CN1454933A - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
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- CN1454933A CN1454933A CN 03117583 CN03117583A CN1454933A CN 1454933 A CN1454933 A CN 1454933A CN 03117583 CN03117583 CN 03117583 CN 03117583 A CN03117583 A CN 03117583A CN 1454933 A CN1454933 A CN 1454933A
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Abstract
The photosolidifying resin composition comprises multifunctional aliphatic acrylic acidified polyurethane, styrene-(methyl) acrylate copolymer, acrylate containing aromatic ring and photoinitiator. The refractive index of the solidified resin is 1.47-1.55. Said resin composition is applicable to preparation of sheet materials of Fresnel lens, etc. whose surface has microfine structure, and has the features of high replication efficiency, convenient use, easy demoulding, good yellowing resistance and excellent adhesive force with plastic base material.
Description
1, technical field the present invention relates to a kind of resin combination of uV curable, this resin combination and transparent plastic substrate have excellent sticking power, be specially adapted to the microtexture of replicated surfaces, as Fenier lens of liquid crystal display, rear projection television screen etc.
2, technical background large-scale production surface has the big area sheet material of microtexture; as Fenier lens of rear projection type televisions etc.; effective means is to adopt photocuring technology, injects liquid resin between mould that microtexture is arranged and transparent substrate, sees through the base material irradiation and makes resin solidification.Solidified resin and base material are bonded as one, after peeling off from mould, have just duplicated the microtexture of mould on the solidified resin layer.Use photocuring technology can make resin less than one minute solidify in the time, therefore this photocuring production technique of duplicating (hereinafter to be referred as optical reproduction) has very high production efficiency, and is easy to use.Use the Fenier lens in the optical reproduction production transmission-type fluorescent screen, existing multinomial patent is introduced, but the light-cured resin that is used for optical reproduction is still few, in the open book (application number 99103415.5) of Chinese patent, mentioned that this light curing resin composition is suitable for preparing the Fenier lens of high refractive index resins sheet based on the light curing resin composition of acrylic acid modified bisphenol-A type Resins, epoxy, acrylated bisphenol-A polyester.But experienced professional person knows, the resin that contains the dihydroxyphenyl propane class formation is easy to flavescence under the effect of light, thermooxidizing, therefore the aging resistance of the resin of this method preparation is relatively poor, and the resin of this method is bad to the tack of polyacrylate(s) synthetic glass simultaneously.The specific refractory power that this patent will provide a kind of and synthetic glass and the transparent organic substrate adhesion property of polystyrene type excellence, curing speed height, be easy to demoulding, solidify the back resin layer is at 1.47-1.55, resin combination that the xanthochromia performance is good.
3. summary of the invention light curing resin composition of the present invention comprises following component: polyfunctional acrylated aliphatic urethane (component A); Melt index is at methacrylic ester and the cinnamic multipolymer (component B) of 1-10g/10min; The acrylate (component C) of solubilized component B; The acrylate (component D) that contains aromatic ring; Radical photoinitiator (component E); Below will be to above-mentioned every being illustrated.
Composition A is the aliphatics propylene acidylate urethane of 2-5 functionality, and molecular weight is at 1200-8000.In order to make light curing resin composition be convenient to construction, the molecular weight of composition A is preferably in 1200-6000, and functionality is at 2-3.Composition A can be with polyethers or polyester polyol; 6 methylene diisocyanates or not different and ketone vulcabond, Methylcyclohexyl diisocyanate, hydrogenated diphenyl methane diisocyanate etc. prepare with the acrylate of hydroxyl, existing multiple commercial aliphatics propylene acidylate urethane.In resin combination of the present invention, the consumption of composition A will influence composition viscosity, curing speed and with the sticking power of base material, consumption is at 10-70%, preferably at 15-40%.
Composition B is the multipolymer (PSM) of vinylbenzene (St) and (methyl) acrylate, can increase the sticking power of resin combination and base material, the soft or hard characteristic of adjustment resin with multiple (methyl) acrylate and St copolymerization.Preferably (methyl) acrylate has methyl methacrylate (MMA), butyl methacrylate (BMA), Isooctyl methacrylate, ethyl propenoate, methacrylic acid (MA) etc.; The chemical structure of PSM resin can be represented with following chemical structural formula:
R
1=H, CH
3The content of St is at 10-60% among n=2～12PSM, and the content of (methyl) methyl acrylate is at 20-70%, and the content of other (methyl) acrylate can contain a spot of (methyl) vinylformic acid at 10-50%.PSM can prepare with the free radical polymerisation process of routine.Composition B can reduce the volumetric shrinkage of light curing resin composition when photocuring in the present invention, adjust the specific refractory power of light curing resin composition, improve the sticking power of resin combination and base material simultaneously, change the composition of component among the composition B, can make light curing resin composition good adhesive all be arranged comprising synthetic glass, polystyrene and multiple transparent organic sheet.The consumption 5-50% of composition B is preferably at 10-30%.
The effect of composition C mainly is dissolving composition B, adjusts the viscosity of composition.Selectable composition C comprise (methyl) acrylate, the hydroxyl of constituent B (methyl) acrylate, contain (methyl) acrylate of aromatic ring, as benzene oxygen ethyl (methyl) acrylate etc.The consumption of composition C is at 10-40%.
Composition D is difunctionality (methyl) acrylate, comprise two (methyl) acrylate, neighbour of dibasic alcohol-, right-or-two basic esters of acryloyl-oxy second (third) of phthalic acid etc.Components D can improve the hardness of laser curing velocity, cured article and resistance to marring etc., but consumption is too much, and the volumetric shrinkage when solidifying is excessive with making, and reduces the precision of replica.The consumption of components D is at 8-50%.Preferably at 10-40%.
Composition E is the light trigger of free radical type, comprises the methyl phenyl ketone of benzoin ether, replacement, the acyl group phenyl phosphorus oxide of replacement etc., as the light trigger trade names 1173,184,651,819 of Ciba company, the structure of TPO representative.The consumption of composition E is at 1-5%.
For the benefit of the package stability of resin combination also can add Pyrogentisinic Acid's class stopper, and consumption is at 0.01-0.6%.
Implementation method is following with one group of example explanation the present invention, the composition B that uses in the example prepares as follows: the preparation of PSM: load onto motor machine stirring, prolong and dropping funnel on the three-necked bottle of a 500ml, the top of prolong links to each other with separating atmospheric with oil sealing, top at dropping funnel imports nitrogen, and three-necked bottle places the heating oil bath; Add ethyl acetate 200ml, under agitation slowly be blown into nitrogen, during the widely different stream of beginning, by the solution of 80g St, 80g MMA, 32g BMA, 8g MA monomer and 3g initiator A IBN, the speed of dropping is advisable with the widely different flow velocity degree of may command in the addition funnel in bottle.Add the back at whole monomers and continue reaction 2 hours, be warmed up to 100 ℃ and reacted again 2 hours, then the solution in the bottle is slowly joined in 1500 liters of methyl alcohol of stirring, after filtration, obtain white product after the drying.Can make the multipolymer of different St content with class methods.
The preparation of light curing resin composition: take by weighing the composition B of design flow, it in bottle at the bottom of component C joins the garden, is stirred 5 hours down up to whole dissolvings at 65 ℃, stop heating.Resin EB270 (composition A), components D and the light trigger (composition E) that adds UCB. S.A. (BE) Bruxelles Belgium stirs together and got resin combination in 1 hour.
Change the composition and the ratio of composition, can make performance light curing resin composition not, see Table 1.
Four kinds of light curing resin compositions of table 1. (weight, gram)
Annotate: POEA: benzene oxygen ethyl propylene acid esters; HPA: vinylformic acid hydroxy propyl ester; PDDA: the two acrylyl oxy-ethyl esters of neighbour-phthalic acid; HDDA: hexylene glycol double methacrylate.Other code name is seen in the literary composition and is explained.
| Resin No | ?????A????B?????????????C?????????????????D?????????E |
| ???EB270??PSM??POEA??HPA???MMA???BA???PDDA??HDDA??819?184 | |
| ????1 ????2 ????3 ????4 | ????20????16????10????10????0?????0????20????0?????2???2 ????25????15????5?????9?????20????0????20????0?????2???2 ????36????0?????0?????10????30????0????0?????20????2???2 ????35????0?????0?????10????25????7????9?????10????2???2 |
The performance of resin combination: resin combination is after vacuum outgas, be poured on the Fei Nieer mirror template of nickel, place the poly (methyl methacrylate) plate of the about 2mm of thickness thereon, control glue thickness is at about 0.1mm, see through poly (methyl methacrylate) plate with about 45 seconds of the high voltage mercury lamp radiation of 80w/cm, lamp is apart from about 15cm.With between blade incision plastic plate and the mould solidified resin is peeled off from mould, estimate release property by the complexity of peeling off: after between blade incision resin and the mould, resin sheet promptly open easily for demolding performace excellent; Have part filament shape to stay on the mould in the resin of back if strip down, demolding performace is poor; If can completely strip off, but needing bigger strength, then is that release property is general; The hardness of cured article is represented with pencil hardness; Specific refractory power is measured with Abbe refractometer; The volumetric shrinkage of resin solidification is measured with capillary tube technique; The sticking power of resin and base material is passed judgment on cross-hatching: it is excellent adhering to zero level, and the 1-2 level is good, and 3-4 is differential.The performance of four kinds of resin combinations shown in the table 1 collects in the table 2, and as can be seen, the present invention has solved control regulation and control specific refractory poweres preferably, solidified the key issue of the optical reproduction such as sticking power of volumetric shrinkage, release property and resin and base material.
Table 2, the performance after four kinds of resin combinations solidify
| ??NO | Specific refractory power hardness release property sticking power volumetric shrinkage |
| ??1 ??2 ??3 ??4 | 1.53 good 9 1.49 H of good 9 1.48 2H of excellent 8 1.53 H of 2H differ from 9 |
Claims (7)
1. the resin combination of a uV curable, A-G constitutes by component, and the specific refractory power of solidifying the back resin can be used for superfine structure surface, as the making of big area Fenier lens sheet material at 1.47-1.55.
2. the described component A of claim 1 is a kind of two or aliphatics (methyl) the propylene acidylate urethane of trifunctional, molecular weight 1200-8000g/mol.Component A is by (methyl) crylic acid hydroxy ester, molecular weight aliphatics dihydroxyl or trihydroxy-compound and aliphatic polyisocyante at 100-3000, as hexamethylene diisocyanate, not different and reactions such as ketone vulcabond, Methylcyclohexyl diisocyanate, hydrogenated diphenyl methane diisocyanate make.Consumption 10-50 part of component A.
3. the described component B of claim 1 is the multipolymer of vinylbenzene and (methyl) acrylate, is expressed as follows with chemical structural formula:
R
1=H, CH
3K.L.M.N represents the formation percentage ratio of component, K:0.1-0.6, L:0.2-0.7; M:0-0.05; N:0.1-0.5; N:2-8.
Consumption 5-30 part of component B.
4. the described component C of claim 1 is the acrylate of simple function, comprises methyl methacrylate, butyl methacrylate, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, benzene oxygen ethyl propylene acid esters, vinylformic acid norborneol ester etc.Consumption 10-40 part of component C.
5. the described component D of claim 1 is the bifunctional acrylate, particularly including between (adjacent-, right-)-the two basic esters of acryloyl-oxy second (third) of phthalic acid, consumption 10-40 part.
6. the described component E of claim 1 is a light trigger, is made up of 0.5-3 part acylphosphine oxide class and 0.5-4 part substituted acetophenone type free base light trigger.
7. the described component F of claim 1 is the phenol stablizer, as Resorcinol, p methoxy phenol etc.Consumption is 0.01-0.6 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117583 CN1454933A (en) | 2003-04-01 | 2003-04-01 | Photocurable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117583 CN1454933A (en) | 2003-04-01 | 2003-04-01 | Photocurable resin composition |
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|---|---|
| CN1454933A true CN1454933A (en) | 2003-11-12 |
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| CN 03117583 Pending CN1454933A (en) | 2003-04-01 | 2003-04-01 | Photocurable resin composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805422A (en) * | 2009-02-18 | 2010-08-18 | 日本化药株式会社 | Optical lens energy ray curable resin composition and cured article thereof |
| CN102471424A (en) * | 2009-07-21 | 2012-05-23 | 太阳控股株式会社 | Photocurable resin composition |
| CN103218081A (en) * | 2013-04-12 | 2013-07-24 | 深圳欧菲光科技股份有限公司 | Double-layer touch screen and preparation method for same |
| CN103235660A (en) * | 2013-04-12 | 2013-08-07 | 深圳欧菲光科技股份有限公司 | Double-layer touch screen and manufacturing method thereof |
| CN104937000A (en) * | 2013-03-28 | 2015-09-23 | 太阳油墨制造株式会社 | Active energy ray-curable resin composition and cured article thereof |
| CN105745273A (en) * | 2013-09-05 | 2016-07-06 | 株式会社大赛璐 | Resin composition and cured article thereof |
| CN108368190A (en) * | 2015-12-17 | 2018-08-03 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealing agent and liquid crystal display panel and its manufacturing method |
-
2003
- 2003-04-01 CN CN 03117583 patent/CN1454933A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805422A (en) * | 2009-02-18 | 2010-08-18 | 日本化药株式会社 | Optical lens energy ray curable resin composition and cured article thereof |
| CN101805422B (en) * | 2009-02-18 | 2013-10-23 | 日本化药株式会社 | Energy ray-curable resin composition and cured product for optical lens sheet |
| CN102471424A (en) * | 2009-07-21 | 2012-05-23 | 太阳控股株式会社 | Photocurable resin composition |
| CN102471424B (en) * | 2009-07-21 | 2015-02-18 | 太阳控股株式会社 | Photocurable resin composition |
| CN104937000A (en) * | 2013-03-28 | 2015-09-23 | 太阳油墨制造株式会社 | Active energy ray-curable resin composition and cured article thereof |
| CN104937000B (en) * | 2013-03-28 | 2019-07-05 | 太阳油墨制造株式会社 | Actinic energy ray curable resion composition and its solidfied material |
| CN103235660A (en) * | 2013-04-12 | 2013-08-07 | 深圳欧菲光科技股份有限公司 | Double-layer touch screen and manufacturing method thereof |
| CN103218081A (en) * | 2013-04-12 | 2013-07-24 | 深圳欧菲光科技股份有限公司 | Double-layer touch screen and preparation method for same |
| CN105745273A (en) * | 2013-09-05 | 2016-07-06 | 株式会社大赛璐 | Resin composition and cured article thereof |
| KR101838830B1 (en) | 2013-09-05 | 2018-03-14 | 주식회사 다이셀 | Resin composition and electronic device |
| CN105745273B (en) * | 2013-09-05 | 2019-05-07 | 株式会社大赛璐 | Resin combination and its solidfied material |
| CN108368190A (en) * | 2015-12-17 | 2018-08-03 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealing agent and liquid crystal display panel and its manufacturing method |
| CN108368190B (en) * | 2015-12-17 | 2019-12-31 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal display panel, and method for producing same |
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