201038649 六、發明說明： 【發明所屬之技術領域】 高吸水性樹脂廣泛地運用於農業或園藝方面的水保持劑、建築 中的抗露珠凝結綱及移除石油巾水份的材料，或是_線中的外層水 包覆劑以及衛生用品如尿布、婦女衛生用品、拋棄式的擦巾等。 7 【先前技術】 Ο Ο 技藝界已知的高吸水性樹脂的成分材料有;殿粉_丙婦猜㈣ starchac__丨e)接枝聚合物（日本專利公開公 49(1974)-43,395)，中和之澱粉姻酸接枝聚合物（日本專利公° 51 (1976)·125,468)’ 4化乙觸酸_丙湘嫩物（日本專利公開公報^ 52(1977)-14,689)，水解丙烯腈共聚物或丙_胺共聚物（日本: 昭53 (刪)部9)，及部份中和聚丙稀酸（日本專利公開公= 55(1_)·84,3⑷㈣今高吸水性樹脂之製備方式咖丙烯酸: 酸鹽進行如《麵狀高财_齡最切份也最驗敵益，^ 因為丙烯酸鹽共聚物的補__酸可迅速由商場上購得1製得的二吸 =樹脂具有高的吸水能力，製造成本低廉，故成為最普遍化的高吸:性 聚合丙稀酸及丙烯酸鹽形成高吸水性樹脂的方法可由數種已方 法製得’如祕棘合反應、逆姆浮贼妓應、減聚纽 體噴麗或塗基質场行聚合反鱗方I在這龄法中，逆相^ 洋液聚合反應竭卿合反應必彡細到有機鋪，但是若無法有朗、 控制聚合反應時的«，有機_將造成反&魏溫度錢壓力的增加， 會產生起火現象甚至引發爆炸，進而威脅到操作現場人員的安全以及造成 環境污染_，其成品也有有機溶賴㈣疑慮，再者，制逆相懸浮液 201038649 聚合反應所製造出的高吸水性樹脂，其形狀呈現圓球型，且粒徑不大，使 用於紙尿布時’無法有效的固定於紙漿或其他纖維狀的吸收體上，使用上 十分不便。利用水溶液聚合反應製造高吸水性樹脂，就沒有上述的問題產 生（美國專利彳鄉⑵彳號），水溶液聚合方式是將製造之高吸水性樹脂所 需的水溶性不飽和單體與聚合引發劑，在具有旋轉娜器的容器中進行聚 合反應時，-方面經由麟器的旋轉臂所產生的剪切力，將聚合反應後所 生成的水凝膠體，形成較小的顆粒，如此，提高了生產效率，也可以獲得 可溶出成份少的高吸水性樹脂。 【發明内容】 製造高吸水性樹脂係以引發自由基進行聚合反應，其所需的含酸基 單體除了丙烯酸外，尚可使用其它具有不飽合雙鍵的水溶性單體，如:甲基 丙烯酸、馬林酸、富馬酸、2-丙烯醯胺-2-甲基丙燒續酸等。單體選用不特 定限制只可使用-種，亦可合併錄賴-起仙，亦可視情況需要添加 具有不飽和雙鍵其他親水性的單體，如:丙烯醯胺、f基丙顧胺、丙稀酸 2-烴基乙酿 '甲基丙烯酸2-烴基乙醋、丙烯酸甲酉旨、丙_楚乙醋、二甲胺 丙烯丙烯醯胺、氯化丙烯醯胺基三曱銨等（美國專利4,〇57,52彳號、 4,062,817 號、4,525,527 號、4,286,082 號及 4,295,987 號），但添加量以 不破壞高吸水性樹脂之物性為原則。 在進行自由基聚合反應時，單體水溶液濃度並沒有特別的限制，但 較佳濃度宜控制在重量百分比20wt。/。至55wt%間，適當濃度為3〇wt%至 45wt%之間，濃度在重量百分比2〇wt%以下時，聚合後水凝膠太軟且有黏 ] 生不利機械加工，添加濃度在重量百分比55^%以上，接近飽和濃度，不 易凋配且反應太快反應熱不易控制，不飽和單體水溶液pH值不低於5 〇， + PH低於5.0時，聚合後水凝膠體内殘存單體含量過高，導致高吸水性 201038649 樹脂之物性不佳。 在進行自由基聚合反應前單體水溶 ^ . 中亦可添加水溶性面分子以 降低成本，此專水溶性高分子如：部份卷彳卜< & _ 吾化或元全皂化的聚乙烯醇、聚乙 -醉、聚丙_、聚丙_胺、珊歧粉衍生物如纖維素，丙稀酸 曱基纖維素，乙基纖維素等聚合物；此等水溶性高分子的分子量並不特別 限定’其中較佳的水溶性高分子驗粉、部份4化或完全皂化的聚乙稀醇 等早獨或混合使用。高吸水性樹脂含此等水溶性高分子的添加適當重量百 分比為0至20wt%，但以0至10wto/〇較佳，0 $ ςνΛ/+0/ 议征υ至5wt%尤佳，添加超過2〇wt〇/〇 Ο 時會影響物性，使物性變差。 在進行自由基反應後就可使而吸水性樹脂具有適當交聯度，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適當的添加劑量 在重量百分比0_001wt%至5wt%之間(以反應物總固形份為基準），更適當 的用量重量百分比在0.01wt%至3wt%之間，添加劑量在重量百分比 0_001wt%以下聚合後之水凝膠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，降低樹脂性能。 〇 含酸基單體之羧酸基應該部份中和以控制成品之pH值，使其呈中性 或微酸性，中和所用之中和劑為週期表中鹼金族或鹼土族的氫氧化物或是 碳酸化合物，如：氫氧化鈉、氩氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳 酸氫卸或氨類化合物；中和劑可皁獨使用一種或多種混合使用。含酸基單 體之羧酸基部份中和成鈉鹽或鉀鹽或銨鹽，中和濃度莫耳百分比為 45mol°/〇至85mol%，宜為50mol%至75mol°/。，中和濃度莫耳百分比為 45mol°/〇以下時成品之pH值會偏低，t和濃度莫耳百分比為85mol%以上 時成品之pH值會偏高，成品pH值非呈中性或微酸性時，若不慎與人體 接觸時均不太適合，也較不安全。 201038649 預聚合反應由聚合引發劑的分解產生自由基開始，聚合引發劑可選 用熱分解型引發劑，適合的熱分解型引發劑有過氧化物，如：過氧化氬、 第二丁基過氧化物、過氧化醯胺或過硫酸鹽(銨鹽、鹼金屬鹽)等及偶氮化 合物，如：2_2’-偶氮基雙(2-脒基丙烷)二鹽酸鹽、2.2，-偶氮基雙(N,N_二伸 曱基異丁脒)二鹽酸鹽；亦可使用還原劑使其成為氧化還原型引發劑，如： 酸性亞硫酸鹽、硫代硫酸鹽、抗壞血酸或亞鐵鹽；或將氧化還原型引發劑 和熱分解型引發劑合併使用。魏是氧化還原引發紙進行反應產生自由 基’當自由基娜至單體上㈣«纽應驗行，由於聚合反應進行時 會釋放出大量的歸而使溫度升高，當溫度到賴分解型引發綱分解溫 度時’又會引發第二段熱分解型引發劑的分解，而使整個聚合反應更臻於 元玉般自由基聚合反應引發劑適當用量為重量百分比為〇.〇〇1至Ί〇(以 中和丙稀酸鹽重量為基準）’更適當用量則在重量百分比〇1至5之間，使 用重里百分比D.QG1以下時，反應太慢不繼濟效益；使用重量百分比1〇 以上時’反應太快反應熱不g控制且容$聚合過度*形成凝狀固體。 聚合引發劑也可選用紫外光型引發劑，如：二苯甲嗣、二苯甲_ 生物、2,2_二曱氧基-1,2-二笨基乙烧·*!，、笨偶姻、苯偶姻醚、跌其氧化 填、节基_、樟麟等，經岭外光施加於光引發劑產生自由基進行自 由基聚合反應，或以光引發舰熱分解型或氧化還引發剩，紫外光 照光進行預聚合反應，得到所需的凝膠體。 凝膠體可雜何形式之粉碎機進行粉碎，糾後凝膠體之直徑以 mm以下為宜，以0.05 mm至15〇咖間較佳，粒徑大於2 〇〇晒 之凝膠體難新送回反應財進行再細碎。粒徑議酬以下之凝膠體 進行洪乾、粉碎處理後’易產生成品細粉量提高，粒徑2咖m以上之凝 膠體進仃縣時’容㈣為熱料效果不佳，導致成品在赫單體偏高， 其他物性表現不佳之缺點，_酸鹽_體_粒大小分佈越窄，不僅可 201038649 使凝膠體在烘乾後物性表現達观錄態，而且有册控繼乾的時間及 溫度，篩選完成後再進行烘乾。 上洪乾溫度以溫度富匚至180。〇進行烘乾為宜，供乾溫度i〇〇〇c以下 烘t乞時間太久’不具經濟效益，供乾溫度彻。〇以上供乾做聯劑提早進 订=聯反應’使付賴的錢難巾，目交聯度過高而無法有效的去除殘 存單體，達到降低殘存單體之效果。 Ο201038649 VI. Description of the invention: [Technical field to which the invention pertains] Superabsorbent resins are widely used in water retaining agents for agriculture or horticulture, anti-dew condensation in buildings, and materials for removing water from petroleum towels, or The outer layer of water coating agent in the line and sanitary articles such as diapers, feminine hygiene products, disposable wipes, and the like. 7 [Prior Art] 成分 成分 The constituent materials of the superabsorbent resin known in the artisan are: 宫粉_丙妇猜(4) starchac__丨e) graft polymer (Japanese Patent Publication No. 49(1974)-43,395), Neutralized starch-glycolic graft polymer (Japanese Patent Publication No. 51 (1976) 125, 468) '4-B-Acetate_Binxiang Tender (Japanese Patent Publication No. 52 (1977)-14, 689), hydrolyzed acrylonitrile Copolymer or acrylamine copolymer (Japan: Sho 53 (deleted) part 9), and partially neutralized polyacrylic acid (Japanese Patent Publication No. 55 (1_)·84, 3 (4) (four) Preparation of high water-absorbent resin Acrylic acid: The acid salt is as good as the "the most expensive and the most indifferent to the surface," because the acrylate of the acrylate copolymer can be quickly purchased from the market. High water absorption capacity and low manufacturing cost, so it is the most popular high absorption: the method of polymerizing acrylic acid and acrylate to form a super absorbent resin can be obtained by several methods, such as the secret reaction, the reverse reaction In the age of the thief, the condensed squirting or the smear of the smear or the smear of the smear The reaction must be fine to the organic shop, but if it is impossible to control the polymerization, the organic _ will cause an increase in the pressure of the anti-Wei temperature, which will cause a fire or even an explosion, which threatens the personnel of the operation site. Safety and environmental pollution _, the finished product also has organic solvents (4) doubts, in addition, the reverse-phase suspension 201038649 polymerization produced by the superabsorbent resin, its shape is spherical, and the particle size is not large, use When it is used in paper diapers, it cannot be effectively fixed on pulp or other fibrous absorbents, which is very inconvenient to use. The use of aqueous solution polymerization to produce superabsorbent resins does not have the above problems (US Patent Township (2) nickname) The aqueous solution polymerization method is a method in which a water-soluble unsaturated monomer and a polymerization initiator required for the superabsorbent resin to be produced are polymerized in a vessel having a rotating rotator, and the The shearing force, the hydrogel formed after the polymerization reaction, forms smaller particles, thus improving production efficiency and also obtaining A superabsorbent resin having a small amount of soluble components. [Production] A superabsorbent resin is produced to initiate a polymerization reaction by initiating a radical, and the acid group-containing monomer required may be used in addition to acrylic acid, and other unsaturated doubles may be used. The water-soluble monomer of the bond, such as: methacrylic acid, marinic acid, fumaric acid, 2-propenylamine-2-methylpropionic acid, etc. The monomer can be used without any specific limitation. It can be combined with the singularity, and it is also necessary to add other hydrophilic monomers with unsaturated double bonds, such as: acrylamide, f-propyl amide, acrylic acid 2-hydrocarbyl styrene 2 methacrylic acid 2 - a hydrocarbyl acetoacetate, a propyl acrylate, a propyl acetonitrile, a dimethylamine propylene acrylamide, a chlorinated acrylamide ruthenium amide, and the like (U.S. Patent No. 4, No. 57,52, No. 4,062,817, 4,525,527 No. 4,286,082 and 4,295,987), but the addition amount is based on the principle of not impairing the physical properties of the superabsorbent resin. The concentration of the aqueous monomer solution is not particularly limited in carrying out the radical polymerization reaction, but the preferred concentration is preferably controlled to 20 wt% by weight. /. Between 55wt%, the appropriate concentration is between 3〇wt% and 45wt%, and the concentration is less than 2〇wt% by weight. After the polymerization, the hydrogel is too soft and sticky. The concentration is in the weight percent. 55^% or more, close to saturation concentration, not easy to withstand and react too fast. The reaction heat is not easy to control. The pH value of the unsaturated monomer aqueous solution is not less than 5 〇. When the pH is lower than 5.0, the residual hydrogel remains after polymerization. Excessive body content leads to poor water absorption of the highly absorbent 201038649 resin. In the monomer water solution before the radical polymerization reaction, a water-soluble surface molecule may be added to reduce the cost. The special water-soluble polymer is, for example, a partial roll of a <& _ _ or a full saponified poly Vinyl alcohol, polyethyl-dr-d, poly-propanoid, poly-propanoid, sulphur derivative such as cellulose, cyanoacrylate cellulose, ethyl cellulose and other polymers; the molecular weight of these water-soluble polymers is not In particular, the preferred water-soluble polymer test powder, partially or fully saponified polyethylene glycol, etc., are used alone or in combination. The superabsorbent resin containing such water-soluble polymer is added in an appropriate weight percentage of 0 to 20% by weight, but preferably 0 to 10 wto/〇, 0 ς Λ Λ / + 0 / υ υ to 5% by weight, preferably more than When 2〇wt〇/〇Ο, it will affect the physical properties and make the physical properties worse. After the radical reaction is carried out, the water-absorbent resin can have a proper degree of crosslinking, and the superabsorbent resin colloid has appropriate processability. 'Radical polymerization crosslinking agent. Suitable additive amount is 0-001 wt% to 5 wt% by weight. Between % (based on the total solids of the reactants), a more appropriate amount by weight is between 0.01% by weight and 3% by weight, and the amount of the additive is less than 0_001% by weight. The hydrogel after polymerization is too soft and sticky. Sexually unfavorable mechanical processing, the amount of the additive is too low in water absorption of 5 wt% or more, and the resin property is lowered. The carboxylic acid group of the hydrazine-containing monomer should be partially neutralized to control the pH of the finished product to make it neutral or slightly acidic. The neutralizing agent used for neutralization is an alkali metal or alkaline earth hydrogen in the periodic table. The oxide or the carbonic acid compound, such as: sodium hydroxide, potassium argon oxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, hydrogencarbonate or ammonia compound; the neutralizing agent can be used alone or in combination. The carboxylic acid group of the acid group-containing monomer is neutralized to a sodium salt or a potassium salt or an ammonium salt, and the neutralizing concentration of the molar percentage is from 45 mol / 〇 to 85 mol %, preferably from 50 mol % to 75 mol ° /. When the concentration of neutralization concentration is below 45mol ° / 〇, the pH value of the finished product will be low. When the percentage of concentration of m and concentration is 85mol% or more, the pH value of the finished product will be higher, and the pH value of the finished product is not neutral or micro. When it is acidic, it is not suitable if it is inadvertently contacted with the human body, and it is also less safe. 201038649 Prepolymerization begins with the decomposition of a polymerization initiator to generate a radical. The polymerization initiator may be a thermally decomposable initiator. Suitable thermal decomposition initiators have peroxides such as argon peroxide and second butyl peroxidation. , guanidinium peroxide or persulfate (ammonium salt, alkali metal salt), etc. and azo compounds, such as: 2_2'-azobis(2-amidinopropane) dihydrochloride, 2.2,-azo a double (N,N-di-decylisobutyl) dihydrochloride; a reducing agent can also be used as a redox initiator, such as: acidic sulfite, thiosulfate, ascorbic acid or ferrous iron a salt; or a combination of a redox type initiator and a thermal decomposition type initiator. Wei is a redox-initiated paper that reacts to generate free radicals. 'When the free radicals are on the monomer (4), the new ones should be tested. As the polymerization proceeds, a large amount of carbon will be released, and the temperature will rise. When the temperature is decomposed, it will cause the decomposition of the second stage thermal decomposition type initiator, and the whole polymerization reaction will be more suitable for the elemental polymerization initiator. The appropriate amount is 重量.〇〇1 to Ί〇 (Based on the weight of neutralized acrylate) 'More suitable amount is between 至1 and 5 by weight. When the weight percentage is below D.QG1, the reaction is too slow and not beneficial; use weight percentage above 1〇 When the reaction is too fast, the reaction heat is not controlled and the amount of polymerization is excessive* to form a condensed solid. The polymerization initiator may also be selected from an ultraviolet light type initiator, such as: benzophenone, benzophenone _ biological, 2,2 dioxin-1,2-diphenyl ketone**, Marriage, benzoin ether, drop of its oxidative filling, nodal base _, unicorn, etc., the external light applied to the photoinitiator to generate free radicals for free radical polymerization, or photo-induced thermal decomposition or oxidation Remaining, ultraviolet light is prepolymerized to obtain the desired gel. The gel can be pulverized by any type of pulverizer. The diameter of the gel is preferably less than mm, preferably between 0.05 mm and 15 〇, and the particle size is greater than 2 〇〇. Send back the reaction money and then shred it. The gel body with the following particle size is subjected to flooding and pulverization treatment, and it is easy to produce a fine powder of the finished product. When the gel with a particle size of 2 g or more is in the county, the capacity is not good, resulting in poor heat effect. The shortcomings of the finished product in the high monomer, other physical properties are not good, the narrower the distribution of _acid_body_particle size, not only 201038649, the physical properties of the gel after drying are up to the state of record, and there is a book control Dry time and temperature, and then dry after screening. The upper flooding temperature is rich in temperature to 180. 〇 Drying is appropriate, for dry temperature below i〇〇〇c. Drying for too long. ‘No economic benefit, dry temperature. 〇 供 〇 〇 〇 提 提 提 = 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联 联Ο
、乾燥後進行粉碎、筛選固定粒徑，再進行表面交聯劑塗覆處理。筛 L固定粒彳工以a〇6mm至lGQmm間為宜，以Q1Qmm至Q咖瞧間較 ，，粒徑_晒卩下細粉使成品粉塵提高，粒徑i 〇〇晒以上粒子使成 品吸水速率變慢，丙烯_聚合物_粒大小分佈越窄越好。 高吸水性樹脂為不轉之親水性聚讀，繼内部財均勻性的架 橋結構、’-般為了改善品質如：提高吸收速率、提高膠體強度、提高抗結 塊陡、液體細±等，會在旨的表面再作進—辣橋，此表面交聯處理 即利用具有能與酸基反應之多官能基交·，在此之统有許多專利提 出’如.分散兩吸水性樹脂與交聯劑於有機溶射進行表面交聯處理 (广A姻繼、Jp_A姻防、Jp姻26〇2、 A58 117222)’使用無機粉直接將交卿般卿溶液混人高吸水性樹 脂t(JP-A60·纏6、JP嫌255814)，添加交聯做 -1-113406)，使用有機溶劑、水及多元醇進行表面處理 A-1-292004、美國專利6346569號）使用有機溶液、水、趟化合物 JPA-2-153903)等;這些表面處理的方法雖能提高壓力下吸水倍率， 但恐造成保持力下降過多料隨果，降财際應狀性能。〇 二▲根據本發明，於表面處理時亦能一併使用的交聯劑為多元醇如：丙 二酵' 乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、I〆丁二醇、 7 201038649 二脛基曱基丙院、山梨醇等；或多元胺如：乙二胺、二乙二胺、三乙二胺、 紅二胺’·或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 - '、以二醇聚縮水甘_、乙二醇二縮水甘油醚、二乙二醇二縮水甘油 祕、聚乙二醇二縮水甘_、雙丙三醇聚縮水甘_等；亦可使用碳酸亞 烴酿如^二醇碳_、4•甲基_1|3_二氧雜環戍m 4,5_m3_ 氧雜％戊燒-2-嗣、4,4-二甲基_1|3_二氧雜環戊烧_2_酮、*乙基_ι 3_二氧 雜環戊垸-2-酮、仏氧雜環己紋酮、4紅甲基氧雜環己烧_2_ 酮或1,3-二氧雜環庚焼_2,等。交聯劑的用法可單獨使用或兩種以上混合 使用。交聯劑的適當添加劑量在重量百分比〇 〇〇鳩至_%之間(以反 應物總，形份為基準），更適當的用量在〇 〇〇5禮。至祕之間，交聯劑 量在重量百分比㈣彳赠似下時紐顯出效果，㈣劑添加劑量 罝百刀比10wt%以上時，吸水性太低，降低樹脂性能。 【擬解決之問題】 T者環保意識抬頭，衛生用品等吸水性樹s旨製品處理方式常常採用 燃燒或是土壌掩埋，且聚丙烯系的吸水性_雖然價格便宜，但卻無法被 土壤有效地分解，造成環境的重大諸。具有生物可分觸的吸水性樹醋 長久以來—錄研絲，包括經由聚t谷紐倾轉減合物（日本專 利特開平11-343339，特開平7_224163，特開平7_3〇〇563等）共同反應所 生產的吸水性樹酯；或多醣水凝朦體（美國專利65 國大陸專利公開⑽410463A號）、雪蓮果（中國大陸專利=魔料（中 C_4=544A號）等天然物質作為交聯劑。以上作法雖有助於吸水性樹醋廢 棄物的^理’但多醣類化合物處理過程娜，製作出的高吸水性樹醋過於 軟爛’性能低落，無法達到現今衛生用品所需功能。且聚个谷氨酸製程 須以培養财讀難動放躲雜，且生麵射必紐 但增加生產成本且程序複雜許多。 201038649 【解決問題之技術手段】 有鑑於此，本發明提供—種新穎製造方法，即使用-種生物可分解 里之交聯劑就可以製造出具有高度易分解的高吸水性樹脂，不但可達到 保綠處理的結果’亦不需要再次添購格外設備而增加生產成本。< 本發明的主要技術特徵在於進行自由絲合反應前先添加内部交聯 劑於未反應單體溶液中，此自由基聚合反應交聯劑選自具有至少為兩個之 不飽和雙鍵的化合物或環氧掛合物，所述之交聯劑令親水基團的分子 〇 量比例(Hydr〇philic ProP〇rtion index，簡稱 HPI 值)須在 65%以上，75% 以上更佳，交侧結構巾之賴和雙鍵為末端魏，·樹敝合物末端 具有環氧樹酯化合物。 交聯劑親水基BJ分子量轉HPI)=交聯舰水基團分子量/交聯劑 分子量x1QQ°/。’其交聯劑如：聚乙二醇二丙烯酸酯(n>13)，聚丙二醇二丙 烯酸酯(n>13)，乙氧化三烴甲基丙烷三丙烯酸酯(n=1〇~35)、聚乙二醇二縮 水甘油_>9)、丙二醇二縮水甘油_>9)、甘油义士二縮水甘油鍵、山 梨醇聚縮水甘油鍵、聚丙三醇聚縮水甘油醚、乙二醇二縮水甘油醚、二乙 二醇二縮水甘油鰱及雙丙三醇聚縮水甘油輕等。 依上交聯劑親水機團的分子量比例在65〇/0以上製成的本發明高度 易分解的高吸水性樹酯，在已知評估高吸水性樹酯分解的方法中，已有使 用L-抗壞血酸或在生理鹽水溶解的高吸水性樹酯測量可溶份組成的量 (JP-A05-247221、JP-A-07-059813、JP-A-08-337726)，本發明參考上述 專利方法，以含有0.005wt%濃度的L-抗壞血酸的生理鹽水溶液使高吸水性 樹酯溶脹至30g/g ’經過3小時與24小時後進行膠體強度測試，得 之膠體強度不大於180g ; 24小時後的體強度低於8〇g ^由此， 9 201038649 本發月之目的在提供—種高度易分解的高吸水雜脂的製造方法，該 方法包括： 1. 使種s I基單體的水溶性不飽和單體，中和比率在#至筘莫耳 %之祀’不飽和單體水溶液的濃度在2〇至％重量份之範圍。 2. 添^父聯刈選自具有至少為兩個之不飽和雙鍵的化合物或環氧 樹S曰化D物’其交聯劑之親水基團的分子量比率⑺p丨值)在咖以 上’ 75°/〇以上更佳。 3·賴後的鱗體，以溫度·至露c範圍的熱風乾燥、粉碎、 篩選成半成品。 4_將半成品再進行表面交聯處理。 本發明之上述技鱗徵’侧用該交侧的親水基團的分子量比例 來製造出生物可分解型的高财性細旨，魏水基醜目制—定程度， 親水性大巾胃提升，以具有此特性之交聯賴製成的高吸水性樹醋以 0_005wt/〇L !几壞血酉夂的生理鹽水溶液溶脹至3〇的後，該交聯劑具有高度 的水溶性，會因為尿液、土壌、環境__級性f造成高吸水性樹醋 的分解。 本發明以凝賴強额為狀高财性脑的績贿，係伽德〇 ±0.001g兩吸水性樹S旨緩緩加入3〇m| 〇 9%生理鹽水+〇施％ ^抗壞血 酸，放入電磁餅機·]分鐘，靜置3小時/24小時後，將燒杯置於 STEVENS膠體強度測定儀之平台上，使其正中央正對懸吊柱管。 STEVENS膠體強度測定儀裝置面板上之djgit歸零，設定懸吊柱管之落下 速度為I.Omm/sec，落下距離為25mm。歌結果會顯示於面板上。 本發明之高吸水性樹脂的壓力下吸水倍率，係彻受壓吸收重(壓力 負荷：2GgW)來測定，受壓吸收量係根據_專利Q33946i a號說明書 10 201038649 第七頁令所描述的方法測定； 將初始重量的高吸水性樹腊放在 重量所得數值除以高吸 以20gW的勤，接著將_體置__=，，對粉體加 水性樹脂吸收_的生理鹽水一小時，再將測吸水y、㈣上，讓此高吸 水性樹脂的重量，即得受壓吸收重數值。 ’去除最高值以 本發明之高吸水性細旨的保持力，細五次量测結果 及最低值後，取平均值利用茶袋試驗法測S; ❹ 將0.2g的高吸水性樹脂裝在茶袋裡，並浸泡於〇9%的隊丨水溶液 3〇分鐘’然後將此浸泡後的茶袋置於離心機(重力加速度=25〇g)令離心三 /刀知後秤;t。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。 【實施方式】 以下以實施例詳細說明本發明，但本發明之範圍不受此實例所限制。 貫施例一： 1) 取48%氫氧化納水溶液364_5g緩慢加入450g丙浠酸及486.2g的水的 2000c.c圓錐瓶中，氫氧化鈉/丙烯酸的滴加比率在0.85至0.95範圍内， 滴加時間為2小時，並保持瓶内中和反應系統的溫度在20°C至40°C範 圍内；此時得單體濃度42wt%水溶液，其中7〇mol%(莫耳比)丙烯酸部 份中和為丙烯酸鈉。After drying, the mixture is pulverized, the fixed particle diameter is screened, and the surface crosslinking agent coating treatment is performed. Screening L fixed grain is suitable for a〇6mm to lGQmm, between Q1Qmm and Q curry, the particle size _ drying fine powder to improve the finished dust, the particle size i 〇〇 drying the particles to make the finished product absorb water The rate is slower, and the propylene-polymer_particle size distribution is as narrow as possible. The superabsorbent resin is a non-transfer hydrophilic poly-reading, followed by a bridge structure of internal financial uniformity, '- in order to improve the quality, such as: increasing the absorption rate, increasing the strength of the colloid, increasing the anti-caking steepness, the liquid fine ±, etc. In the surface of the purpose - Spicy bridge, the surface cross-linking treatment uses a multi-functional group capable of reacting with an acid group. There are many patents in this paper, such as dispersing two water-absorbent resins and cross-linking. The agent is subjected to surface crosslinking treatment by organic spraying (Guang A A, Jp_A Marriage Prevention, Jp Marriage 26〇 2, A58 117222). The inorganic powder is directly mixed with the superabsorbent resin t (JP-A60) using inorganic powder. · entangled with 6, JP 255,814), added cross-linking to make -1-113406), surface treatment with organic solvent, water and polyol A-1-292004, US Patent No. 6,346,569) using organic solution, water, hydrazine compound JPA -2-153903) Etc.; Although these surface treatment methods can increase the water absorption rate under pressure, it is feared that the retention force will decrease and the yield will be reduced. According to the present invention, the crosslinking agent which can also be used together in the surface treatment is a polyhydric alcohol such as: propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, I-butanediol, 7 201038649 dimercaptopropyl propylamine, sorbitol, etc.; or polyamines such as: ethylenediamine, diethylenediamine, triethylenediamine, reddiamine'· or have two or two More than one epoxy group compound such as: sorbitol polyglycidol - ', diol polycondensation _, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl secret, polyethylene glycol dihydrate _ , propylene glycol polycondensate _ _, etc.; can also use carbonic acid hydrocarbons such as diol glycol _, 4 • methyl 1 | 3 dioxo oxime m 4, 5 _ m3 oxax pentane-2 -嗣,4,4-dimethyl-1|3_dioxolidine-2-one, *ethyl_ι 3_dioxol-2-one, anthracene A ketone, 4 red methyloxohexan-2-ol or 1,3-dioxepane-2, and the like. The crosslinking agent may be used singly or in combination of two or more. The appropriate amount of the cross-linking agent is between 重量 〇〇鸠 and _% (based on the total amount of the reactants, the form), and a more appropriate amount is used in 〇 〇〇 5 礼. Between the secret and the secret, the amount of the cross-linking agent is effective in the weight percentage (4), and the amount of the additive is (4). When the amount of the additive is more than 10% by weight, the water absorption is too low, and the resin property is lowered. [Problem to be solved] T people's awareness of environmental protection, sanitary articles and other water-absorbing trees are often treated by burning or soil burial, and the water absorption of polypropylene is cheap, but it cannot be effectively soiled. Decomposition, causing major environmental problems. The bio-separable water-absorbing tree vinegar has long been recorded - including the poly-t谷纽 tilting compound (Japanese Patent Laid-Open No. 11-343339, JP-A-7-224163, Special Kaiping 7_3〇〇563, etc.) The water-absorbent resin produced by the reaction; or the polysaccharide hydrogel (US Patent No. 65, Continental Patent Publication (10) 410463A), and the natural substance such as yacon (Chinese patent = magic material (C_4 = 544A)) as a crosslinking agent Although the above method is helpful for the water-absorbing vinegar waste, but the process of treating the polysaccharide compound, the highly absorbent tree vinegar produced is too soft and has low performance, and cannot meet the functions required for today's sanitary products. Moreover, the process of collecting glutamic acid must be difficult to move and cultivate, and the production of raw materials is increased, but the production cost is complicated and complicated. 201038649 [Technical means for solving the problem] In view of this, the present invention provides The novel manufacturing method, that is, the use of a biodegradable cross-linking agent to produce a highly water-absorptive resin which is highly decomposable, can not only achieve the result of green preservation treatment, and does not need to be added again. Adding extra equipment to increase production cost. < The main technical feature of the present invention is that an internal crosslinking agent is added to the unreacted monomer solution before the free silking reaction, and the radical polymerization crosslinking agent is selected from at least a compound of two unsaturated double bonds or an epoxy compound, wherein the cross-linking agent has a molecular weight ratio (Hydriphilic ProP〇rtion index, referred to as HPI value) of more than 65%, 75 % or more is better, the cross-linked structural towel and the double bond are terminal Wei, and the end of the tree chelate has an epoxy resin compound. Crosslinking hydrophilic group BJ molecular weight to HPI) = crosslinked ship water group molecular weight / Crosslinker molecular weight x1QQ ° /. 'The crosslinking agent is, for example, polyethylene glycol diacrylate (n > 13), polypropylene glycol diacrylate (n > 13), ethoxylated trihydrocarbylmethylpropane triacrylate (n = 1 ~ ~ 35), Polyethylene glycol diglycidyl _ > 9), propylene glycol diglycidyl _ > 9), glycerol yoke diglycidyl bond, sorbitol polyglycidyl bond, polyglycerol polyglycidyl ether, ethylene glycol condensed water Glycerol ether, diethylene glycol diglycidyl hydrazine and diglycerin polyglycidol are light. The highly easily decomposable superabsorbent resin of the present invention prepared by the molecular weight ratio of the hydrophilic group of the cross-linking agent of 65 Å/0 or more is used in the method for evaluating the decomposition of the superabsorbent resin. - Ascorbic acid or a highly water-absorptive resin dissolved in physiological saline to measure the amount of soluble component (JP-A05-247221, JP-A-07-059813, JP-A-08-337726), the present invention is referred to the above patent method The superabsorbent resin was swollen to 30 g/g with a physiological saline solution containing a concentration of 0.005 wt% of L-ascorbic acid. After 3 hours and 24 hours, the colloid strength test was performed to obtain a colloid strength of not more than 180 g; after 24 hours The bulk strength is less than 8 〇g ^. Thus, the purpose of this month is to provide a highly self-decomposing method for the manufacture of highly water-absorbent hetero-lipids, which comprises: 1. Dissolving the water of the species s I-based monomer For the unsaturated monomer, the neutralization ratio is in the range of from 〇 to % by weight of the aqueous solution of the unsaturated monomer. 2. The addition of a parent to a compound having at least two unsaturated double bonds or an epoxy tree S-deuterated D's molecular weight ratio (7) p丨 of the hydrophilic group of the crosslinking agent is above the coffee' More preferably 75°/〇. 3. The scales after drying are dried, pulverized, and screened into semi-finished products by hot air in the range of temperature to dew. 4_ The semi-finished product is subjected to surface cross-linking treatment. The above-mentioned technical scale of the present invention uses the molecular weight ratio of the hydrophilic group on the side to produce a biodegradable type of high-yield fine-grained, Wei Shui-based ugly-predetermined degree, hydrophilic big towel stomach lift, After the superabsorbent vinegar having the cross-linking property of this property is swollen to 3 以 with a physiological saline solution of 0_005wt/〇L! several bad blood, the cross-linking agent has high water solubility, which is due to urine. Liquid, soil, and environment __ grade f cause decomposition of highly absorbent tree vinegar. The invention is characterized by a strong stagnation of a high-yield brain, which is a 8000g two-absorbent tree S. Slowly added 3〇m| 〇9% physiological saline + %%% ascorbic acid, put Into the electromagnetic cake machine ·] minutes, after standing for 3 hours / 24 hours, place the beaker on the platform of the STEVENS colloidal strength tester, so that the center is facing the suspension column tube. The djgit on the panel of the STEVENS colloidal strength tester is zeroed, and the drop speed of the suspension column tube is set to I.Omm/sec, and the drop distance is 25 mm. The song results will be displayed on the panel. The water absorption capacity under pressure of the superabsorbent resin of the present invention is measured by the pressure absorption weight (pressure load: 2 GgW), and the pressure absorption amount is according to the method described in the Japanese Patent Publication No. Q33946i No. 10 201038649, page 7 Determination; the initial weight of the superabsorbent wax is placed in the weight obtained by dividing the high absorption by 20gW, then the body is set to __=, and the powder is added with the aqueous resin to absorb the physiological saline for one hour, and then The water absorption y, (4) will be measured to give the weight of the superabsorbent resin, that is, the pressure absorption weight value. 'Removal of the highest value with the retention of the high water absorption of the present invention, after five measurements and the lowest value, the average value is measured by the tea bag test method; ❹ 0.2 g of the super absorbent resin is placed in the tea bag Inside, and soaked in 〇 9% of the team 丨 aqueous solution for 3 ' ' then place the soaked tea bag in a centrifuge (gravity acceleration = 25 〇 g) so that the centrifuge three / knife know the scale; t. The obtained value is first subtracted from the weight of the blank group tea bag which is not filled with the super absorbent resin (operating in the same step) and then divided by the weight of the polymer to obtain the retention value. [Embodiment] Hereinafter, the present invention will be described in detail by way of examples, but the scope of the invention is not limited by this example. Example 1: 1) 48% sodium hydroxide aqueous solution 364_5g was slowly added to 450g of propionic acid and 486.2g of water in a 2000c.c conical flask. The sodium hydroxide/acrylic acid dropping ratio was in the range of 0.85 to 0.95. The dropping time is 2 hours, and the temperature of the neutralization reaction system in the bottle is maintained in the range of 20 ° C to 40 ° C; at this time, a monomer concentration of 42 wt% aqueous solution is obtained, wherein 7 〇 mol% (mole ratio) of the acrylic portion The neutralization is sodium acrylate.
2) 加入2.25g的乙氧化三烴甲基丙烷三丙烯酸酯（n=14)(Aldrich 41219-8) , HPI值為67.54%。中和的丙烯酸溶液，並維持溫度於20°C 左右。 11 201038649 3) 再加入〇.〇48g雙氧水，〇 6g亞疏酸氳鈉及〇.6g過琉酸铵’並使用均質 乳化機(廠牌：IKA，型號T25 Basic，轉速=16〇〇〇rPm)攪拌5秒鐘以引 發反應’得一不透明狀不飽和單體水溶液。 4) 待不透明狀不飽和單體水溶液形成水凝膠體後’利用切式粉碎機將反應 後的凝膠體切碎，並筛選出粒徑大小為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0.1mm〜0.85mm固定粒徑， 得粉狀高吸水性樹脂。 6) 秤取此高吸水性樹脂1〇〇g，加入乙二醇碳酸酯/水/曱醇==1/1/1(重量比) 溶液3.6g，以215°C溫度加熱處理10分鐘，即得高吸水性樹脂，茶袋 保持力為30_8g/g，20g/cm2壓力下吸水倍率27.5g/g，3小時/24小時凝 膠體強度為112/68g。 實施例二： 重覆實施例一’於步驟2)中加入3.38g的乙氧化三烴曱基丙烷三丙烯酸酯 (n=14)，其餘同實例一。茶袋保持力為28 12g/g，2〇g/cm2壓力下吸水 倍率25.92g/g ’ 3小時/24小時膠體強度為i58/65g。 實施例三： 重覆實施例一，但中和度提高至75mol%。其餘同實例一，得高吸水 性樹脂，茶袋保持力為39 25g/g , 2〇g/cm2壓力下吸水倍率16 85g/g，3 小時/24小時膠體強度為95/38g。 實施例四： 重覆實施例二’於步驟2)中將乙氧化三煙甲基丙烧三丙烯賴(n=14) 改為2.7g聚乙二酵二曱基丙烯酸酯⑺=13)㈧伽⑶，455〇〇_8)，Hp丨值為 12 201038649 80_38。/〇，得高吸水性樹脂，茶势仅姓士 * _ 衣保持力為41.38g/g，20g/cm2壓力下吸水 倍率13.27g/g，3小時/24小時膠體強度為議知 實施例五： 重覆實施例四，於步驟2)加人48g %乙二醇二曱基丙稀酸醋 (n=13) ’得高性能高吸水性樹脂’茶袋保持力為32 95g/g ，20g/cm2 壓力 下吸水倍率2G.37g/g ’ 3小時/24小時顧強度為_3g。 實施例六： 〇 重覆實施例-，但在步驟6)改以1,3丙二醇/水/甘油=1/1/1(重量比) 溶液2.9g ’以175°C溫度加熱處理58分鐘，得高性能高吸水性樹脂，茶 袋保持力為24.68g/g，20g/cm2壓力下吸水倍率13 68g/g，3小時/24小 時膠體強度為105/49g。 比較例一： 重覆實施例-’於步驟2)中改加入1 1g的聚乙二醇二τ基丙稀酸酿 (n=3)(Aldrich ’ 47562_9)，HPI值為51.16%，得高性能高吸水性樹脂，茶 # 1 袋保持力為18.68g/g，20g/cm2壓力下吸水倍率i9 68g/g，3小時/24小 時膠體強度為.285/116g。 比較例二： 重覆實施例一，於步驟2)中改加入〇_45g聚丙二醇二縮水甘油醚 (n=2)( Aldrich，40757-7)，HP丨值為54.03%，得高吸水性樹脂，茶袋保 持力為20.18，0cm2壓力下吸水倍率18.38 , 3小時/24小時膠體強度為 315/180g 〇 比較例三: 13 201038649 重覆實施例一，於步驟2)中改加入0.45g聚乙二醇二縮水甘油醚 (n=1)( Aldrich，40907-3)，HPI值為22.43%，得高吸水性樹脂，茶袋保 持力為19.28，20cm2壓力下吸水倍率15.79，3小時/24小時膠體強度為 389/163g。 比較例四： 重覆比較例三，於步驟2)中改加入0.38g聚乙二醇二縮水甘油醚 (n=1)( Aldrich，40907-3)，HPI值為22.43%，得高吸水性樹脂，茶袋保 持力為26.65，20cm2壓力下吸水倍率19.28，3小時/24小時凝膠體強度 為 295/147g。 【圖式簡單說明】 【主要元件符號說明】 142) 2.25 g of ethoxylated trihydrocarbylmethylpropane triacrylate (n = 14) (Aldrich 41219-8) was added, and the HPI value was 67.54%. Neutralize the acrylic solution and maintain the temperature at around 20 °C. 11 201038649 3) Add 〇.〇48g hydrogen peroxide, 〇6g sodium sulfite and 〇.6g ammonium perrhenate' and use homogenizer (label: IKA, model T25 Basic, speed = 16〇〇〇rPm The mixture was stirred for 5 seconds to initiate the reaction to obtain an aqueous solution of an opaque unsaturated monomer. 4) After the aqueous solution of the opaque unsaturated monomer is formed into a hydrogel body, the gel after the reaction is chopped by a cutter mill, and a gel having a particle size of 2 mm or less is selected. 5) Drying at a temperature of 130 ° C for 2 hours; screening a fixed particle diameter of 0.1 mm to 0.85 mm by a sieve to obtain a powdery superabsorbent resin. 6) Weigh 1 〇〇g of this superabsorbent resin, add 3.6 g of glycol carbonate / water / decyl alcohol = 1 / 1 / 1 (weight ratio) solution, heat treatment at 215 ° C for 10 minutes, That is, a highly water-absorptive resin having a holding power of 30_8 g/g, a water absorption ratio of 27.5 g/g under a pressure of 20 g/cm 2 and a gel strength of 112/68 g at 3 hours/24 hours was obtained. Example 2: Example 1 was repeated. In step 2), 3.38 g of ethoxylated trihydrocarbamidol propane triacrylate (n = 14) was added, and the remainder was the same as in Example 1. The tea bag retention was 28 12 g/g, and the water absorption rate under a pressure of 2 〇g/cm 2 was 25.92 g/g '3 hours/24 hours of colloidal strength i58/65 g. Example 3: Example 1 was repeated, but the degree of neutralization was increased to 75 mol%. The same as in the first example, a highly water-absorptive resin was obtained, the tea bag retention force was 39 25 g/g, the water absorption ratio under the pressure of 2 〇g/cm 2 was 16 85 g/g, and the colloidal strength at 3 hours/24 hours was 95/38 g. Example 4: Repeating Example 2 in step 2), changing acetyl trimethyl methacrylate tripropylene hydride (n=14) to 2.7 g polydiacetonitrile dimercapto acrylate (7)=13) (eight) Gamma (3), 455〇〇_8), Hp丨 value is 12 201038649 80_38. / 〇, to obtain a highly water-absorbent resin, the tea potential only surname * _ clothing retention force of 41.38g / g, 20g / cm2 under water pressure absorption ratio of 13.27g / g, 3 hours / 24 hours colloidal strength is known as the fifth embodiment : Repeat step 4, in step 2) add 48g% ethylene glycol dimercapto acrylate vinegar (n = 13) 'to obtain high performance super absorbent resin' tea bag retention of 32 95g / g, 20g / The water absorption capacity under the pressure of cm2 is 2G.37g/g '3 hours/24 hours, the strength is _3g. Example 6: 〇 Repeated Example -, but in step 6) changed to 1,3 propylene glycol / water / glycerol = 1 / 1 / 1 (by weight) solution 2.9g 'heated at 175 ° C temperature for 58 minutes, A high-performance superabsorbent resin was obtained, the tea bag retention force was 24.68 g/g, the water absorption ratio under the pressure of 20 g/cm 2 was 13 68 g/g, and the colloidal strength at 3 hours/24 hours was 105/49 g. Comparative Example 1: In the repeated example - 'in step 2), 11 g of polyethylene glycol di-t-butyl acrylate acid (n = 3) (Aldrich ' 47562_9) was added, and the HPI value was 51.16%. The performance is high water-absorbent resin, the tea #1 bag retention force is 18.68 g/g, the water absorption ratio under the pressure of 20 g/cm2 is i9 68 g/g, and the colloid strength is 3.285/116 g at 3 hours/24 hours. Comparative Example 2: By repeating Example 1, in step 2), 〇_45g of polypropylene glycol diglycidyl ether (n=2) (Aldrich, 40757-7) was added, and the HP enthalpy value was 54.03%, resulting in high water absorption. Resin, tea bag retention force is 20.18, water absorption ratio under pressure of 18.cm2 is 18.38, 3 hours/24 hour colloidal strength is 315/180g 〇Comparative Example 3: 13 201038649 Repeating Example 1, in step 2), add 0.45g poly Glycol diglycidyl ether (n=1) (Aldrich, 40907-3), with a HPI value of 22.43%, a highly water-absorbent resin, a bag retention of 19.28, a water absorption ratio of 15.79 at 20 cm2, and a colloid of 3 hours/24 hours. The strength is 389/163 g. Comparative Example 4: Repeating Comparative Example 3, in step 2), 0.38 g of polyethylene glycol diglycidyl ether (n=1) (Aldrich, 40907-3) was added, and the HPI value was 22.43%, resulting in high water absorption. Resin, tea bag retention force was 26.65, water absorption rate under the pressure of 20 cm2 was 19.28, and gel strength was 295/147 g at 3 hours/24 hours. [Simple description of the diagram] [Explanation of main component symbols] 14