UV固化丙烯酸粉末涂料的制備

1、UV固化丙烯酸粉末涂料的制備韋麗玲,魯建民,劉亞康,王猛(北京化工大學(xué)材料科學(xué)與工程學(xué)院,100029摘要:以環(huán)氧型聚丙烯酸酯-甲基丙烯酸酯樹(shù)脂為光固化樹(shù)脂,Irgacure2959、Irgacure651、Irgacure184等為光引發(fā)劑制得了UV固化丙烯酸粉末清漆,研究了單組分和雙組分光引發(fā)劑種類及用量對(duì)固化程度和漆膜性能的影響,探討了固化工藝。結(jié)果表明,采用3%的Irgacure2959單組分光引發(fā)劑或115%Irgacure2959和115%Irgacure651復(fù)合光引發(fā)劑體系,130下流平10m in,固化30s,所得涂膜具有較佳的綜合性能。關(guān)鍵詞:UV固化;丙烯酸粉末涂料;光引

2、發(fā)劑;清漆;涂膜性能中圖分類號(hào):T Q63016文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):0253-4312(200507-0025-030引言紫外光(UV固化粉末涂料是一項(xiàng)最新的粉末涂料技術(shù),在歐洲已處于市場(chǎng)開(kāi)發(fā)的早期階段。它是一項(xiàng)將傳統(tǒng)粉末涂料和UV固化技術(shù)相結(jié)合的新技術(shù),具有無(wú)VOC排放、節(jié)省能源(耗能僅為熱固化粉末涂料的1/51/10、固化速度快(01110s、生產(chǎn)效率高、適合流水線生產(chǎn)、適合涂覆熱敏基材等優(yōu)點(diǎn),雖然目前所有的UV涂料只占市場(chǎng)份額的6%1,但市場(chǎng)發(fā)展?jié)摿艽?。UV固化粉末涂料由光固化樹(shù)脂、光引發(fā)劑、顏料、填料、助劑等組成。光固化樹(shù)脂是UV固化粉末涂料的主要成膜物,是決定涂料性質(zhì)和涂膜性

3、能的主要成分。而光引發(fā)劑是成膜物的重要組成部分,它使大分子交聯(lián)固化,賦予其更好的力學(xué)強(qiáng)度。本文以自制的環(huán)氧型聚丙烯酸酯-甲基丙烯酸酯樹(shù)脂為光固化樹(shù)脂,探討單組分和雙組分光引發(fā)劑體系種類、用量對(duì)固化程度和漆膜性能的影響,通過(guò)選擇適當(dāng)?shù)墓袒に?制得了具有較佳綜合性能的UV固化丙烯酸粉末涂料。1實(shí)驗(yàn)部分1.1原料Irgacure2959、Irgacure651、Irgacure184:Ciba Geigy 產(chǎn)品;二苯甲酮、米氏酮:化學(xué)純,上海群力化工廠;液體流平劑等其他助劑均為工業(yè)品。感光性樹(shù)脂為實(shí)驗(yàn)室自制,由甲基丙烯酸與G MA類丙烯酸樹(shù)脂3反應(yīng)制得4,相對(duì)分子質(zhì)量30004000,碘值23 2

4、7g/100g樹(shù)脂,軟化點(diǎn)9815。1.2UV固化丙烯酸粉末涂料的制備與固化將光引發(fā)劑、液體流平劑、其他助劑加入溶有感光性樹(shù)脂的反應(yīng)瓶中,升溫?cái)嚢枋蛊涑浞只旌?而后在高真空下脫除低沸點(diǎn)溶劑,待冷卻后將其粉碎,180目過(guò)篩,即得到符合要求的UV固化丙烯酸粉末涂料。同時(shí),取馬口鐵板除銹去油,用粉末噴涂試驗(yàn)機(jī)(HV8080H型,北京盛域王靜電設(shè)備有限公司將粉末噴涂于其上,將馬口鐵板置于烘箱中在120 140下流平10m in,然后在紫外光固化機(jī)(GY1UV500W/II(S,保定特種光源電器廠上輻照30s使涂膜固化。1.3涂膜性能測(cè)試光澤、硬度、沖擊性、流平性分別按國(guó)家標(biāo)準(zhǔn)G B/ T9754198

5、8、G B/T67391996、G B/T17311993、G B17501979進(jìn)行測(cè)試。采用劃格法測(cè)定涂膜附著力。耐溶劑性以丙酮浸泡24h進(jìn)行測(cè)試。固化程度采用溶劑提取法測(cè)定。取約500mg涂膜(mo,用46層擦鏡紙包裹,在索氏提取器中用甲苯提取24h,隨后置于紅外燈下干燥至恒質(zhì)量,稱質(zhì)量(m,按如下式計(jì)算:固化程度=m/mo×100%5。2結(jié)果與討論2.1單組分光引發(fā)劑對(duì)涂膜性能的影響光引發(fā)劑能夠吸收紫外光輻射的能量,產(chǎn)生引發(fā)聚合反應(yīng)的活性中間體,它是紫外光固化體系中必不可少的組分,對(duì)整個(gè)體系的固化速率起著關(guān)鍵作用。不同光引發(fā)劑的光引發(fā)效果不同,光引發(fā)劑種類對(duì)固化程度與涂膜性能

6、的影響見(jiàn)表1。從表1可以看出,當(dāng)不使用光引發(fā)劑時(shí),粉末清漆基本沒(méi)有發(fā)生固化反應(yīng),在所使用的幾種光引發(fā)劑中,I gracure2959、I gra2 cure651、I gracure184的光引發(fā)效果都較高,其中I gra2第35卷第7期涂料工業(yè)Vol.35No.7 2005年7月P A I N T&COATI N GS I N DUSTRY Jul.2005cure2959的光固化程度最高。表1單組分光引發(fā)劑種類對(duì)固化程度的影響光引發(fā)劑種類固化程度/%空白樣0111I gracure65190133I gracure295994158Irgacure18491120二苯甲酮84176

7、光引發(fā)劑用量215%(以樹(shù)脂計(jì)。單組分光引發(fā)劑種類對(duì)涂膜性能的影響見(jiàn)表2。表2單組分光引發(fā)劑種類對(duì)涂膜性能的影響性能光引發(fā)劑種類Irgacure651Irgacure2959Irgacure184二苯甲酮光澤96151021190149117硬度4H5H4H3H流平性較好好好較好耐沖擊性/c m<5<5<5<5附著力/級(jí)2234耐溶劑性好好好好光引發(fā)劑用量215%。由表2可見(jiàn),Irgacure2959單組分作光引發(fā)劑時(shí),得到的涂膜光澤、硬度、流平性、耐沖擊性、附著力等性能都優(yōu)于Irgacure651、Irgacure184、二苯甲酮光引發(fā)劑,這說(shuō)明幾種光引發(fā)劑在單獨(dú)使用

8、時(shí),Irga2 cure2959的光固化性能最佳。這是由于在紫外光作用下I gracure2959分解生成活潑的甲基自由基,甲基自由基有較高的反應(yīng)性,可高效地引發(fā)雙鍵聚合;另一個(gè)原因是I gracure2959的吸收波長(zhǎng)與紫外光固化儀的輻射波長(zhǎng)匹配較好。選用Irgacure2959單組分為光引發(fā)劑,當(dāng)光引發(fā)劑的用量改變時(shí),粉末清漆的固化程度呈先升后降的趨勢(shì),見(jiàn)表3。表3I rgacure2959用量對(duì)固化程度和涂膜性能的影響性能/%1234固化程度/%50185831159213877103光澤981410211100179918硬度3H5H5H4H流平性較好好好好耐沖擊性/c m<55

9、5<5附著力/級(jí)3223耐溶劑性較好好好好從表3可以看到,當(dāng)光引發(fā)劑的濃度較低時(shí),涂膜的固化程度也較低,這可能是由于在低濃度下,光引發(fā)劑產(chǎn)生的自由基少,主要被O2所消耗,而難于引發(fā)雙鍵加成;隨著光引發(fā)劑用量的增加,粉末清漆的固化程度逐漸提高。但當(dāng)光引發(fā)劑濃度超過(guò)一個(gè)臨界值之后,提高光引發(fā)劑的濃度反而會(huì)使固化程度降低,較合適的引發(fā)劑用量在3%左右。表3亦給出了Irgacure2959用量改變時(shí)涂膜性能的變化情況。從表中可以看出,隨光引發(fā)劑用量的增加,涂膜光澤、流平性等提高,進(jìn)一步增加時(shí)光澤、附著力有所降低,當(dāng)光引發(fā)劑用量為2%3%時(shí)涂膜具有較好的整體綜合性能。由此可見(jiàn),提高引發(fā)劑用量可改善

10、涂膜性能,但太高的引發(fā)劑濃度會(huì)因其自身及分解產(chǎn)物在固化涂層中的存留而損傷涂膜性能。因此,綜合固化程度與涂膜性能的影響,單組分光引發(fā)劑選用Irgacure2959,其用量為3%較適宜。2.2復(fù)合光引發(fā)劑體系對(duì)涂膜性能的影響復(fù)合光引發(fā)劑體系與單組分光引發(fā)劑體系的不同在于前者能拓寬吸收紫外波長(zhǎng)的范圍,以達(dá)到與輻射波長(zhǎng)的匹配,從而使體系固化更完全。本文研究了4種體系對(duì)固化程度和涂膜性能的影響,結(jié)果如表4所示。表4復(fù)合光引發(fā)劑體系對(duì)固化程度和涂膜性能的影響性能體系組成I gracure651+I gracure2959I gracure651+I gracure184Irgacure184+I grac

11、ure2959二苯甲酮+Irgacure2959固化程度/%96157931249217372133光澤113109515102199117硬度4H3H4H3H流平性好較好好較好耐沖擊性/c m555<5附著力/級(jí)2234耐溶劑性好好好好各光引發(fā)劑組分用量都為115%。從表4可以看出,I gracure651加I gracure2959體系的固化程度要比其他光引發(fā)劑復(fù)合體系的高,涂膜性能也呈現(xiàn)出相同的規(guī)律,因此I gracure651加I gra2 cure2959復(fù)合引發(fā)體系為較佳的選擇。除了體系的組成影響其固化行為外,各組成的用量也會(huì)對(duì)涂膜性能產(chǎn)生影響。I gracure2959加I

12、 gra2 cure651復(fù)合光引發(fā)劑各組分用量對(duì)固化程度和涂膜性能的影響見(jiàn)表5。由表5可見(jiàn),I gracure2959與I gracure651兩者比例為11且總用量為3%時(shí)體系固化程度最高,所得涂膜綜合性能最佳,任一組分比例的降低都會(huì)使固化程度和涂膜性能降低,這說(shuō)明在I gracure2959與I gracure651兩種光引發(fā)劑間可能存在某種協(xié)同作用,當(dāng)光引發(fā)劑在光照下產(chǎn)生自由基后,一種光引發(fā)劑產(chǎn)生的自由基成為了另一種光引發(fā)劑光活化劑,防止其發(fā)生初級(jí)自由基聚合,使產(chǎn)生自由基的效率提高,從而提高了引發(fā)效率和固化程度,改善了涂膜性能。因此I gracure651+I gracure2959復(fù)

13、合引發(fā)體系用量以115%+115%較為合適。表5I gracure2959+I gracure651用量對(duì)涂膜性能的影響性能I gracure2959用量+I gracure651用量(質(zhì)量分?jǐn)?shù)/%1+21+1115+1152+1固化程度/%86158921439615785192光澤10914108151131010615硬度4H3H5H3H流平性好好好較好耐沖擊性/c m<5<55<5附著力/級(jí)3222耐溶劑性好好好好2.3光固化工藝對(duì)涂膜性能的影響與熱固化粉末涂料一樣,固化工藝對(duì)光固化粉末涂料的涂膜性能有著重要的影響。表6給出了不同流平溫度對(duì)涂膜性能的影響。表6流平溫度

14、對(duì)涂膜性能的影響性能流平溫度/120130140光澤106141131010917硬度5H4H4H 流平性較好好較好耐沖擊性/c m<555附著力/級(jí)323耐溶劑性好好好Irgacure2959+Irgacure651為115%+115%。從表6可以看出當(dāng)流平溫度為130時(shí),涂膜的流平性好,相應(yīng)地由于充分流平,涂膜的光澤、附著力都比流平溫度為120和140時(shí)得到的涂膜高。因此本體系最佳流平溫度為130。此外,實(shí)驗(yàn)表明130下流平10m in后涂膜性能基本穩(wěn)定,流平10 m in即可,而在固化30s后延長(zhǎng)光照時(shí)間對(duì)固化程度和涂膜性能影響不大。當(dāng)涂膜在紫外光輻射固化后,實(shí)驗(yàn)發(fā)現(xiàn),如果在高溫下

15、繼續(xù)流平一段時(shí)間例如10 m in,涂膜的流平性和光澤有所提高。3結(jié)語(yǔ)對(duì)環(huán)氧型聚丙烯酸酯-甲基丙烯酸酯光固化體系,采用3%的Irgacure2959單組分光引發(fā)劑或115% Irgacure2959+115%Irgacure651復(fù)合光引發(fā)劑體系, 130流平10m in,固化30s,所得涂膜除耐沖擊性較差外,其他性能較佳。參考文獻(xiàn)1Tho mas Ja worek,Heinz2Hil m ar Banko wsky,Rainer K oniger1Radiati onCurable Materials Princi ples and Ne w Pers pectives1Macr o mol

16、 Sy mp,2000,(159:197-2052M ills P1U ltravil ote Curable Powder Coatings1Metal Finishing,1998,(1:38-413陳松,劉亞康,魯建民,等1G MA類丙烯酸粉末罩光清漆的制備1涂料工業(yè),2004,34(2:23-254韋麗玲,魯建民,劉亞康,等1UV固化丙烯酸粉末涂料用樹(shù)脂的合成1涂料工業(yè),2004,34(11:23-255王德海,江欞編1紫外光固化材料-理論與應(yīng)用1北京:科學(xué)出版社,2001收稿日期2004-12-21中國(guó)顏料發(fā)展戰(zhàn)略及技術(shù)研討會(huì)即將召開(kāi)由全國(guó)無(wú)機(jī)顏料信息站和國(guó)家化工行業(yè)生產(chǎn)力促進(jìn)中心鈦

17、白分中心主辦的中國(guó)顏料發(fā)展戰(zhàn)略及技術(shù)研討會(huì)將于2005年10月2426日在杭州召開(kāi)。會(huì)議將研討國(guó)外反傾銷對(duì)中國(guó)顏料行業(yè)的影響,中國(guó)顏料行業(yè)國(guó)家標(biāo)準(zhǔn)的制定情況,中國(guó)顏料工業(yè)的技術(shù)現(xiàn)狀、發(fā)展趨勢(shì)及市場(chǎng)動(dòng)向。同時(shí),將邀請(qǐng)國(guó)內(nèi)外顏料行業(yè)知名專家共同探討中國(guó)顏料行業(yè)的發(fā)展戰(zhàn)略。詳情請(qǐng)聯(lián)系電話:0519-*(周樹(shù)軍傳真:0519-*E-mail:p ig ment第35卷第8期涂料工業(yè)Vol.35No.8 2005年8月P A I N T&C OATI N GS I N DUST RY Aug.2005Prepara ti on and Perfor mance of Nano-ZnO Hybr

18、i d Coa ti n gs/LU Xi ou-p ing/TUL I AO G ON GYE.-2005,35(7.-15A nano Zn O hybrid emulsi on with core-shell structure has been devel oped based on styrene,butyl acrylate,acrylic acid,oleic acid and surface modified nano Zn O.The influence of functi onal monomers,dis persants,incor porati on technol

19、ogy of nano Zn O on perfor mance of e mulsi on and coatings fil m is discussed.It has shown that the varieties,a mount and dis persing methods of dis persants are criteria on the stability of dis persi on syste m;Op ti m u m dis persi on of Zn O is available when pH value of the media is910;W hen1/2

20、surface modified nano Zn O is incor porated before copoly merizati on and the rest(another1/2of nano Zn O is blended after copoly merizati on,the hybrid e mulsi on and coatings fil m show the best perfor mance.Key W ords:nano Zn O,hybrid e mulsi on,dis persant,core-shell structure,technol ogySyn the

21、sis of UV Cur i n g Sa tura ted Polyester Resi n Powder/CHE N J ian-shan,LUO J ie,T AN Hui-p ing,et al/TUL I AO G ON GYE. -2005,35(7.-59The title phot osensitive polyester resin with ter m inal double bonds has been synthesized thr ough catalytic esterificati on of carboxyl ter m i2 nated polyester

22、with ep ichl or ohydrin,which is then ter m inated of acrylates by phase transfer reacti on.The influence of rati o of ter m inated carboxyl t o ep ichl or ohydrin,a mount of catalyst,and reacti on te mperature on extent of reacti on and the influence of concentrati on of alkali s oluti on,reacti on

23、 temperature and ti m e and amount of catalyst on phase transfer reacti on are discussed f or deter m inati on of the op ti m u m synthesis conditi ons.The p repared phot osensitive polyester resin can meet require ment of UV curing p r ocess.Key W ords:UV curing,acrylic modificati on,saturated poly

24、ester,powder,synthesisD evelop m en t of Polyether Poly isocyana te Prepoly m er/N I Yu-wei,ZHANG Shong,LE NG J ing/TUL I AO G ON GYE.-2005,35(7.-1012The title polyether polyis ocyanate p repoly mer with excellent perfor mance has been devel oped based on polyether polyols and T D I.The structure of

25、 the p repoly mer is characterized.The p r operties of p repoly mer and its acrylic polyurethane coatings are discussed.Key W ords:polyether polyols,T D I,p repoly mer,polyurethane coatingsPrepara ti on of Aqueous Polyurethane D ispersi on w ith A lcoholys a te of Veget able O ils/ZHOU Ying-p ing,CU

26、 I J ing-feng,Y ANG Bao-p ing,et al/TUL I AO G ON GYE.-2005,35(7.-1215An ambient te mperature cr osslinkable aqueous polyurethane dis persi on has been devel oped thr ough alcoholysis of drying oils with glycer2 ol,f or m ing a inter mediate alcoholysate,which is then reacted with multifuncti onal m

27、onomer DMP A,compound polyols,and m ixture of T D I/HD I thr ough step additi on poly merizati on.Characterizati on of monomers,alcoholysate and aqueous polyurethane dis persi on indicated the target p r oduct is obtained.An a mbient cr osslinkable aqueous polyurethane coatings is for mulated by use

28、 of this high perfor mance waterborne resin as binder.Key W ords:a mbient cr osslinking,aqueous polyurethane,alcoholysis,waterborne coatings,I R characterizati onPr i n c i ple of One-Step Prepara ti on and D evelop m en t of H i ghly Substituted Ethyl Cellulose/L I Hong-qing,Z OU Hua-sheng, X I A O

29、 Lei,et al/TUL I AO G ON GYE.-2005,35(7.-1620The reacti on mechanis m and technol ogy of p reparati on of the title one-step highly substituted cellul ose with t oluene as diluent is devel2 oped by orthogonal experi m ents.The structure of p r oduct is characterized by use of I R and H1NMR.It is fou

30、nd that the op ti m u m technical conditi ons are:(based on27gra m s of cellul oset oluene180g,concentrati on of Na OH s oluti on60%(m/m,ethyl chl oride477.5g, at140f or13h,the ethoxy content can be up t o44.8%(m/m.Key W ords:highly substituti on,ethyl cellul ose,one-step method,synthesis,mechanis m

31、I nfluence of E m ulsi on Poly m er i za ti on Technology on Perfor mance of Am b i en t Crossli n k i n g Acryli c E m ulsi on Pa i n t/ZHANGMei, YI N Yan-bai,W E N Shen-lei,et al/TUL I AO G ON GYE.-2005,35(7.-2124The influence of three different e mulsi on poly merizati on technol ogies,s op-free,

32、m icr o-s oap and conventi onal e mulsi on poly meriza2 ti ons on the a mbient cr osslinking acrylic e mulsi on paints based on diacet oneacyl oa m ide(DAAMas cr osslinking monomer and adi p ic hy2 drazine as hardener.It is shown that conventi onal e mulsi on poly merizati on p r ocess leads t o high gl oss fil m and s oap-free or m icr o-s oap p r ocesses will lead t o good water resistance and l ower f oa m ing.Key W ords:a mbient cr osslinking,acryli