之水溶液混合進行加熱交聯反應處理，亦可得到具 有抗頁化能力之咼吸水性樹脂，而此黃化抑制劑添加於高吸水性 樹脂之劑量可為樹脂總量之〇.lwt%〜lwt%，最佳添加量為〇 ι%， 其添加对可將黃讀湖祕水或絲含5Qwt%〜胸％，較佳 為含10wt%有機溶劑之水溶液’此所述之有機溶劑可為甲醇、乙 醇、異丙醇、丙醇、丙酮、丁酮或曱基異丁_。待高吸水性樹脂 進行表面交聯反應塗覆處理後，以溫度卿至23叱範圍内進行 加熱處理’使黃化_舰均勻快速的進行反應，達到本發 明之效果。熱處理溫度90。(:町，反應_較久科具_效益， 熱處理溫度23(TC以上，樹脂易劣化影響品質。熱處理時間以3〇 分鐘至150分鐘為宜’其熱處理溫度高顺處辦間短，熱處理 溫度低時，則熱處理溫度時間較長。 熱處理可使用普通的乾燥器或加讎即可完成，適用於本發 明的祕縣置包括：麟式混合乾聽、轉鼓式乾㈣、臺式 乾燥器/’IL化床乾燥器、氣流式乾燥器以及紅外線乾燥器等。 13 201200529 為顯示本發明之高吸水性樹脂的壓力下吸水倍率，本發明則 利用丈壓吸收重(壓力負荷：2〇g/cm2及49g/cm2)來測定。其受壓吸 收量的測定，係根據歐洲專利0339461 A號說明書第七頁中所描 述的方法，將初始重量的高吸水性樹脂放在有篩網底部的圓柱體 中，對粉體加壓20g/cm2及49g/cm2的壓力，接著將此圓柱體置於 吸收性需求測試器上，讓高吸水性樹脂吸收〇 9%的氣化鈉水溶液 一小時，再將測得的吸水重量數值除以高吸水性樹脂的重量，即 得受壓吸收重數值。 本發明之保持力係利用命袋試驗法測定，並以五次量測結果 去除最高值以及最低值後取其平均值；將02g的高吸水性樹脂裝 在茶袋裡，並浸泡於0.9%的NaCl水溶液20分鐘，然後將此浸泡 後的荼袋置於離心機離心(直徑23cm、轉速14〇〇rpm)三分鐘後秤 重。所得之數值先減去未充填高吸水性樹脂的空白組茶袋重(以相 同步驟操作)再除以聚合物重即得保持力數值。 評估高吸水性樹脂黃化程度之方法與CN 1137159C所記敘 相同’所用色度偵測儀為SZ- Σ 80 COLORMEASURING SYSTEM(Nippon Denshoku Kogyo Co.，Ltd)，恆溫恆溼器為欣千祥 製造，型號為AJH-80，試驗條件為攝氏9〇度及7〇%RH下放置兩 周，再分析其色度變化。 以下以參考及較佳實施例詳細說明本發明；但本發明範圍則 不受這些實施例所限制。 14 201200529 參考例： 1) lOOc.c圓錐瓶中加入3〇g丙烯酸(台塑公司林園AE廠生產)及 32.4g的水；另外在lOOc.c圓錐瓶中稱取48%氫氧化納水溶液 24.3g ’於冰冷下將氫氧化鈉水溶液缓緩加入丙烯酸水溶液中進 行中和；此時得單體濃度42wt%水溶液，其中70mol%(莫耳比） 丙烯酸部份中和為丙烯酸鈉。 2) 加入0.046g的丙三醇聚乙二醇三縮水甘油醚(n=7)於部分中和 鲁 的丙烯酸溶液，並維持溫度於20°C左右。 3) 再加入0.016g L-抗壞血酸，〇.2g過硫酸鈉及〇.2g之2.2·偶氮基 雙(2-脒基丙烷)二鹽酸鹽以起始反應。 4) 反應後將此高吸水性樹脂利用切式粉碎機切成2mm直徑以下 的凝膠體。 5) 以130°C溫度乾燥2小時；利用篩網篩選〇 lmm〜0 85mm固定 粒徑’得粉狀南吸水性樹脂。 • 6)秤取上列方法製得之高吸水性樹脂i〇g，加入乙二醇碳酸酯/水 = 1/1(重量比)溶液〇.4g，以混合機進行固液混合，再以215。〇溫 度加熱處理10分鐘。 7) 冷卻後，即得保持力32.5g/g且20g/Cm2壓力下吸水倍率 30.1g/g，49g/cm2壓力下吸水倍率22 8g/g之高吸水性樹脂⑷。 8) 取局吸水性樹脂(a)進行評估高吸水性樹脂黃化程度’其結果請 詳表一0 15 201200529 賞施例一： 1) 秤取參考例(1)〜(5)所製得的高吸水性樹脂1〇g，加入乙二醇碳 酸酯/水/=1/1(重量比)溶液〇.4g，再加入〇」重量％之含1〇wt% 的2-(6-丁基-3(Z)-己烯_ι，5·雙炔基笨胺水溶液(水/丙酮=9/1)以 混合機進行固液混合，再以215。(：溫度加熱處理10分鐘。 2) 冷卻後，即得保持力32.4g/g且20g/cm2壓力下吸水倍率 30.2g/g，49g/cm2壓力下吸水倍率22 3g/g之高吸水性樹脂(b)。 實施例二： 秤取99重量％參考例之高吸水性樹脂(a)，加入丨重量％之 含10wt%的2-(6-丁基·3(Ζ)-己烯-1，5·雙炔基苯胺水溶液(水/丙酮 =9/1)，混合均勻後再進行評估高吸水性樹脂(其保持力為32 lg/g 且20g/cm壓力下吸水倍率3〇.3g/g，49g/cm2壓力下吸水倍率 22.5g/g)黃化程度，其結果請詳表一。 實施例三： 秤取98重量％參考例之高吸水性樹脂(a)，加入2重量％之 含10wt%的2-(6-丁基-3(Z)·己烯-l，5-雙炔基苯胺水溶液(水/丙酮 =-9/1)，混合均勻後再進行評估高吸水性樹脂(其保持力為32〇g/g 且20g/cm壓力下吸水倍率3〇2g/g，49g/cm2壓力下吸水倍率 22.6g/g)黃化程度，其結果請詳表一。 實施例四： 秤取99重量％參考例之高吸水性樹脂(a)，加入1重量。/〇之 含10wt%的2-(3_(Ζ)-11烯-i，5-雙炔基笨腈水溶液(水/丙^飢）， 16 201200529 混合均2勻後再進行評估高吸水性樹脂（其保持力為32.1g/g且 20g/cm壓力下吸水倍率3〇她，49麵2壓力下吸水倍率泣她) 黃化程度’其結果請詳表一。 實施例五： 秤取98冑量％參考例之高吸水性樹脂⑻，加入2重量％之 3 10wt/。的2-(3-(Ζ)-11稀·ι,5-雙诀基苯腈水溶液(水/丙自㈣⑴， 混合均勻後再進行雜高吸水性劃旨（其料力為322的且 籲20gW壓力下吸水倍率见她，辦/‘壓力下吸水倍率η测 黃化程度，其結果請詳表一。 比較例一： 秤取99重量。/。參考例之高吸水性樹脂⑻，加入i重量％的 N，N’ -次甲級__ ’混合均勻後再進行評估高吸水性樹脂 (其保持力為32她且2Gg/em2壓力下吸水料3Q2g/g，49〆 壓力下吸水倍率22.6g/g)黃化程度，其結果請詳表一。 鲁比較例二： 取"重量％參考例之高吸水性樹脂⑻與1重量％之含 〇.5祕的i•祕亞乙基酸(m齡51公開的著色抑 制劑)的水溶液混合，進行乾燥後再進行評估高吸水性樹脂(其保持 力為32.2g/g且20g/cm2壓力下吸水倍率3〇4g/g，49_2壓力下 吸水倍率22.2g/g)黃化程度，其結果請詳表一。 201200529 比較例三： 筛將參考例之高吸水性樹脂_行分級，將樹脂 來U粒役8觸则之高吸水性樹腊(其保持力為儿峨且 琴力下吸水倍率3Z3g/g，修¥壓力下吸水倍率 』5.5g/g)，再進行評估高吸水性樹脂黃化程度，其結果請詳表一。 比較例四： …以JIS標準筛將實施例二之高吸水性樹脂⑻進行分級，將樹 脂筛選為粒徑3〇(M50um之高吸水性樹脂(其保持力為32域· 20g/cm壓力下吸水倍率28 3g/g，49g/cm2壓力下吸水倍率Ester, polyoxyethylene glyceryl triacrylate, tris, trimethylolpropane trimethacrylate, • bis(2-propenyl)amine, ethylene diacrylate diacrylate polyoxyethylene glyceride, 201200529 A propylene glycol vinegar, etc. can also be used with compounds having two or more epoxy groups, such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, ethylene glycol diglycidyl hydrazine, two Ethylene glycol diglycidyl _, polyethylene glycol diglycidyl test, dipropylene glycol polyglycidyl hydrazine and the like. The superabsorbent resin has a suitable degree of crosslinking after the radical reaction, and the superabsorbent resin colloid has appropriate processability. The radical polymerization crosslinking agent may be used singly or in combination of two or more. The appropriate amount of the additive is between 5% by weight and 5% by weight based on the total solids of the reactants, and more preferably in an amount of from 3% by weight to 3% by weight. The added dose is below the weight percentage of o.ooiwt%, and the hydrated body after polymerization is too soft and sticky to be unfavorably mechanically processed; the amount of the additive is more than 5% by weight, the water absorption is too low, and the performance of the superabsorbent resin is lowered. The reaction is initiated by the decomposition of the radical polymerization initiator to generate a radical. The radical initiator is optionally provided with a thermal decomposition initiator, and the suitable thermal decomposition type starting is a peroxide such as hydrogen peroxide. , di-tert-butyl peroxide, guanidinium peroxide 2 persulfate (_, difficult to test gold), and even I compounds such as: 22, _ azobis (2-cyanopropyl) Hydrochloride, 2 2 ' _ azo bis (indole, Ν _ diexetylmethyl isobutyl hydride): hydrochloride; can also use a reducing agent, making it a redox initiator, such as: Forming a salt, a thiosulfate, an ascorbic acid or a ferrous salt; or combining a redox type initiator and a thermal decomposition type initiator to give S. First, the redox initiator is an advanced hydrazine reaction to generate a radical, and its radical is transferred to the monomer to initiate polymerization. = Ingress: When the hydrazine polymerization reaction, a large amount of heat is released and the temperature is raised to the field. Upon reaching the decomposition temperature of the thermally decomposable initiator, decomposition of the second stage 201200529 thermal decomposition initiator is initiated, making the overall polymerization more complete. A suitable amount of the radical polymerization initiator is generally 5% by weight to 10% by weight based on the weight of the neutralized acrylate. 'More suitable amount is between 〇1wt% and 5% by weight'. When 〇.〇〇lwt% or less, the reaction is too slow, which is unfavorable economical efficiency. 'When the weight is used, the percentage of tb is lGwt% or more. 'The reaction is too fast. The reaction heat is not easy to control. The t-reaction can be carried out in a conventional batch reaction vessel or on a conveyor belt reactor, and the superabsorbent resin obtained by the reaction is first cut into a small gel having a volume of 10 mm 3 or less by a mincer and then subjected to screening. . Screen the diameter of the gel with a fixed particle size of 2.00 mm or less, with 005 coffee! 5 bribes are better. Since the gel having a particle diameter of 0.05 mm or less is subjected to drying and pulverization treatment, the amount of fine powder of the finished product is easily increased, and the gel having a particle diameter of 2.0 〇 mm or more is dried, which is liable to cause a finished product due to poor heat conduction effect. In the case where the residual monomer is high, there is a disadvantage that the physical property is not good. The more the size distribution of the acrylate condensate, the better the physical properties of the gel after drying, and it is beneficial to control the drying time and temperature. Therefore, a gel having a particle diameter of more than 2.00 mm and less than 〇 5 mm or less is returned to the mincer for re-reaction and mincing. The dry temperature is 100 degrees Celsius. ^ 18 (rc drying, if the dry temperature is below i〇o °c, the drying time is too long to be economical; if it is dried to (10). The above-mentioned flooding will make the cross-linked fiber cross-linking early' In the subsequent drying process, since the crosslinking degree is too high, the monomer cannot be removed, and the effect of the residual monomer is lowered. 201200529 [Embodiment] The hydrophilic polymer dissolved in the water-absorbent resin forest has uniform internal meaning. In order to improve the quality, such as increasing the absorption rate, colloid strength, anti-caking property and liquid permeability, the raw bridge will be built into the surface of the resin. The bridging of this surface cross-linking treatment That is, the use of a polyfunctional crosslinking agent capable of reacting with an acid group has been disclosed in the prior patent application, for example, dispersing a superabsorbent resin and a crosslinking agent in an organic solvent for surface crosslinking treatment. ( JP 'A-56-1316〇8 ' JP-A-57-44627 . JP-A-58-42602 . 58 117222 ) 'Using inorganic powder to directly crosslink the crosslinker with the crosslinker; Resin treatment (JP_A60_163956, claw A_60 255814), added After the mixture is treated with steam (JP.A, small 113 wounds), the solvent, water and polyol are surface-treated (JP-A-1-292004, US Patent No. 6,346,569) using organic solution, water, hydrazine (ether) The method of surface treatment such as compound (JP_A_2_1539〇3) can increase the absorption rate and increase the water absorption rate under the force of Niu, but cause the adverse effect of the paving force to decrease more than 'there is a decrease in the performance of the actual application. According to the present invention The cross-linking agent capable of simultaneously performing the cross-linking reaction in the surface treatment may be a poly-alcohol such as glycerol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylidene propanol, 1,4 butyl a diol, a triaminomethine, a sorbitol, etc.; or a polyamine such as ethylenediamine, diethylenediamine, triethylenediamine, polyethylenediamine; or two or more rings Oxygen compounds such as: mountain _ polyglycidol, polyglycerol polyglycidyl hydrazine, ethylene glycol diglycidyl (10), diethylene glycol diglycidide, polyethylene glycol diglycidyl _, double propylene Alcohol polycondensation, etc., can also be 201200529 ketone, 4,5-dimercapto-l,3-dioxacyclo _2_2_嗣, 4,4_dimethylhydrazine.:oxacyclononan-2-one, 4-ethyl-1,3·dioxol-2-one, u-diox Heterocyclic hexane_2_ 酉, 4,6-dimercapto-1,3·dioxanthene-2__ or u-dioxepane-2-one, etc. The usage may be used singly or in combination of two or more. The appropriate amount of the additive is between _lwt% and w% by weight (based on the total solid squeegee of the reactants), and a more appropriate amount is used in 〇.QQ5wt%S 5 plus Between the %. The cross-linking agent additive can not show the effect when the weight is less than 1: G.GGlwt%. When the weight percentage is more than l〇wt%, the water absorption is too low, and the resin can be lowered at this stage. Adding the yellowing inhibition of the present invention to the cross-linking reaction towel to enhance the anti-yellowing effect of the high water absorption, and the addition method is to dissolve the yellowing inhibitor in water or dissolve in 50 wt%~l〇wt〇/ 0 ' is preferably in an aqueous solution containing 1 〇 to % organic solvent, and the organic ridge agent may be methanol, ethanol, isopropanol, propanol, _, methyl ethyl ketone, methyl isobutyl ketone 're-finance Age added to the suction of Weishu Gu liquid, its yellowing inhibitor The total added amount eds Superabsorbent% secret, optimal addition amount () .l_0.5wt%. After the surface-crosslinking agent is applied to the superabsorbent resin to be added, the rhodium-inhibiting agent is further added at 9GC to 23〇. (: Fan_heat treatment, the surface cross-linking agent and the I cross-linked ship are uniformly and rapidly reacted (4) to achieve the object of the present invention. If the heat treatment temperature is 9 (Τγ^τ ^ lower 'parent reaction time is too long Without economical shame, and the treatment temperature is 23〇hx, the resin is easily deteriorated and affects the quality. 201200529 According to the surface treatment effect to be obtained, the heat treatment temperature adjustment principle can be used. When the heat treatment temperature is high, the heat treatment time is short, and the heat treatment temperature is low. The heat treatment time is longer, and the heat treatment time is preferably 30 minutes to 15 minutes. The superabsorbent resin treated by the treatment principle has anti-yellowing ability. The heat treatment device suitable for the present invention includes Mixing dryer, drum dryer, bench top drying crucible, fluidized bed dryer, airflow dryer, infrared dryer, etc. In addition, only superabsorbent resin for surface cross-linking treatment is applied, The aqueous solution containing the yellowing inhibitor is mixed and subjected to a heat crosslinking reaction treatment, and a water-absorbent resin having an anti-page property can also be obtained, and the yellowing inhibits The dosage of the agent added to the superabsorbent resin may be 〇.1wt%~lwt% of the total amount of the resin, and the optimal addition amount is 〇ι%, and the addition thereof may be 5Qwt%~thorax% of the yellow reading lake secret water or silk. Preferably, it is an aqueous solution containing 10% by weight of an organic solvent. The organic solvent described herein may be methanol, ethanol, isopropanol, propanol, acetone, methyl ethyl ketone or decyl isobutyl ruthenium. After the combined reaction coating treatment, the heat treatment is carried out in the range of temperature to 23 ', so that the yellowing_ship is uniformly and rapidly reacted to achieve the effect of the present invention. The heat treatment temperature is 90. (: town, reaction _ longer time) _ Benefits, heat treatment temperature 23 (above TC, the resin is easy to deteriorate and affect the quality. The heat treatment time is preferably from 3 〇 to 150 minutes.) The heat treatment temperature is high, and the heat treatment temperature is low. The heat treatment can be completed by using a common drier or twisting. The secret county set suitable for the present invention includes: a cymbal mixed dry listening, a drum dry (four), a table dryer / an 'IL bed dryer, an air flow type Dryers, infrared dryers, etc. 13 2 01200529 In order to show the water absorption ratio under pressure under the pressure of the super absorbent resin of the present invention, the present invention is measured by using a pressure absorption load (pressure load: 2 〇g/cm 2 and 49 g/cm 2 ). The measurement of the pressure absorption amount is According to the method described in the seventh page of the specification of European Patent No. 03369461 A, an initial weight of the super absorbent resin is placed in a cylinder having a bottom of the screen, and the powder is pressurized at a pressure of 20 g/cm 2 and 49 g/cm 2 . Then, the cylinder is placed on an absorbent demand tester, and the superabsorbent resin absorbs 9% of the sodium carbonated aqueous solution for one hour, and then the measured water absorption weight value is divided by the weight of the superabsorbent resin. The pressure-receiving weight value of the present invention is determined by the life bag test method, and the highest value and the lowest value are removed after five measurement results, and the average value is taken; 02 g of the super absorbent resin is placed in the tea bag, The solution was immersed in a 0.9% NaCl aqueous solution for 20 minutes, and then the soaked sputum bag was placed in a centrifuge for centrifugation (diameter 23 cm, rotation speed 14 rpm) for three minutes and then weighed. The obtained value is first obtained by subtracting the weight of the blank group tea bag which is not filled with the super absorbent resin (operating in the same step) and dividing by the weight of the polymer to obtain the retention value. The method for evaluating the degree of yellowing of the superabsorbent resin is the same as that described in CN 1137159C. The colorimeter used is SZ- Σ 80 COLORMEASURING SYSTEM (Nippon Denshoku Kogyo Co., Ltd), and the constant temperature and humidity device is manufactured by Xin Qianxiang. The model number is AJH-80, and the test conditions are 9 degrees Celsius and 7〇% RH for two weeks, and then the color change is analyzed. The invention is described in detail below with reference to the preferred embodiments; however, the scope of the invention is not limited by these examples. 14 201200529 Reference example: 1) Add 3〇g acrylic acid (produced by Formosa Plastics AE factory) and 32.4g water to lOOc.c conical flask; and weigh 48% sodium hydroxide aqueous solution in lOOc.c conical flask 24.3g 'Sodium hydroxide aqueous solution was slowly added to the aqueous acrylic acid solution for neutralization under ice cooling; at this time, a monomer concentration of 42 wt% aqueous solution was obtained, in which 70 mol% (mole ratio) of the acrylic acid was partially neutralized to sodium acrylate. 2) Add 0.046 g of glycerol polyethylene glycol triglycidyl ether (n = 7) to partially neutralize the acrylic acid solution and maintain the temperature at around 20 °C. 3) Further, 0.016 g of L-ascorbic acid, 2 g of sodium persulfate and 2 g of 2.2·azobis(2-amidinopropane) dihydrochloride were added to initiate the reaction. 4) After the reaction, the superabsorbent resin was cut into a gel having a diameter of 2 mm or less by a cutter. 5) Drying at a temperature of 130 ° C for 2 hours; screening the 〇 lmm~0 85 mm fixed particle size by a sieve to obtain a powdery south water-absorbent resin. • 6) Weigh the super absorbent resin i〇g prepared by the above method, add 4 g of glycol carbonate/water = 1/1 (weight ratio) solution, mix and solidize with a mixer, and then 215. Heat treatment at 〇 for 10 minutes. 7) After cooling, a superabsorbent resin (4) having a holding capacity of 32.5 g/g and a water absorption ratio of 30.1 g/g under a pressure of 20 g/cm 2 and a water absorption ratio of 22 8 g/g under a pressure of 49 g/cm 2 was obtained. 8) Take the water-absorbent resin (a) and evaluate the degree of yellowing of the superabsorbent resin. The results are shown in Table 1 0 15 201200529 Appreciation Example 1: 1) Weighing the reference examples (1) to (5) 1 g of superabsorbent resin, adding 4 g of ethylene carbonate/water/=1/1 (by weight) solution, and then adding 〇% by weight of 2-(6-butyl) containing 1% by weight. A solution of the base-3(Z)-hexene_ι,5·diacetylenylamine (water/acetone=9/1) was mixed with a mixer, and then 215. (: heat treatment for 10 minutes. 2 After cooling, the superabsorbent resin (b) having a holding capacity of 32.4 g/g and a water absorption ratio of 30.2 g/g under a pressure of 20 g/cm 2 and a water absorption ratio of 22 3 g/g under a pressure of 49 g/cm 2 was obtained. Example 2: Scale 99% by weight of the superabsorbent resin (a) of the reference example was added, and 10% by weight of a 2-(6-butyl·3(Ζ)-hexene-1,5·di- alkynylaniline aqueous solution (weight %) was added. Water/acetone = 9/1), and the mixture was uniformly evaluated, and the superabsorbent resin was evaluated (the holding power was 32 lg/g and the water absorption ratio under the pressure of 20 g/cm was 3 〇.3 g/g, and the water absorption ratio under the pressure of 49 g/cm 2 22.5g / g) degree of yellowing, the results are detailed in Table 1. Example 3: weighing 98% by weight of the reference example Superabsorbent resin (a), adding 2% by weight of a 10% by weight aqueous solution of 2-(6-butyl-3(Z)·hexene-1,5-diynylaniline (water/acetone=-9/ 1) After the mixture was uniformly mixed, the superabsorbent resin was evaluated (the holding power was 32 〇g/g and the water absorption ratio under the pressure of 20 g/cm was 3 〇 2 g/g, and the water absorption ratio under the pressure of 49 g/cm 2 was 22.6 g/g). The degree of the reaction is shown in Table 1. Example 4: 99% by weight of the superabsorbent resin (a) of the reference example was weighed, and 1 wt./〇 of 10 wt% of 2-(3_(Ζ)-11 was added. Alkene-i,5-diacetylenic acid nitrile aqueous solution (water/c; hunger), 16 201200529 After mixing and homogenizing, the superabsorbent resin was evaluated (the retention force was 32.1 g/g and the water was absorbed under a pressure of 20 g/cm). The magnification is 3〇, she is soaked under the pressure of 49 faces and 2, and the degree of yellowing is as follows. The results are shown in Table 1. Example 5: Weighing 98胄% of the superabsorbent resin (8) of the reference example, adding 2% by weight 3 10wt /. 2-(3-(Ζ)-11 稀·ι,5-bis-mercaptobenzonitrile aqueous solution (water / propylene from (4) (1), after mixing evenly, the hetero-high water absorption is carried out (the material force is 322 and called 20gW under the pressure of water absorption rate see her, do / 'pressure under water absorption ratio η The degree of yellowing is measured, and the results are shown in Table 1. Comparative Example 1: Weighing 99 weights. /. Reference superabsorbent resin (8), adding i% by weight of N, N' - sub-class A __ 'mix evenly After that, the degree of yellowing of the superabsorbent resin (the retention force of 32 and her absorbent material at 3 Gg/em2 pressure, 3Q2 g/g under pressure of 2 Gg/em2 and the water absorption ratio of 22.6 g/g at 49 Torr) was evaluated. The results are shown in Table 1. Comparative Example 2: Take the "% by weight reference example of the superabsorbent resin (8) mixed with 1% by weight of an aqueous solution containing •.5 secret i•mythracene acid (mature 51 open color inhibitor) After drying, the degree of yellowing of the superabsorbent resin (retention force of 32.2 g/g and water absorption ratio of 3〇4g/g under pressure of 20g/cm2 and water absorption ratio of 22.2g/g under pressure of 49_2) was evaluated. Detailed table 1. 201200529 Comparative Example 3: The high-absorbency resin of the reference example is classified as a sieve, and the resin is used to granulate the high-absorbency tree wax of 8 touches (the retention force is 峨 and the water absorption ratio under the force is 3Z3g/g, Under the pressure of the pressure, the water absorption ratio is 5.5 g/g, and the degree of yellowing of the superabsorbent resin is evaluated. The results are shown in Table 1. Comparative Example 4: The high water-absorbent resin (8) of Example 2 was classified by a JIS standard sieve, and the resin was sieved to a particle size of 3 Å (M50 um super absorbent resin (the holding force was 32 domains · 20 g / cm pressure) Lower water absorption ratio 28 3g/g, water absorption ratio under pressure of 49g/cm2
20.5g/g)，再進行評估高吸水性樹脂黃化程度，其結果呈於表一之 中。 表一· 著色度(YI值） ----- 測試前 —--- 測試後 著色度變化 參考例 8.9 56.8 47.9 實施例一 一 9.0 ----- 11.1 2.1 實施例二 8.9 10.9 2.0 實施例三 8.9 --- 11.2 2.3 實施例四 8.9 10.7 1.8 實施例五 8.9 11.6 2.7 比較例一 8.9 16.8 7.9 18 201200529 比較例二 8.9 36.7 27.8 比較例三 8.9 11.3 2.4 比較例四 8.9 11.0 2.1 由參考例之色度變化我們可以發現未添加黃化抑制劑者，於 兩週後之色度變化達到47.9，而由實施例一〜五可以發現當添加 O.lwt%重量百分比之黃化抑制劑’即可有效達到防止高吸水性樹 脂黃化之效果，且不論是於表面交聯階段或表面交聯後添加黃化 鲁抑制劑，皆有達到防止高吸水性樹脂黃化之效果，其高吸水性樹 脂於兩週後之色度變化約為1,8〜2.7。此外由比較例一可以發現使 用CN 1137159C專利所記述之黃化抑制劑，經由本發明人之較嚴 苛方式5平估，其尚吸水性樹脂之色度變化約為7 9，與本發明之黃 化抑制劑（色度變化1.8〜2.7)，比财較大落差；另外再由比較例 二所得結果可以明瞭’由爪祕__51所提出之黃化抑制劑， 經由測试後其抗黃化能力也遠不如本發明之表現。最後，由比較 例一及四明，㊉吸水性樹脂之顆粒大小對本發明之黃化抑 制劑並不會有聽錢化造鎌大之差異；由本發賴使用之丙 烯酸’均為-般耗之丙_ ’並不需經過純化流似去除阻聚 劑’此可說明本發明之黃變_舰不會受限餘㈣之含 寡限定。 【圖式簡單說明】 【主要元件符號說明】20.5 g/g), the degree of yellowing of the superabsorbent resin was evaluated, and the results are shown in Table 1. Table 1 · Coloring degree (YI value) ----- Before test ----- Test colorimetric change reference example 8.9 56.8 47.9 Example one 9.0 ----- 11.1 2.1 Example 2 8.9 10.9 2.0 Example 8.9 --- 11.2 2.3 Example 4 8.9 10.7 1.8 Example 5 8.9 11.6 2.7 Comparative Example 1 8.9 16.8 7.9 18 201200529 Comparative Example 2 8.9 36.7 27.8 Comparative Example 3 8.9 11.3 2.4 Comparative Example 4 8.9 11.0 2.1 Color of Reference Example Degree change, we can find that the chromaticity change reached 47.9 after two weeks without adding the yellowing inhibitor, and it can be found that the addition of 0.1% by weight of the yellowing inhibitor can be effective from Examples 1 to 5. The effect of preventing the yellowing of the superabsorbent resin is achieved, and the addition of the yellowing inhibitor in the surface crosslinking stage or the surface crosslinking has the effect of preventing the yellowing of the superabsorbent resin, and the super absorbent resin is The chromaticity change after two weeks is about 1,8~2.7. In addition, it can be found from Comparative Example 1 that the yellowing inhibitor described in the CN 1137159C patent is used, and the chromaticity change of the water-absorbent resin is about 7.9 by the inventor's more severe method. The yellowing inhibitor (chrominance change 1.8~2.7) has a larger difference than the financial one; in addition, the result obtained by the second comparative example can clarify the yellowing inhibitor proposed by the claw __51, which is resistant to yellow after the test. The ability to process is also far less than the performance of the present invention. Finally, from the comparative examples 1 and 4, the particle size of the ten water-absorbent resin does not have a large difference in the yellowing inhibitor of the present invention; the acrylic acid used in the present invention is a general consumption. C - ' does not need to pass through the purification stream to remove the polymerization inhibitor' This can explain the yellowing of the invention _ ship will not be limited by the qualifier (4). [Simple diagram description] [Main component symbol description]