CN102786640A - Energy ray curable resin composition for optical lens sheet, cured object thereof and optical lens sheet - Google Patents
Energy ray curable resin composition for optical lens sheet, cured object thereof and optical lens sheet Download PDFInfo
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- CN102786640A CN102786640A CN2012101504035A CN201210150403A CN102786640A CN 102786640 A CN102786640 A CN 102786640A CN 2012101504035 A CN2012101504035 A CN 2012101504035A CN 201210150403 A CN201210150403 A CN 201210150403A CN 102786640 A CN102786640 A CN 102786640A
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- propenoate
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Abstract
The invention provides an energy ray curable resin composition for an optical lens sheet, a cured object thereof and an optical lens sheet. The resin composition of an optical lens is suitable for being formed on a substrate, and is good in mold release, mold reproducibility and bonding property with substrate film, and is high in endurance (scratch resistance). The energy ray curable resin composition of an optical lens sheet for formation on a substrate comprises 30-70 mass part of polyethylene oxide modifying bisphenol A-type II (methyl) acrylic ester (A) which is expressed in the following formula (1) (in the formula, R1 and R2 individually represent hydrogen atom or methyl, m and n individually represent positive number from 5 to 10), 3-50 mass part of single (meth) acrylate (B) having a phenylate structure, 3-20 mass part of polyfunctional (methyl) acrylate which has over three (methyl) acrylic acid and is modified by a caprolactone or an ethylene oxide, 3-20 mass part of carbamic acid ester (meth) acrylate oligomer (D) having a tetramethylene glycol structure, and 1-10 mass part of a photopolymerization initiator (E).
Description
Technical field
Ultraviolet-curing resin composition is used to employed Fresnel Lenses, lens pillar etc. are shaped in employed prismatic lens, projection TV set etc. in the backlight of liquid crystal indicator optical lens, rear projection screen etc. on base material.
As far as these optical lens; Because the requirement that reduces cost in recent years improves, therefore, the tendency of the sheet number minimizing of optical sheet is arranged; At present, the weather resistance (being called scuff resistance, scratch resistance etc.) for other optical sheets contact of directly not contacting the time has high-level requirement.
As giving the material of weather resistance to resin layer itself, in patent documentation 1, manifest weather resistance, but the resin combination that contains the little material of vinylformic acid equivalent there is the strong tendency of crimp tendency through using the little material of vinylformic acid equivalent, not preferred as optical sheet.In addition, when trial manifested weather resistance with the little material of vinylformic acid equivalent, have following problem: the cured film hardening became fragile, and is particularly impaired easily owing to contacting with the optical sheet that contains the organic or inorganic filler.
In patent documentation 2; Proposed to utilize the combination of specific resin to use resin, being combined as of said specific resin as optical lens: amount to repeat number and be 0 ~ 8 oxyethane modification two (methyl) propenoate, have 2 aromatic nucleus and 1 (methyl) acryl compound, have 1 aromatic nucleus and 1 (methyl) acryl compound, have the compound of (methyl) acryl more than 3 and as the combination of compounds that contains ethylenically unsaturated group beyond optional member above-mentioned.The scuff resistance (scratch resistance) of two (methyl) propenoate that amounts to repeat number and be 0 ~ 8 oxyethane modification is poor, is not suitable under the situation that requires scuff resistance (scratch resistance), using.This is because though epoxy alkane modification meeting hardening in short-term, the while also can become fragile.In addition, in the embodiment of patent documentation 2, only used diacrylate with thioether skeleton, known usually: though the tendency that has specific refractory power to rise when using the resin contain sulphur atom, stink strengthens, and the remarkable variation of photostabilization.Therefore, in recent years optical lens with resin combination in, have the problem on using.
As stated, do not obtain having concurrently the resin combination that the desired characteristic of common optical lens is high light line transsmissivity, mold releasability property, base material adhesivity and high-durability as yet.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2010-126670 communique
Patent documentation 2: No. 4457960 communique of Japanese Patent
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide excellent, the high cured article of weather resistance (scuff resistance, scratch resistance) of resin combination and light transmittance, mold releasability property of the optical lens that is applicable to that lens pillar, prism, microlens etc. are shaped on base material.
The means that are used to deal with problems
The inventor concentrates on studies in order to address the above problem, and the result finds that ultra-violet solidified resin composition and cured article thereof with specific composition can address the above problem, thereby has accomplished the present invention.
That is, the present invention provides
(1) a kind of energy ray curable resin composition of the optical lens that is used on base material, being shaped; It contains bisphenol A-type two (methyl) propenoate (A) 30 ~ 70 mass parts of the polyethylene oxide modification shown in the formula (1) respectively; List (methyl) propenoate (B) 3 ~ 50 mass parts with phenylate structure; Has more than 3 (methyl) acryl and with multifunctional (methyl) propenoate (C) 3 ~ 20 mass parts after caprolactone or the oxyethane modification; Carbamate (methyl) origoester acrylate (D) 3 ~ 20 mass parts and Photoepolymerizationinitiater initiater (E) 1 ~ 10 mass parts with tetramethylene glycol structure
(in the formula (1), R
1, R
2Represent Wasserstoffatoms or methyl respectively independently, m and n are repeat number, represent 5 ~ 10 positive number respectively independently).
(2) like (1) described energy ray curable resin composition; It is characterized in that (methyl) propenoate (B) with phenylate structure is for being selected from the group that is made up of phenoxy ethyl (methyl) propenoate, phenoxy polyethoxye (methyl) propenoate, orthoxenol (methyl) propenoate, orthoxenol monosubstituted ethoxy (methyl) propenoate, orthoxenol polyethoxye (methyl) propenoate, p-phenyl phenol (methyl) propenoate, p-phenyl phenol monosubstituted ethoxy (methyl) propenoate, p-phenyl phenol polyethoxye (methyl) propenoate more than one.
(3) like (1) described energy ray curable resin composition; Wherein, carbamate (methyl) origoester acrylate (D) that has a tetramethylene glycol structure is that to make molecular weight be carbamate (methyl) origoester acrylate that (methyl) acrylate reactions of 500 ~ 1000 diol compound, polyisocyanate compound and hydroxyl obtains.
(4) like each described energy ray curable resin composition in (1) ~ (3), wherein, polyisocyanate compound has ring structure.
(5), wherein, utilize viscosity under 25 ℃ that E type viscometer records for below the 2000mPas like each described energy ray curable resin composition in (1) ~ (4).
(6) a kind of cured article, it obtains through utilizing energy-ray irradiation that each described energy ray curable resin composition is solidified.
(7) a kind of optical lens, it has (6) described cured article.
The invention effect
Resin combination of the present invention has good stability, the release property from mould, mould circulation ratio, with the good adhesion of base material film.In addition, weather resistance (scuff resistance, scratch resistance) excellence.Therefore, be specially adapted to the optical lens that lens pillar, prism, microlens etc. are shaped on base material.
Embodiment
The total repeat number of using among the present invention (m+n in the above-mentioned general formula (1)) is the effect that bisphenol A-type two (methyl) propenoate (A) of 10 ~ 20 polyethylene oxide modification has the scuff resistance (scratch resistance) that improves cured article.When amounting to repeat number and be beyond 10 ~ 20 the scope, though obtain more crisp firmly cured article.As concrete example; Can enumerate: dihydroxyphenyl propane two (methyl) propenoate of dihydroxyphenyl propane two (methyl) propenoate of dihydroxyphenyl propane two (methyl) propenoate of 10 moles of oxyethyl group modifications, 18 moles of oxyethyl group modifications, 20 moles of oxyethyl group modifications etc., above-mentioned substance can easily obtain with the form of commercially available article.Particularly, can enumerate: the system NEWFRONTIER BPE-10 of Di-ichi Kogyo Seiyaku Co., Ltd. (in the general formula (1), R
1=H, R
2=H, m=5, n=5), Di-ichi Kogyo Seiyaku Co., Ltd. system NEWFRONTIER BPEM-10 (R
1=CH
3, R
2=CH
3, m=5, n=5), the system NEWFRONTIER BPE-20 of Di-ichi Kogyo Seiyaku Co., Ltd. (in the general formula (1), R
1=H, R
2=H, m=10, n=20), Hitachi Chemical Co., Ltd. system FANCRYL FA-321A (R
1=H, R
2=H, m=5, n=5), Hitachi Chemical Co., Ltd. system FANCRYL FA-3218A (R
1=H, R
2=H, m=9, n=9), Hitachi Chemical Co., Ltd. system FANCRYL FA-321M (R
1=CH
3, R
2=CH
3, m=5, n=5), the system FANCRYL FA-3218M (R of Hitachi Chemical Co., Ltd.
1=CH
3, R
2=CH
3, m=9, n=9), the system NK ESTER A-BPE-10 (R of Xin Zhong village chemical industry Co., Ltd.
1=H, R
2=H, m=5, n=5), Xin Zhong village chemical industry Co., Ltd. system NK ESTER A-BPE-20 (in the general formula (1), R
1=H, R
2=H, m=10, n=20), Xin Zhong village chemical industry Co., Ltd. system NK ESTER BPE-500 (R
1=CH
3, R
2=CH
3, m=5, n=5), the system NK ESTER BPE-900 (R of Xin Zhong village chemical industry Co., Ltd.
1=CH
3, R
2=CH
3, m=8, n=9), the system BLEMMER PDBE-450 (R of Japan Oil Co
1=CH
3, R
2=CH
3, m=5, n=5), Sartomer system SR602 (R
1=H, R
2=H, m=5, n=5), Sartomer system SR480 (R
1=CH
3, R
2=CH
3, m=5, n=5), MIWON system MIRAMER M2100 (R
1=H, R
2=H, m=5, n=5) etc.
As (methyl) propenoate (B) that uses in the resin combination of the present invention, can enumerate following material with phenylate structure.
To cumyl phenoxy terepthaloyl moietie (methyl) propenoate; Tribromo phenyl (methyl) propenoate; Oxyethyl group modification tribromo phenyl (methyl) propenoate; Propoxy-modification tribromo phenyl (methyl) propenoate; Phenoxy hydroxypropyl (methyl) propenoate; Phenoxy polyoxyethylene glycol (methyl) propenoate; Nonylphenoxy polyoxyethylene glycol (methyl) propenoate; Nonylphenoxy W 166 (methyl) propenoate; Phenoxy ethyl (methyl) propenoate; Phenoxy polyethoxye (methyl) propenoate; Nonylphenol (methyl) propenoate; Oxyethyl group modification nonylphenol (methyl) propenoate; Polyethoxye modification nonylphenol (methyl) propenoate; Orthoxenol (methyl) propenoate; Orthoxenol monosubstituted ethoxy (methyl) propenoate; Orthoxenol polyethoxye (methyl) propenoate; P-phenyl phenol (methyl) propenoate; P-phenyl phenol monosubstituted ethoxy (methyl) propenoate; P-phenyl phenol polyethoxye (methyl) propenoate; Orthoxenol epoxy group(ing) (methyl) propenoate; P-phenyl phenol epoxy group(ing) (methyl) propenoate etc.Preferred especially phenoxy ethyl (methyl) propenoate, orthoxenol monosubstituted ethoxy (methyl) propenoate and orthoxenol polyethoxye (methyl) propenoate.These have phenylate structure (methyl) propenoate and can use separately, also can mix multiple the use.
The effect that has (methyl) acryl more than 3 and have the scuff resistance (scratch resistance) that improves cured article with multifunctional (methyl) propenoate (C) after caprolactone or the oxyethane modification.Under situation about using not, though cured article becomes fragile firmly with (methyl) propenoate of caprolactone or oxyethane modification.As having (methyl) acryl more than 3 and, can enumerating: polyethoxye modification trimethylolpropane tris (methyl) propenoate, polyethoxye modification tetramethylolmethane four (methyl) propenoate, polyethoxye modified glycerol three (methyl) propenoate, polyethoxye modification Dipentaerythritol five (methyl) propenoate, polyethoxye modification Dipentaerythritol six (methyl) propenoate, polycaprolactone modification trimethylolpropane tris (methyl) propenoate, polycaprolactone modification Dipentaerythritol five (methyl) propenoate, polycaprolactone modification Dipentaerythritol six (methyl) propenoate, caprolactone modification three (acryloxy ethyl) isocyanuric acid ester, polycaprolactone modification three (acryloxy ethyl) isocyanuric acid ester, polyethoxye modification three (acryloxy ethyl) isocyanuric acid ester etc. with the concrete example of multifunctional (methyl) propenoate (C) after caprolactone or the oxyethane modification.Preferred especially polyethoxye modification trimethylolpropane tris (methyl) propenoate, polycaprolactone modification three (acryloxy ethyl) isocyanuric acid ester, polycaprolactone modification Dipentaerythritol five (methyl) propenoate, polycaprolactone modification Dipentaerythritol six (methyl) propenoate.
The contained carbamate with tetramethylene glycol structure (methyl) origoester acrylate (D) also has the effect of the scuff resistance (scratch resistance) that improves cured article in the resin combination of the present invention.As concrete example, for example can enumerate: make that diol compound and organic multiple isocyanate react, then addition hydroxyl (methyl) propenoate and the reaction product that obtains etc.
As spendable diol compound among the present invention, for example can enumerate: gather 1,4-butyleneglycol, 3-methyl isophthalic acid, 4-butyleneglycol etc.Can easily obtain the diol compound of each any molecular weight with the form of commercially available article, in the present invention, preferred molecular weight 500 ~ 1000 gathers 1,4-butyleneglycol compound especially.
As spendable organic multiple isocyanate among the present invention, for example can enumerate: 1,4-fourth vulcabond, 1; Hexamethylene-diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 2; 4, chain stable hydrocarbon isocyanic ester such as 4-trimethyl hexamethylene diisocyanate, cyclic saturated hydrocarbon isocyanic ester such as isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methane diisocyanate, methylene-bis (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, HTDI; 2,4 toluene diisocyanate, 1,3-xylylene diisocyanate, PPDI, 3; 3 '-dimethyl--4,4 '-vulcabond, 6-sec.-propyl-1,3-phenyl diisocyanate, 1; Aromatic polyisocyanates such as 5-naphthalene diisocyanate etc.; Preferred cyclic saturated hydrocarbon isocyanic ester, wherein, preferred tolylene diisocyanate or isophorone diisocyanate.
Concrete example as spendable hydroxyl (methyl) propenoate among the present invention; For example can enumerate: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 1; The 6-caprolactone affixture of 4-butanediol ester, polyethyleneglycol (methyl) propenoate, W 166 list (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, (methyl) vinylformic acid 2-hydroxy methacrylate, 2-hydroxyl-3-phenoxy propyl (methyl) propenoate etc., preferred (methyl) vinylformic acid 2-hydroxy methacrylate.
The carbamate with tetramethylene glycol structure (methyl) origoester acrylate (D) that uses among the present invention can utilize ordinary method to be synthesized into through using above-mentioned diol compound, organic multiple isocyanate and hydroxyl (methyl) propenoate.That is, for example, obtain reaction product (I), then,, obtain carbamate (methyl) propenoate thus reaction product (I) addition hydroxyl (methyl) propenoate through diol compound and organic multiple isocyanate are carried out addition.
When building-up reactions product (I), with respect to hydroxyl 1 equivalent of above-mentioned glycol, NCO 1.1 ~ 2.0 equivalents of organic multiple isocyanate are reacted, 1.3 ~ 2.0 equivalents are reacted.Temperature of reaction is generally 60 ~ 100 ℃.With NCO reach the reaction before 5.0 quality % below the moment as reaction end.
In addition, in order to reduce viscosity, also can add the compound of not participating in reacting during reaction as thinner.(methyl) propenoate that particularly, can use the structure with hydroxyl is as thinner.
In the reaction of reaction product (I) and hydroxyl (methyl) propenoate,, hydroxyl 0.95 ~ 1.1 equivalent of hydroxyl (methyl) propenoate is reacted with respect to NCO 1 equivalent of reaction product (I).Temperature of reaction is generally 60 ~ 100 ℃.With NCO reach the reaction before 0.1 quality % below the moment as reaction end.In addition; In order to promote these reactions; Sometimes for example use two LAURIC ACID 99 MIN salt compounds such as tertiary amines such as triethylamine, benzyl methylamine, dibutyl tin laurate, two LAURIC ACID 99 MIN dioctyl tins as catalyzer; But in the present invention, owing to, therefore do not use stanniferous catalyzer in recent years to the worry increase of environment and the severization of rules and regulations.In addition, for the polymerization in preventing to react, for example can use stoppers such as quinhydrones, hydroquinone monomethyl ether, p methoxy phenol, para benzoquinone.The addition of stopper is generally 0.001 ~ 5 quality % with respect to reaction mixture integral body, is preferably 0.01 ~ 1 weight %.In addition, in resin combination of the present invention, carbamate (methyl) origoester acrylate (D) with tetramethylene glycol structure can use separately, also can mix multiple the use.
As Photoepolymerizationinitiater initiater contained in the resin combination of the present invention (E), can enumerate: bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, bitter almond oil camphor ethyl isobutyl ether; Methyl phenyl ketone, 2; 2-diethoxy-2-phenyl methyl phenyl ketone, 2; 2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, oligomeric acetophenones such as [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone]; Anthraquinone classes such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; 2, thioxanthene ketones such as 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-clopenthixal ketone; Ketal classes such as methyl phenyl ketone dimethyl ketal, benzyl dimethyl ketal; UVNUL MS-40,4-benzoyl--4 '-methyldiphenyl thioether, 4,4 '-benzophenones such as two methylamino UVNUL MS-40; 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide, phenylbenzene-phosphinoxidess such as (2,4,6-Three methyl Benzene formyl) phosphine oxide etc.Be preferably acetophenones, can further preferably enumerate 2-hydroxy-2-methyl-phenyl-propane-1-ketone, 1-hydroxy-cyclohexyl-phenyl ketone.In addition, in resin combination of the present invention, Photoepolymerizationinitiater initiater (E) can use separately, also can mix multiple the use.
In addition; Consider viscosity, specific refractory power, adhesivity of the resin combination of the present invention of gained etc., can in resin combination of the present invention, mix one or more (methyl) propenoate except that composition (A), composition (B), composition (C), composition (D) and use.As this (methyl) propenoate, can use simple function (methyl) propenoate, difunctionality (methyl) propenoate, intramolecularly to have multifunctional (methyl) propenoate, polyester (methyl) propenoate, epoxy (methyl) propenoate of (methyl) acryl more than 3 etc.
As simple function (methyl) propenoate; For example can enumerate: ester ring type (methyl) propenoate such as isobornyl (methyl) propenoate, two cyclopentyl (methyl) propenoate, dicyclopentenyl (methyl) propenoate, two cyclopentenes oxygen base ethyl (methyl) propenoate, (methyl) cyclohexyl acrylate; (methyl) benzyl acrylate, oxyethyl group modification cresols (methyl) propenoate, propoxy-modification cresols (methyl) propenoate, NSC 6366 benzoic ether (methyl) propenoate, morpholine (methyl) propenoate etc. have (methyl) propenoate of aromatic nucleus; Caprolactone (methyl) propenoate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate etc. have heterocyclic (methyl) propenoate; Imide (methyl) propenoate with imide ring structure; Butyleneglycol list (methyl) propenoate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, dipropylene glycol (methyl) propenoate etc. have (methyl) propenoate of hydroxyl; (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid butoxy ethyl ester, (methyl) NSC 20949, (methyl) tert-butyl acrylate, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid isooctadecane base ester, the different tetradecyl ester of (methyl) vinylformic acid, (methyl) lauryl acrylate etc. have (methyl) propenoate of alkyl, (methyl) propenoate of polyvalent alcohols such as oxyethyl group Diethylene Glycol (methyl) propenoate, 2-ethylhexyl Trivalin SF (methyl) propenoate, polyoxyethylene glycol (methyl) propenoate, W 166 (methyl) propenoate etc.
As difunctionality (methyl) propenoate; Can enumerate: special valeral modification TriMethylolPropane(TMP) two (methyl) propenoate of hydroxyl, oxyethyl group modified bisphenol A two (methyl) propenoate, propoxy-modified bisphenol A two (methyl) propenoate, oxyethyl group modified bisphenol F two (methyl) propenoate, propoxy-modified bisphenol F two (methyl) propenoate, oxyethyl group modified bisphenol S two (methyl) propenoate, propoxy-modified bisphenol S two (methyl) propenoate, polymer with bis phenol A oxyethyl group two (methyl) propenoate, polymer with bis phenol A propoxy-two (methyl) propenoate, Bisphenol F polyethoxye two (methyl) propenoate, hexahydrophthalic acid two (methyl) propenoate etc. have the acrylated thing, 1 of isocyanic ester such as (methyl) propenoate, diacrylate isocyanuric acid ester of aromatic nucleus; 4-butyleneglycol two (methyl) propenoate, 1; 6-pinakon two (methyl) propenoate, 1,9-nonanediol two (methyl) propenoate etc. have two (methyl) propenoate of polyvalent alcohols such as ester ring type (methyl) propenoate, ethylene glycol bisthioglycolate (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, Ucar 35 two (methyl) propenoate, W 166 two (methyl) propenoate such as (methyl) propenoate, tristane dimethanol (methyl) propenoate, two cyclopentyl diacrylates of straight chain methylene radical structure etc.
As multifunctional (methyl) propenoate that has (methyl) acryl more than 3 at intramolecularly; Can enumerate: three (acryloxy ethyl) isocyanuric acid ester etc. has multifunctional (methyl) propenoate of isocyanurate ring, multifunctional (methyl) propenoate of polyvalent alcohols such as tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, tripentaerythritol six (methyl) propenoate, tripentaerythritol five (methyl) propenoate, trimethylolpropane tris (methyl) propenoate, ditrimethylolpropane four (methyl) propenoate.
As polyester (methyl) propenoate, can enumerate: the reaction product of diol compound and diprotic acid or its acid anhydride is polyester glycol and (methyl) acrylic acid reaction product etc.
As epoxy (methyl) propenoate; Can enumerate: the terminal glycidyl ether of the propylene oxide adduct of bisphenol A type epoxy resin, bisphenol f type epoxy resin, linear phenolic epoxy resin, dihydroxyphenyl propane, fluorenes epoxy resin, epoxy resin such as bisphenol-s epoxy resin and (methyl) acrylic acid reaction product etc.
The usage ratio of each composition of resin combination of the present invention is considered specific refractory power, second-order transition temperature (Tg), viscosity and the adhesivity etc. of expectation and is confirmed; Composition (A)+composition (B)+composition (C)+composition (D) is being made as under the situation of 100 mass parts; The content of composition (A) is 30 ~ 70 mass parts, is preferably 40 ~ 65 mass parts.The content of composition (B) is 3 ~ 50 mass parts, is preferably 10 ~ 45 mass parts.The content of composition (C) is 3 ~ 20 mass parts, is preferably 5 ~ 15 mass parts.The content of composition (D) is 3 ~ 20 mass parts, is preferably 5 ~ 15 mass parts.Composition (E) is 1 ~ 10 mass parts with respect to total amount 100 mass parts of composition (A)+composition (B)+composition (C)+composition (D), is preferably 3 ~ 7 mass parts.
Conveniences when operating in order to improve etc. except that mentioned component, can according to circumstances make up in resin combination of the present invention and contain releasing agent, skimmer, flow agent, photostabilizer, inhibitor, stopper and static inhibitor etc.Can also further add polymer class such as acrylic polymers, polyester elastomer, urethane polymer and paracril as required.Though also can add solvent, preferably not add solvent.
Resin combination of the present invention can be through preparing each composition mixed dissolution according to ordinary method.For example, each composition packed into to be had in the round-bottomed flask of whipping appts, TM, and stirs 0.5 ~ 6 hour down at 40 ~ 80 ℃, can obtain resin combination of the present invention thus.
With regard to the viscosity of resin combination of the present invention, the viscosity of the transfer printing property of the shape when being suitable for being manufactured on the optical lens that is shaped on the base material and the operability of processibility is preferably used E type viscometer (TV-200; East machine industry corporate system) 25 ℃ of viscosity down that record are the following compsn of 2000mPas.
Resin combination of the present invention can utilize energy-ray easily to be cured.At this,, can enumerate: particle beam such as hertzian wave such as ultraviolet ray, visible rays, infrared rays, X ray, gamma-rays, laser beam, alpha-ray, β ray, electron beam etc. as the concrete example of energy-ray.In the present invention, preferred ultraviolet ray, laser beam, visible rays or electron beam wherein.
Through resin combination of the present invention being shone above-mentioned energy-ray, can obtain cured article of the present invention according to ordinary method.The specific refractory power of resin combination of the present invention is generally 1.51 ~ 1.59, is preferably 1.53 ~ 1.57.Specific refractory power can utilize Abbe refractomecer (model: DR-M2, the Atago of Co., Ltd. system) etc. to measure.
Of the present inventionly for example can obtain: have to be coated with on the pressing mold of shape of lens pillar, prism etc. this resin combination layer is set through following method at the optical lens that is shaped on the base material; Bonding backboard as transparent substrate (for example on this layer; The film of processing by the blend of polymethacrylate resin, polycarbonate resin, polystyrene resin, vibrin or these polymkeric substance etc.) or the glass substrate after being prone to adhesion process etc. and handling; Then; Utilize high voltage mercury lamp etc. this resin combination to be solidified, then cured article is peeled off from this pressing mold from this transparent substrate side irradiation energy ray.
Optical lens of the present invention comprises the lens that makes through any method of manufacture; For example can obtain: on the pressing mold of shape, be coated with this resin combination layer is set with lens pillar, prism etc. through following method; Bonding backboard as transparent substrate (for example on this layer; The film of processing by the blend of polymethacrylate resin, polycarbonate resin, polystyrene resin, vibrin or these polymkeric substance etc.) or the glass substrate after being prone to adhesion process etc. and handling; Then, utilize high voltage mercury lamp etc. this resin combination to be solidified, then cured article is peeled off from this pressing mold from this transparent substrate side irradiation energy ray.
[embodiment]
Below, illustrate in greater detail the present invention through embodiment.But the present invention does not receive any qualification of following examples.Need to prove the unit of numerical value " part " expression mass parts.
Obtain ultraviolet-curing resin composition of the present invention and cured article according to the composition shown in following examples.In addition, evaluation method and the metewand for resin combination and cured film is described below.
(1) viscosity: use E type viscometer (TV-200; Toki Sangyo Co., Ltd.'s system), under 25 ℃, measure.
(2) specific refractory power (25 ℃): use Abbe refractomecer (DR-M2; The Atago of Co., Ltd. system), measure the specific refractory power (25 ℃) of the uv curing resin layer after solidifying.
(3) release property: expression makes resin after the curing difficulty the during demoulding from mould.
Zero the demoulding from the mould is good
When having any problem the perhaps demoulding slightly, the △ demoulding peels off sound
Have residual on * demoulding difficulty or the mould
(4) mould circulation ratio: coating and shaping ultraviolet curing resin layer on base material, utilize high voltage mercury lamp (80W/cm, ozone free) to carry out 1000mJ/cm
2Irradiation make its curing.Observe the surface shape of the ultraviolet curing resin layer after solidifying and the surface shape of mould.
Zero circulation ratio is good.
* circulation ratio is bad.
(5) adhesivity: the sample that in the evaluation of mould circulation ratio, uses is carried out the adhesivity evaluation according to JIS K5600-5-6.For evaluation result, be evaluated as zero with 0 ~ 2, with 3 ~ 5 be evaluated as *.
(6) scuff resistance: use mould on the PET base material, to form prism shape and make test film.The delustring face of involutory diffusion sheet on test film, and then place the counterweight of 100g is above that observed the scratch that produces along with the vertical direction stretching of prismatic pattern diffusion sheet the time.Diffusion sheet uses commercially available article (haze value 50%).
Zero not damaged ~ have slightly damage
* damage arranged
Embodiment 1
Will be as NEWFRONTIER BPE-10 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (A); Polymer with bis phenol A oxyethyl group diacrylate (in the general formula (1), R
1=H, R
2=H, m=5, n=5)) 40 parts, as NEWFRONTIER PHE (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (B); The vinylformic acid phenoxy ethyl) 5 parts, equally as KAYARAD OPP-1.5 (Nippon Kayaku K. K's system of composition (B); Orthoxenol polyethoxye propenoate) 40 parts, as KAYARAD THE-330 (Nippon Kayaku K. K's system of composition (C); TriMethylolPropane(TMP) polyethoxye triacrylate) 10 parts, as KAYARAD UX-0937 (Nippon Kayaku K. K's system of composition (D); The polyethers urethane acrylate oligomer) 5 parts, as Irgacure184 (BASF Japan Co., Ltd. system of composition (E); 1-hydroxyl-cyclohexyl-phenyl ketone) 5 parts are heated to 60 ℃ and mixing, obtain resin combination of the present invention.Utilize high voltage mercury lamp to this resin combination irradiation 1000mJ/cm
2Irradiation dose ultraviolet ray and obtain cured film, and measure specific refractory power.
In addition, to make thickness be about 50 μ m to this resin combination of coating on the prism mould, bonding above that easy to be bonding PET film (COSMOSHINE A4300, thickness 100 μ m spin in Japan) as base material, utilize again high voltage mercury lamp from it quadrature penetrate 1000mJ/cm
2The ultraviolet ray of irradiation dose, peel off after it is solidified, obtain prismatic lens of the present invention.
Evaluation result
Viscosity: 300mPas, specific refractory power: 1.557, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: zero
Embodiment 2
Will be as NEWFRONTIER BPE-1060 part of composition (A), as NEWFRONTIER PHE-2 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (B); Phenoxy diethoxy propene acid esters) 10 parts, as KAYARAD DPCA-60 (Nippon Kayaku K. K's system of composition (C); Dipentaerythritol polycaprolactone six propenoate) 15 parts, as KAYARAD UX-093715 part of composition (D), as Darocur1173 (BASFJapan Co., Ltd. system of composition (E); 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone) 5 parts are heated to 60 ℃ and mixing, obtain resin combination of the present invention.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens of the present invention with embodiment 1.
Evaluation result
Viscosity: 800mPas, specific refractory power: 1.531, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: zero
Embodiment 3
Will be as NEWFRONTIER BPE-20 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (A); Polymer with bis phenol A oxyethyl group diacrylate (in the general formula (1), R
1=H, R
2=H, m=10, n=10)) 30 parts, as 10 parts of the NEWFRONTIER PHE of composition (B), equally as KAYARAD OPP-1 (Nippon Kayaku K. K's system of composition (B); Orthoxenol monosubstituted ethoxy propenoate) 30 parts, as KAYARAD DPCA-120 (Nippon Kayaku K. K's system of composition (C); Dipentaerythritol polycaprolactone six propenoate) 10 parts, as 20 parts of the KAYARAD UX-0937 of composition (D), be heated to 60 ℃ and mix as 5 parts of the Irgacure184 of composition (E), obtain resin combination of the present invention.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens of the present invention with embodiment 1.
Evaluation result
Viscosity: 850mPas, specific refractory power: 1.548, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: zero
Embodiment 4
Will as 30 parts of the NEWFRONTIER BPE-10 of composition (A), as 5 parts of the NEWFRONTIER PHE of composition (B), equally as 45 parts of the KAYARAD OPP-1.5 of composition (B), as SR-9035 (the Sartomer system of composition (C); TriMethylolPropane(TMP) polyethoxye triacrylate) 5 parts, as KAYARAD UX-093715 part of composition (D), be heated to 60 ℃ and mix as Darocur11735 part of composition (E), obtain resin combination of the present invention.The viscosity of this resin combination (25 ℃) is 500mPas.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens of the present invention with embodiment 1.
Evaluation result
Viscosity: 500mPas, specific refractory power: 1.560, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: zero
Comparative example 1
Make routine 3 compound (the 4 mol propylenes acid affixture of bisphenol A diglycidyl ether) according to the embodiment 3 synthetic document of patent documentation 1 (TOHKEMY 2010-126670 communique), with 90 parts of compounds, KAYARAD DPHA (the Nippon Kayaku K. K's system of making example 3; Dipentaerythritol acrylate) 10 parts, Irgacure184 (BASFJapan Co., Ltd. system; 1-hydroxyl-cyclohexyl-phenyl ketone) 2 parts are heated to 60 ℃ and mixing, obtain being used for the resin combination of comparison.The viscosity of this resin combination (50 ℃) is 9400mPas.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.The viscosity of this comparative example is very high, so poor in processability, and release property is also poor, therefore, is inappropriate for continuous molding processing.
Evaluation result
Viscosity: 9400mPas, specific refractory power: 1.550, release property: *, the mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Comparative example 2
Embodiment 1 synthetic routine 1 urethane acrylate according to patent documentation 2 (No. the 4457960th, Japanese Patent); 22.5 parts of compounds, two (4-acryloxy ethoxyl phenenyl) 20 parts of thioethers, 25 parts of adjacent phenyl propenoate, 10 parts of benzyl methacrylates, 17.5 parts of tetrahydrofurfuryl acrylates, 5 parts of Viscoat 295s, the Irgacure184 of synthetic example 1 are heated to 60 ℃ and mixing for 5 parts, obtain being used for the resin combination of comparison.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.
Evaluation result
Viscosity: 70mPas, specific refractory power: 1.560, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Comparative example 3
Will be as NEWFRONTIER BPE-4 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (A); Polymer with bis phenol A oxyethyl group diacrylate (in the general formula (1), R
1=H, R
2=H, m=2, n=2)) 40 parts, as 5 parts of the NEWFRONTIER PHE of composition (B), equally as KAYARAD OPP-1.540 part of composition (B), as 10 parts of the KAYARAD THE-330 of composition (C), as 5 parts of the KAYARAD UX-0937 of composition (D), be heated to 60 ℃ and mix as 5 parts of the Irgacure184 of composition (E), obtain being used for the resin combination of comparison.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.
Evaluation result
Viscosity: 300mPas, specific refractory power: 1.566, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Comparative example 4
Will be as FANCRYL FA-328 (Hitachi Chemical Co., Ltd.'s system of composition (A); Polymer with bis phenol A oxyethyl group diacrylate (in the general formula (1), R
1=H, R
2=H, m=4, n=4)) 30 parts, as 5 parts of the NEWFRONTIER PHE of composition (B), equally as 40 parts of the KAYARAD OPP-1.5 of composition (B), as 20 parts of the KAYARAD THE-330 of composition (C), as 5 parts of the KAYARAD UX-0937 of composition (D), be heated to 60 ℃ and mix as Irgacure1845 part of composition (E), obtain being used for the resin combination of comparison.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.
Evaluation result
Viscosity: 200mPas, specific refractory power: 1.555, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Comparative example 5
Will be as 60 parts of the NEWFRONTIER BPE-10 of composition (A), as NEWFRONTIER PHE-2 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (B); Phenoxy diethoxy propene acid esters) 5 parts, as KAYARAD PET-30 (Nippon Kayaku K. K's system of composition (C); Pentaerythritol triacrylate) 20 parts, as 15 parts of the KAYARAD UX-0937 of composition (D), be heated to 60 ℃ and mix as 5 parts of the Darocur1173 of composition (E), obtain being used for the resin combination of comparison.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.
Evaluation result
Viscosity: 900mPas, specific refractory power: 1.535, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Comparative example 6
Will be as 60 parts of the NEWFRONTIER BPE-10 of composition (A), as NEWFRONTIER PHE-2 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system of composition (B); Phenoxy diethoxy propene acid esters) 10 parts, as KAYARAD DPHA (Nippon Kayaku K. K's system of composition (C); Dipentaerythritol acrylate) 15 parts, as 15 parts of the KAYARAD UX-0937 of composition (D), be heated to 60 ℃ and mix as 5 parts of the Darocur1173 of composition (E), obtain being used for the resin combination of comparison.In addition, the specific refractory power of the resin layer that likewise obtains with embodiment 1 is measured.
The resin combination that use obtains likewise obtains prismatic lens with embodiment 1.
Evaluation result
Viscosity: 900mPas, specific refractory power: 1.539, release property: zero, mould circulation ratio: zero, adhesivity: zero, scuff resistance: *
Evaluation result by embodiment 1 ~ 4 and comparative example 1 ~ 6 shows, have the resin combination of the present invention of specific composition release property, mould circulation ratio, with the good adhesion of substrate film, weather resistance (scuff resistance, scratch resistance) excellence.Therefore, be applicable to the optical lens that for example lens pillar, prism, microlens etc. are shaped on base material, can suppress owing to contacting the shape defect that produces with other optical sheets.
Industrial applicability
Ultra-violet solidified resin composition of the present invention and cured article thereof mainly are specially adapted to the optical lens that lens pillar, prism, microlens etc. are shaped on base material.
Claims (7)
1. the energy ray curable resin composition of an optical lens that is used on base material, being shaped; It contains bisphenol A-type two (methyl) propenoate (A) 30 ~ 70 mass parts of the polyethylene oxide modification shown in the formula (1) respectively; List (methyl) propenoate (B) 3 ~ 50 mass parts with phenylate structure; Has more than 3 (methyl) acryl and with multifunctional (methyl) propenoate (C) 3 ~ 20 mass parts after caprolactone or the oxyethane modification; Carbamate (methyl) origoester acrylate (D) 3 ~ 20 mass parts and Photoepolymerizationinitiater initiater (E) 1 ~ 10 mass parts with tetramethylene glycol structure
In the formula (1), R
1, R
2Represent Wasserstoffatoms or methyl respectively independently, m and n represent 5 ~ 10 positive number respectively independently.
2. energy ray curable resin composition as claimed in claim 1; Wherein, (methyl) propenoate (B) that has a phenylate structure is for being selected from the group that is made up of phenoxyethyl acrylate, phenoxy polyethoxye propenoate, orthoxenol (methyl) propenoate, orthoxenol monosubstituted ethoxy (methyl) propenoate, orthoxenol polyethoxye (methyl) propenoate, p-phenyl phenol (methyl) propenoate, p-phenyl phenol monosubstituted ethoxy (methyl) propenoate, p-phenyl phenol polyethoxye (methyl) propenoate more than one.
3. energy ray curable resin composition as claimed in claim 1; Wherein, carbamate (methyl) origoester acrylate (D) that has a tetramethylene glycol structure is that to make molecular weight be the urethane acrylate oligomer that (methyl) acrylate reactions of 500 ~ 1000 diol compound, polyisocyanate compound and hydroxyl obtains.
4. like each described energy ray curable resin composition in the claim 1 ~ 3, wherein, polyisocyanate compound has ring structure.
5. like each described energy ray curable resin composition in the claim 1 ~ 3, wherein, utilize viscosity under 25 ℃ that E type viscometer records for below the 2000mPas.
6. cured article, it obtains through utilizing the energy-ray irradiation that each described energy ray curable resin composition is solidified.
7. optical lens, it has the described cured article of claim 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-110084 | 2011-05-17 | ||
| JP2011110084A JP5692804B2 (en) | 2011-05-17 | 2011-05-17 | Energy ray curable resin composition for optical lens sheet and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102786640A true CN102786640A (en) | 2012-11-21 |
| CN102786640B CN102786640B (en) | 2017-04-12 |
Family
ID=47152242
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210150403.5A Expired - Fee Related CN102786640B (en) | 2011-05-17 | 2012-05-15 | Energy ray curable resin composition for optical lens sheet, cured object thereof and optical lens sheet |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5692804B2 (en) |
| CN (1) | CN102786640B (en) |
| TW (1) | TW201250386A (en) |
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| CN104761679A (en) * | 2015-03-31 | 2015-07-08 | 长兴（广州）精细涂料有限公司 | Light-cured lens and manufacturing method thereof |
| CN105408775A (en) * | 2013-05-23 | 2016-03-16 | 三菱丽阳株式会社 | Optical film, method for producing optical film, and surface light-emitting body |
| CN109073167A (en) * | 2016-04-15 | 2018-12-21 | 锋翔科技有限公司 | Cured method and system is irradiated using the radiation of narrow width |
| CN112204073A (en) * | 2018-06-01 | 2021-01-08 | 上海富吉医疗器械有限公司 | Polymer material and intraocular lens |
| CN112745793A (en) * | 2019-10-31 | 2021-05-04 | 味之素株式会社 | Curable composition |
| CN113646342A (en) * | 2019-03-29 | 2021-11-12 | 太阳油墨制造株式会社 | Black photosensitive resin composition, cured product thereof, and display device provided with masking layer formed from cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012241127A (en) * | 2011-05-20 | 2012-12-10 | Hitachi Chemical Co Ltd | Photocurable resin composition, and photocurable resin composition varnish and photocurable resin composition cured product using the same |
| KR102058263B1 (en) * | 2013-01-31 | 2019-12-20 | 산요가세이고교 가부시키가이샤 | Active-energy-ray-curable composition for optical members, cured article, and optical lens and sheet or film for optical lenses each produced using said cured article |
| KR102188999B1 (en) | 2013-11-28 | 2020-12-09 | 제이엔씨 주식회사 | Photocurable inkjet ink |
| CN104977633B (en) * | 2014-04-08 | 2018-07-17 | 株式会社巴川制纸所 | Protective film, film laminate and polarizer |
| US10358572B2 (en) * | 2015-02-25 | 2019-07-23 | Dic Corporation | Curable composition, cured product thereof, and optical member |
| JP2018135512A (en) * | 2017-02-23 | 2018-08-30 | 三洋化成工業株式会社 | Active energy ray-curable resin composition |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201250386A (en) | 2012-12-16 |
| JP5692804B2 (en) | 2015-04-01 |
| CN102786640B (en) | 2017-04-12 |
| JP2012242464A (en) | 2012-12-10 |
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