CN100451045C - Composition curable with actinic ray and use thereof - Google Patents
Composition curable with actinic ray and use thereof Download PDFInfo
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- CN100451045C CN100451045C CNB038029790A CN03802979A CN100451045C CN 100451045 C CN100451045 C CN 100451045C CN B038029790 A CNB038029790 A CN B038029790A CN 03802979 A CN03802979 A CN 03802979A CN 100451045 C CN100451045 C CN 100451045C
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Abstract
A composition curable with actinic energy rays which, when cured so as to have a thickness of 60 microm, gives a cured film having the following properties. When the cured film is scratched with a diamond indenter having a tip diameter of 15 microm under a perpendicular load of 235 mN, it recovers from the resultant scratch marks in an atmosphere of 25 DEG C and a relative humidity of 50% based on the self-healing ability of the film. The composition curable with actinic energy rays is hence useful as a coating material or coating composition for products required to have marring resistance.
Description
Technical field
The present invention relates to a kind of composition of curable with actinic energy ray of the product that need to be used to erasibility as coating or coating-forming agent.
Background technology
In the open 2001-2744 of Japan special permission, the inventor has proposed the composition of the ultraviolet curable of a kind of carbamate (methyl) origoester acrylate that comprises ultraviolet curable and light trigger.This oligopolymer by will in a part, having three or more isocyanate groups isocyanate prepolymer and (methyl) vinylformic acid hydroxyethyl ester reaction of polycaprolactone modification obtain.
In the cured product of the composition of ultraviolet curable, can repair by self-reparing capability at the scratch that product surface produces.Therefore, this cured product has erasibility.Therefore, the composition of ultraviolet curable can be used as the product that coating or coating-forming agent need to be used to erasibility.
But in some occasion, the erasibility of cured product is not always gratifying.This has limited the application of the composition of ultraviolet curable.
Summary of the invention
An object of the present invention is to provide a kind of composition that can form the curable with actinic energy ray of cured product with excellent erasibility.
To achieve these goals, in one embodiment of the invention, provide the composition of following curable with actinic energy ray.Deriving from the cured product with thickness 60 μ m of said composition, if use the diamond indenter with tip diameter 15 μ m to carry out the scratch mark under normal load 235mN, the self-reparing capability of this scratch mark by described cured product repaired under the atmosphere of 25 degrees centigrade and relative humidity 50% so.
In another embodiment of the present invention, provide the composition of following curable with actinic energy ray.(methyl) alkyl acrylate that said composition comprises by organic isocyanate that will have a plurality of isocyanate groups in a part and polycaprolactone modification reacts carbamate (methyl) acrylate that obtains.This carbamate (methyl) acrylate comprises two or more different carbamate (methyl) acrylate on the caprolactone units repetition values of (methyl) alkyl acrylate residue of each polycaprolactone modification each other.
In another embodiment of the present invention, provide the composition of following curable with actinic energy ray.Said composition comprises the organic isocyanate and two or more carbamate (methyl) acrylate that (methyl) alkyl acrylate of different polycaprolactone modifications reaction obtains on the caprolactone units repetition values of per molecule each other by will have a plurality of isocyanate groups in a part.
In another embodiment of the present invention, provide the composition of following curable with actinic energy ray.Said composition comprises carbamate (methyl) acrylate that carbamate (methyl) acrylate that (methyl) alkyl acrylate reaction by organic isocyanate that will have a plurality of isocyanate groups in a part and polycaprolactone modification obtains and the organic isocyanate by will having a plurality of isocyanate groups in a part and the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate obtain.
In another embodiment of the present invention, provide the composition of following curable with actinic energy ray.Said composition comprises carbamate (methyl) acrylate that obtains by (methyl) alkyl acrylate of organic isocyanate that will have a plurality of isocyanate groups in a part and polycaprolactone modification and the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate.
Embodiment
First embodiment
The composition of the curable with actinic energy ray of first embodiment of the invention is at first described.
The composition of the curable with actinic energy ray of first embodiment comprises two or more different carbamate (methyl) acrylate on the caprolactone units repetition values of (methyl) alkyl acrylate residue of each polycaprolactone modification each other.
The caprolactone units repetition values of (methyl) alkyl acrylate residue of each polycaprolactone modification in average per molecule carbamate (methyl) acrylate is preferably 1-5, more preferably 1-2.5.Maximum difference between two kinds of carbamates (methyl) acrylate on the repetition values of the caprolactone units of (methyl) alkyl acrylate residue of each polycaprolactone modification is preferably smaller or equal to 9, more preferably 4-9.
Every kind of carbamate (methyl) acrylate is by synthesizing (methyl) alkyl acrylate reaction of organic isocyanate and polycaprolactone modification.By mixing these carbamates (methyl) acrylate, prepare the composition of curable with actinic energy ray.
If (methyl) alkyl acrylate of organic isocyanate and polycaprolactone modification reaction, temperature of reaction are preferably normal temperature to 100 degree centigrade, the reaction times is preferably 1-10 hour.
Organic isocyanate is a kind of organic compound that has a plurality of isocyanate groups in a part.The number that is included in the isocyanate groups in a part organic isocyanate is preferably 3 or greater than 3.
The object lesson that has the organic isocyanate of two isocyanate groups in a part comprises diisocyanate monomer such as inferior cresyl vulcabond, naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, eylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, methyl-2,6-two isocyanato-capronate and norbornene alkyl diisocyanates.
The object lesson that has the organic isocyanate of three or more isocyanate groups in a part comprises that isocyanate prepolymer is as by carrying out diisocyanate monomer the compound of ester modified following general formula (1) expression that obtains of tricarbimide, by diisocyanate monomer being carried out the compound of following general formula (2) expression that the affixture modification obtains, by diisocyanate monomer being carried out the compound of biuret modified following general formula (3) expression that obtains, 2-isocyanic ester ethyl-2,6-two isocyanato-capronates and triaminononane triisocyanate.
The R representative
Or
Or
Or
Or-(CH
2)
6-or
Or
R has the identical meanings as above general formula (1) definition.
(methyl) alkyl acrylate of polycaprolactone modification is the compound of a kind of following general formula (4) expression, and has curable with actinic energy ray functional group as end methylene group (CH
2=).The object lesson of (methyl) alkyl acrylate of polycaprolactone modification comprises (methyl) vinylformic acid hydroxyethyl ester of polycaprolactone modification, (methyl) vinylformic acid hydroxypropyl ester of polycaprolactone modification and (methyl) vinylformic acid hydroxyl butyl ester of polycaprolactone modification.
R represents H or CH
3, n is that integer 1-10 and m are integer 1-25.
The composition of curable with actinic energy ray can be used as the coating and the coating-forming agent of the product that needs erasibility.More specifically, the composition of curable with actinic energy ray is used (application or coating) to electrical equipment or electronic installation such as cell phone, wrist-watch, compact disk, CD, audio-frequency apparatus and office automation equipment; Electronic material parts such as touch panel and be used for the anti-reflection plate of cathode tube; Household electrical appliance such as refrigerator, vacuum cleaner and microwave oven; Automotive interior such as odometer and splash pan; The precoating metal foil; The fuel container of vehicle part such as car body, safety lever, spoiler, door handle, bearing circle, head lamp, motorcycle, plating, steam is sedimentary or the aluminum vehicle wheel of sputter and peephole; The top of carport and the roof of natural lighting; The moulded product of plastics such as polyvinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate and ABS resin; Woodwork such as stair, floor, desk, chair, cupboard and other furniture; Fabric and paper; Sunglasses and be used for corrigent ophthalmic lens.
The composition of curable with actinic energy ray is used by known method such as air-atomizing, no gas blowout mist, electrostatic applications, roller coat device, mobile spreader and spin coating.The thickness of filming is preferably about 1-100 μ m.
The composition of curable with actinic energy ray is by solidifying as ultraviolet ray and electron beam irradiation with actinic rays.Uviolizing preferably uses UV light source such as mercury lamp and metal halide lamp to carry out, and is 100-1000mJ/cm so that solidify energy (total light intensity)
2The electron beam irradiation is preferably carried out under acceleration voltage 150-250keV, so that dosage is 1-5Mrad.
Functional element and optical element according to first embodiment are below described.
If the cured product of the composition of the curable with actinic energy ray of first embodiment is molded as predetermined shape or forms the cured layer of being made by the composition of curable with actinic energy ray on the surface of base material, so just formed the functional element and the optical element of first embodiment.It maybe can be the layer that is used for the protecting group material as functional element or optical element that cured layer self can be used as functional element or optical element.
Functional element is a kind of element with certain useful property.The object lesson of functional element comprises optical reflection film, anti-reflective film, polaroid, light-diffusing films, phase lining form, the film that is used to regulate angle of visibility, thermal reflecting coating, ultraviolet screener film, electromagnetic shielding film and is used for the film of touch sensor.Optical element is a kind of element with useful optical characteristics.The object lesson of optical element comprises optical reflection film, anti-reflective film, polaroid, light-diffusing films, phase lining form and is used to regulate the film of angle of visibility.
In the process of preparation functional element and optical element, the composition of curable with actinic energy ray is by solidifying as ultraviolet ray and electron beam irradiation with actinic rays.Be used for photoactinic preferred illuminate condition as mentioned above this moment.
First embodiment has the following advantages.
(a) maximum scratch load (normal load) is defined as critical loading, wherein when using the diamond indenter with tip diameter 15 μ m to produce the scratch mark on sample, the self-reparing capability that this scratch mark can be by this sample is repaired under 25 degrees centigrade of atmosphere with relative humidity 50%.In the cured product of the composition of the curable with actinic energy ray of first embodiment, the value of critical loading is greater than the cured product of conventional ultraviolet curable composition.Particularly, the value of the critical loading that the cured product with thickness 60 μ m (cured film) that uses the composition by the curable with actinic energy ray of first embodiment to form is measured is 235mN (24gf) or be higher than 235mN and optionally as 390mN (40gf) or be higher than 390mN at least.Because cured product has excellent erasibility as mentioned above, the composition of the curable with actinic energy ray of first embodiment can be used as coating or coating-forming agent is used for the special product that needs erasibility consumingly.
(b) if carbamate (methyl) acrylate by will in a part, having three or more isocyanate groups organic compound and (methyl) alkyl acrylate reaction of polycaprolactone modification obtain, then the erasibility of the cured product of the composition of curable with actinic energy ray is improved.
(c) if the repetition values of the caprolactone units of (methyl) alkyl acrylate residue of each polycaprolactone modification is 1-5 in average per molecule carbamate (methyl) acrylate, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.If described mean value is 1-2.5, its effect further increases.
(d) if the maximum difference on the caprolactone units repetition values of (methyl) alkyl acrylate residue of each polycaprolactone modification is 9 or is lower than 9 that then the erasibility of the cured product of the composition of curable with actinic energy ray is improved between two kinds of carbamates (methyl) acrylate.If described maximum difference is 4-9, its effect further increases.
Second embodiment
Below, for the composition of the curable with actinic energy ray of second embodiment, mainly describe its with the difference of the composition of the curable with actinic energy ray of first embodiment.
The composition of the curable with actinic energy ray of second embodiment comprises by with organic isocyanate and two or more carbamate (methyl) acrylate that (methyl) alkyl acrylate of different polycaprolactone modifications reaction obtains on the caprolactone units repetition values of each molecule each other.
The average repetition values of the caprolactone units of (methyl) alkyl acrylate of per molecule polycaprolactone modification is preferably 1-5, more preferably 1-2.5.Maximum difference between (methyl) alkyl acrylate of two kinds of polycaprolactone modifications on the caprolactone units repetition values is preferably 9 or be lower than 9, more preferably 4-9.
Below, for the functional element and the optical element of second embodiment, itself and the functional element of first embodiment and the difference of optical element are described mainly.If the cured product of the composition of the curable with actinic energy ray of second embodiment is molded as predetermined shape or forms the cured layer of being made by the composition of curable with actinic energy ray on the surface of base material, so just formed the functional element and the optical element of second embodiment.
Second embodiment has the following advantages.
(e) composition of the curable with actinic energy ray of second embodiment has the identical advantage of describing at (a) and (b) with first embodiment.
(f) if the average repetition values of the caprolactone units of (methyl) alkyl acrylate of per molecule polycaprolactone modification is 1-5, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.If described mean value is 1-2.5, its effect further increases.
(g) if the maximum difference on the caprolactone units repetition values is 9 or is lower than 9 between (methyl) alkyl acrylate of two kinds of polycaprolactone modifications, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.If described maximum difference is 4-9, its effect further increases.
The 3rd embodiment
Below, for the composition of the curable with actinic energy ray of the 3rd embodiment, the difference of composition of the curable with actinic energy ray of itself and first and second embodiments is described mainly.
The composition of the curable with actinic energy ray of the 3rd embodiment comprises carbamate (methyl) acrylate and carbamate (methyl) acrylate by organic isocyanate and the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate are obtained that obtains by (methyl) alkyl acrylate reaction with organic isocyanate and polycaprolactone modification.
The object lesson of (methyl) vinylformic acid hydroxyalkyl acrylate comprises that the compound of following general formula (5) expression is as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester and (methyl) vinylformic acid hydroxyl butyl ester.
R represents H or CH
3, the 1st, integer 1-10.
If (methyl) alkyl acrylate of polycaprolactone modification and (methyl) vinylformic acid hydroxyalkyl acrylate are generically and collectively referred to as (methyl) acrylate monomer, then (methyl) vinylformic acid hydroxyalkyl acrylate can be considered to wherein that the repetition values of caprolactone units is zero (methyl) acrylate monomer.
The caprolactone units repetition values of each (methyl) acrylate monomer residue is preferably 1-5 in average per molecule carbamate (methyl) acrylate, more preferably 1-2.5.Between two kinds of carbamates (methyl) acrylate on the residue of each (methyl) acrylate monomer the maximum difference of the repetition values of caprolactone units be preferably 9 or be lower than 9,4-9 more preferably.
Below, for the functional element and the optical element of the 3rd embodiment, itself and the functional element of first embodiment and the difference of optical element are described mainly.If the cured product of the composition of the curable with actinic energy ray of the 3rd embodiment is molded as predetermined shape or forms the cured layer of being made by the composition of curable with actinic energy ray on the surface of base material, so just formed the functional element and the optical element of the 3rd embodiment.
The 3rd embodiment has the following advantages.
(h) composition of the curable with actinic energy ray of the 3rd embodiment has the identical advantage that above first embodiment is described in (a).
(i) if carbamate (methyl) acrylate by will in a part, having three or more isocyanate groups organic compound and (methyl) alkyl acrylate or the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate of polycaprolactone modification synthesize, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.
(j) if the caprolactone units repetition values of each (methyl) acrylate monomer residue is 1-5 in average per molecule carbamate (methyl) acrylate, the erasibility of the cured product of curable with actinic energy ray composition is improved so.If described mean value is 1-2.5, its effect further increases.
(k) if the maximum difference of the caprolactone units repetition values of each (methyl) acrylate monomer residue between two kinds of carbamates (methyl) acrylate is 9 or is lower than 9 that the erasibility of the cured product of curable with actinic energy ray composition is improved so.If described maximum difference is 4-9, its effect further increases.
The 4th embodiment
Below, for the composition of the curable with actinic energy ray of the 4th embodiment, the difference of composition of the curable with actinic energy ray of itself and first to the 3rd embodiment is described mainly.
The composition of the curable with actinic energy ray of the 4th embodiment comprises carbamate (methyl) acrylate that obtains by (methyl) alkyl acrylate and the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate with organic isocyanate and polycaprolactone modification.In other words, the composition of the curable with actinic energy ray of the 4th embodiment comprises by with organic isocyanate and two or more carbamate (methyl) acrylate that reaction of different (methyl) acrylate monomer obtains on the caprolactone units repetition values of per molecule each other.
The average repetition values of the caprolactone units of per molecule (methyl) acrylate monomer is preferably 1-5, more preferably 1-2.5.The maximum difference of the caprolactone units repetition values between two kinds of (methyl) acrylate monomers is preferably 9 or be lower than 9, more preferably 4-9.
Below, for the functional element and the optical element of the 4th embodiment, itself and the functional element of first embodiment and the difference of optical element are described mainly.If the cured product of the composition of the curable with actinic energy ray of the 4th embodiment is molded as predetermined shape or forms the cured layer of being made by the composition of curable with actinic energy ray on the surface of base material, so just formed the functional element and the optical element of the 4th embodiment.
The 4th embodiment has the following advantages.
(l) composition of the curable with actinic energy ray of the 4th embodiment has the identical advantage that above first embodiment is described in (a).
(m) if carbamate (methyl) acrylate by will in a part, having three or more isocyanate groups organic compound and (methyl) alkyl acrylate and the reaction of (methyl) vinylformic acid hydroxyalkyl acrylate of polycaprolactone modification synthesize, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.
(n) if the repetition mean value of the caprolactone units of per molecule (methyl) acrylate monomer is 1-5, the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.If described mean value is 1-2.5, its effect further increases.
(o) if the maximum difference of the caprolactone units repetition values of two kinds of (methyl) acrylate monomers is 9 or is lower than 9 that the erasibility of the cured product of the composition of curable with actinic energy ray is improved so.If described maximum difference is 4-9, its effect further increases.
Above-mentioned embodiment can be made following change.
The building-up reactions of carbamate (methyl) acrylate can be carried out in solvent.The object lesson of solvent comprises aromatic hydrocarbon solvent such as toluene and dimethylbenzene; Ketone solvent such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; With ester solvent such as ethyl acetate, propyl acetate, isobutyl acetate and n-butyl acetate.
In the building-up reactions of carbamate (methyl) acrylate, can use catalyzer or polymerization inhibitor.The object lesson of catalyzer comprises dibutyl tin laurate, dibutyl tin diethyl hexaoate and sulfurous acid dibutyl tin.The object lesson of polymerization inhibitor comprises the hydroquinone monomethyl ether.
In the building-up reactions system of carbamate (methyl) acrylate, can add long-chain alcohol.The adding of long-chain alcohol can improve the surface smoothness of cured product of the composition of curable with actinic energy ray, thereby improves the erasibility of cured product.
The object lesson of long-chain alcohol comprises three decyl alcohol, myristyl alcohol, hexadecanol, stearyl alcohol, V-1326, polyoxyl 40 stearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl base ether and Zerol.Preferred long-chain alcohol is to carry out polyether-modified long-chain alcohol, as polyether-modified hexadecyl alcohol.Given the antistatic property of the cured product of making by the composition of curable with actinic energy ray through the adding of polyether-modified long-chain alcohol.
The composition of every kind of curable with actinic energy ray of above-mentioned embodiment can further comprise any compound, silicone compounds and fluorine cpd that contain long chain alkyl group.Compound, silicone compounds and the fluorine cpd that contain long chain alkyl group can improve the surface smoothness of cured product of the composition of curable with actinic energy ray, thereby improve the erasibility of cured product.
The compound, silicone compounds and the fluorine cpd that contain long chain alkyl group preferably have the functional group of curable with actinic energy ray respectively.The compound that contains long chain alkyl group, silicone compounds and the fluorine cpd that have curable with actinic energy ray functional group respectively reduced curable with actinic energy ray composition viscosity and make that the said composition height is firm.They have further improved the adhesivity and the solvent resistance of the cured product and the base material of curable with actinic energy ray composition.
The carbonatoms that is included in the long chain alkyl group in the compound that contains long chain alkyl group is preferably 13-25.This is because the erasibility of the cured product of being made by the composition of curable with actinic energy ray can further be improved.Object lesson with compound that contains long chain alkyl group of 13-25 carbon atom comprises that long-chain alcohol is as three decyl alcohol, myristyl alcohol, hexadecanol, stearyl alcohol, docosyl alcohol, polyoxyethylene cetyl alcohol, the pure and mild Zerol of polyoxyethylene stearyl; The compound of curable with actinic energy ray is as (methyl) tridecyl acrylate, (methyl) vinylformic acid nutmeg base ester, (methyl) vinylformic acid hexadecyl ester, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid docosyl ester and stearoyl-oxy polyethyleneglycol (methyl) acrylate.The compound of curable with actinic energy ray has the functional group of curable with actinic energy ray.
The object lesson of silicone compounds comprise the acrylate modified polydimethylsiloxane of the polydimethylsiloxane of polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, amino modified polydimethylsiloxane, epoxide modified polydimethylsiloxane, fluorine modification and (methyl) (as, " GUV-235 ", trade(brand)name is produced by Toagosei company limited).
The object lesson of fluorine cpd comprises compound such as fluoroalkyl carboxylate salt, fluoroalkyl quaternary ammonium salt and the fluoroalkyl ethylene oxide adduct with fluoro-alkyl group; Compound such as perfluoroalkyl carboxylate, perfluoroalkyl quaternary ammonium salt and perfluoroalkyl ethylene oxide adduct with perfluoro alkyl group; Compound with fluorocarbon group; Tetrafluoro ethylene polymer; The multipolymer of vinylidene fluoride and tetrafluoroethylene; The multipolymer of vinylidene fluoride and R 1216; Fluorine-containing (methyl) acrylate; The polymkeric substance of fluorine-containing (methyl) acrylate; The polymkeric substance of fluorine-containing (methyl) alkyl acrylate; With fluorine-containing (methyl) acrylate and other monomeric multipolymer.The object lesson of fluorine-containing (methyl) acrylate comprises 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluoro hexyl-2-hydroxypropyl) ester; 2-((methyl) acryl oxygen ylmethyl)-2-(hydroxymethyl) propionic acid (3-perfluoro hexyl-2-((methyl) acryl oxygen base) propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluoro capryl-2-hydroxypropyl) ester; 2-((methyl) acryl oxygen ylmethyl)-2-(hydroxymethyl) propionic acid (3-perfluoro capryl-2-((methyl) acryl oxygen base) propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluoro hexyl-(1-hydroxymethyl) ethyl) ester; 2-((methyl) acryl oxygen ylmethyl)-2-(hydroxymethyl) propionic acid (2-perfluoro hexyl-1-((methyl) acryl oxygen ylmethyl ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluoro capryl-(1-hydroxymethyl) ethyl) ester; 2-((methyl) acryl oxygen ylmethyl)-2-(hydroxymethyl) propionic acid (2-perfluoro capryl-1-((methyl) acryl oxygen ylmethyl) ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluoro butyl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluoro hexyl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluoro capryl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluor cyclopentyl-methyl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluor cyclohexyl methyl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (3-perfluor suberyl methyl-2-(methyl) acryl oxygen base propyl group) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluoro butyl-(1-(methyl) acryl oxygen ylmethyl) ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluoro hexyl-(1-(methyl) acryl oxygen ylmethyl) ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluoro capryl-(1-(methyl) acryl oxygen ylmethyl) ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluor cyclopentyl-methyl-((methyl) acryl oxygen ylmethyl) ethyl) ester; (methyl) vinylformic acid perfluoro capryl ethyl ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluor cyclohexyl methyl-(1-(methyl) acryl oxygen ylmethyl) ethyl) ester; 2; 2-two ((methyl) acryl oxygen ylmethyl) propionic acid (2-perfluor suberyl methyl-(1-(methyl) acryl oxygen ylmethyl) ethyl) ester; (methyl) vinylformic acid-2; 2; 2-trifluoroethyl (ester); (methyl) vinylformic acid-2; 2; 3; 3; 3-five fluoropropyls (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 4-seven fluorine butyl (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 5; 5; 5-nine fluorine amyl groups (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 5; 5; 6; 6; 6-11 fluorine hexyls (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 5; 5; 6; 6; 7; 7; 7-ten trifluoro heptyl (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 5; 5; 6; 6; 7; 7; 8; 8; 8-15 fluorine octyl groups (ester); (methyl) vinylformic acid-3; 3; 4; 4; 5; 5; 6; 6; 7; 7; 8; 8; 8-ten trifluoro octyl groups (ester); (methyl) vinylformic acid-2; 2; 3; 3; 4; 4; 5; 5; 6; 6; 7,7,8; 8; 9,9,10; 10; 10-19 fluorine decyls (ester); (methyl) vinylformic acid-3,3,4; 4; 5,5,6; 6; 7,7,8; 8; 9,9,10; 10; 10-17 fluorine decyls (ester); (methyl) vinylformic acid-2-trifluoromethyl-3,3,3-trifluoro propyl (ester); (methyl) vinylformic acid-3-trifluoromethyl-4; 4; 4-trifluoro butyl (ester); (methyl) vinylformic acid-1-methyl-2,2,3; 3; 3-five fluoropropyls (ester); (methyl) vinylformic acid-1-methyl-2,2,3; 3; 3,4,4; 4-seven fluorine butyl (ester); two (methyl) vinylformic acid-2; 2,2-trifluoroethyl ethylene glycol (ester); two (methyl) vinylformic acid-2,2; 3; 3,3-five fluoropropyl ethylene glycol (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 4-seven fluorine butyl glycols (ester); two (methyl) vinylformic acid-2; 2,3,3; 4; 4,5,5; 5-nine fluorine amyl group ethylene glycol (ester); two (methyl) acryllic acid-2; 2,3,3; 4; 4,5,5; 6; 6,6-11 fluorine hexyl ethylene glycol (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5,6,6; 7; 7,7-ten trifluoro heptyl ethylene glycol (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5,6,6; 7; 7,8,8; 8-50 fluorine octyl group ethylene glycol (ester); two (methyl) vinylformic acid-2; 2,3,3; 4; 4,5,5; 6; 6,7,7; 8; 8,9,9; 10; 10,10-19 fluorine decyl ethylene glycol (ester); two (methyl) vinylformic acid-2,2; 3; 3-tetrafluoro butyleneglycol (ester); two (methyl) vinylformic acid-2,2,3; 3; 4,4-hexafluoro pentanediol (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5-octafluorohexane diol (ester); two (methyl) vinylformic acid-2,2,3; 3; 4,4,5; 5; 6,6-ten fluorine heptanediols (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5,6,6; 7; 7-ten difluoro ethohexadiols (ester); two (methyl) vinylformic acid-2,2,3; 3; 4,4,5; 5; 6,6,7; 7; 8,8-ten tetrafluoro nonanediols (ester); two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5,6,6; 7; 7,8,8; 9; 9-ten hexafluoro decanediols (ester); two (methyl) vinylformic acid-2,2,3; 3; 4,4,5; 5; 6,6,7; 7; 8,8,9; 9; 10,10-ten octafluoros, 11 carbon glycol (ester) and two (methyl) vinylformic acid-2,2; 3; 3,4,4; 5; 5,6,6; 7; 7,8,8; 9; 9,10,10; 11,11-20 fluorine 12 carbon glycol (ester).
The composition of every kind of curable with actinic energy ray of above-mentioned embodiment can further comprise the compound that contains curable with actinic energy ray functional group.The compound that contains curable with actinic energy ray functional group reduces the viscosity of the composition of curable with actinic energy ray, and makes that the said composition height is firm.This compound has further improved the adhesivity and the solvent resistance of the cured product and the base material of curable with actinic energy ray composition.
The object lesson that contains the compound of curable with actinic energy ray functional group comprises respectively simple function and polyfunctional monomer and simple function that has (methyl) acryl group respectively and the multifunctional oligopolymer with (methyl) acryl group.More specifically, its example comprises monofunctional monomer such as phthalic acid (methyl) vinylformic acid list hydroxyethyl ester, (methyl) vinylformic acid 2-oxyethyl group polyhexamethylene, (methyl) vinylformic acid phenoxy group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-ethoxy ethoxy ethyl ester, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxypropyl ester, (methyl) vinylformic acid hydroxyethyl ester of polycaprolactone modification, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, the N-vinyl pyrrolidone, acryloyl morpholine, (methyl) isobornyl acrylate, vinyl-acetic ester and vinylbenzene; Two functional monomers such as dimethyltrimethylene glycol two (methyl) acrylate, 1,9-nonane glycol two (methyl) acrylate, 1,6-hexane diol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, propylene glycol two (methyl) acrylate and dipropylene glycol two (methyl) acrylate; Six (methyl) acrylate of the caprolactone affixture of three (methyl) acrylate of three (methyl) acrylate of 3 mole propylene oxide affixtures of polyfunctional monomer such as trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, TriMethylolPropane(TMP), 6 mole ethylene oxide affixtures of TriMethylolPropane(TMP), glycerine propoxy-three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and Dipentaerythritol; With oligopolymer such as unsaturated polyester, polyester (methyl) acrylate, polyethers (methyl) acrylate, acryl (methyl) acrylate, carbamate (methyl) acrylate and epoxy (methyl) acrylate.
The object lesson that contains the compound of curable with actinic energy ray functional group further comprises (methyl) vinylformic acid phenylphenol ethoxylated ester, (methyl) vinylformic acid phenylphenol diethoxy ester, (methyl) vinylformic acid phenylphenol five ethoxylated esters, 1,3-two [2-methacryloyl oxygen base-3-(2,4,6-tribromophenoxy) propoxy-] benzene, two phenoxyethyl alcohol fluorenes two (methyl) acrylate, have carbamate (methyl) acrylate of fluorene skeleton and have (methyl) acrylate of the 6-caprolactone affixture of fluorene skeleton; With (methyl) acrylate of sulfur-bearing as 4; 4 '-two (4-hydroxy phenyl) sulfone two (methyl) acrylate; 4; 4 '-two (4-hydroxyl-oxethyl phenyl) sulfone two (methyl) acrylate; 2; 5-two acryl Oxy-1s; the 4-dithiane; two-2-(methyl) acryl thio-ethyl-sulfide; 1; 4-(methyl) acryl thio phenyl; 4; 4 '-two [2-(methyl) acryl oxygen base] diphenyl sulfide; 4; 4 '-two [2-(methyl) acryl oxygen base oxethyl] diphenyl sulfide; 4; 4 '-two [2-(methyl) acryl oxygen base propoxy-] diphenyl sulfide; 4; 4 '-two [2-(methyl) acryl oxygen base oxethyl] phenylsulfone; 4; 4 '-two [2-(methyl) acryl oxygen base propoxy-] phenylsulfone; 4; two (methyl) acrylate of 4 '-dihydroxy-benzene thioether-ethylene oxide or propylene oxide adduct; (methyl) vinylformic acid thiophenyl ethyl ester [for example; " BX-PTEA " (vinylformic acid thiophenyl ethyl ester); produce by BIMAX chemical company limited]; 1; 3-two [2-(methyl) acryl-3-(1; 3-dithiolane-2-yl) ethylmercapto group-propoxy-] benzene; 2-phenyl-4-acryl sulfenyl methyl isophthalic acid; 3-dithiolane and 4; 4 '-two (Beta-methyl acryloxy ethylmercapto group) sulfobenzide; 2; 5-two (acryloxy ethylmercapto group methyl)-1; 4-dithiane and 1, the inferior dimethylbenzene of 4-two (2--methacryloxy ethylmercapto group).These compounds improve the refractive index of the cured product of curable with actinic energy ray composition.
Every kind of curable with actinic energy ray composition of above-mentioned embodiment can further comprise light trigger.Light trigger improves the curing characteristics such as the accelerated rates of cure of curable with actinic energy ray composition.The object lesson of light trigger comprises the sec.-propyl benzoin ether; the isobutyl-benzoin ether; benzophenone; wheat Qira (Michler) ketone; phenylformic acid o-benzoyl ylmethyl ester; methyl phenyl ketone; 2; 4-diethyl sulfenyl xanthone; 2-chlorothio xanthone; EAQ; ESCAROL 507 isopentyl ester; the ESCAROL 507 ethyl ester; the 1-hydroxycyclohexylphenylketone (for example; " Irgacure 184 "; produce by the different chemical of vapour Bart company limited); 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (for example; " Darocure 1173 "; produce by the different chemical of vapour Bart company limited); 2; 2-dimethoxy-1; the 2-diphenylethane-1-ketone (for example; " Irgacure 651 "; produce by the different chemical of vapour Bart company limited); 2-benzyl-2-dimethylamino-1 (4-morpholino phenyl)-butanone-1; two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide and formic acid methyl-benzyl ester.
The composition of every kind of curable with actinic energy ray of above-mentioned embodiment can further comprise bead.This bead is given the antireflection effect to the cured product of curable with actinic energy ray composition.The object lesson of bead comprises respectively by synthetic resins such as polymethylmethacrylate, nylon, urethane, siloxanes or polycarbonate, or the bead made of rubber; The bead of making by metal such as titanium oxide, titanium dioxide, aluminum oxide, stannic oxide, Indium sesquioxide, zinc oxide, weisspiessglanz, stibiated stannic oxide or stanniferous Indium sesquioxide respectively; The bead of making by silicon-dioxide or glass respectively.
Every kind of curable with actinic energy ray composition of above-mentioned embodiment can further comprise static inhibitor.Static inhibitor is given antistatic property to the cured product of curable with actinic energy ray composition.The object lesson of static inhibitor comprises anionic antistatic agents such as alkylphosphonic, cationic antistatic agent such as quaternary ammonium salt, non-ionic antistatic agent such as Voranol EP 2001 and comprises basic metal such as the static inhibitor of the salt of lithium, sodium or potassium.Preferred static inhibitor is to comprise those of lithium salts.
Every kind of curable with actinic energy ray composition according to above-mentioned embodiment can further comprise solvent, flow agent or uv-absorbing agent.The object lesson of solvent comprises aromatic hydrocarbon solvent such as toluene and dimethylbenzene; Alcoholic solvent such as methyl alcohol, ethanol, isopropyl alcohol, propyl carbinol and isopropylcarbinol; Ketone solvent such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) and pimelinketone; Ester solvent such as ethyl acetate, propyl acetate, n-butyl acetate and isobutyl acetate.The object lesson of flow agent comprises acrylic copolymer and siloxanes flow agent and fluorine flow agent.The object lesson of uv-absorbing agent comprises the uv-absorbing agent based on benzophenone, benzotriazole, oxalic acid N-anilide, triazine and bulky amine.
Embodiment
Below, by reference example and Comparative Examples the present invention is described in more detail.Wherein " part " is meant " weight part ".
(synthesis example 1)
With 50 parts of toluene, 50 parts through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N ", trade(brand)name, produce by Takeda chemical industry company limited, 20.9%), the hydroxyethyl acrylate (" PLACCELFA1 " of 63 parts of polycaprolactone modifications isocyanate content:, trade(brand)name is produced by Daicel chemical industry company limited), 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture kept 5 hours down at 70 degrees centigrade.Then, 63 parts of toluene are added this mixture to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 1.
(synthesis example 2)
With 50 parts of toluene, 50 parts through biuret modified hexamethylene diisocyanate (" DURANATE 24A-90CX ", trade(brand)name, by Asahi Kasei company, N.V. produce, non-volatile content: 90%, 21.2%), the hydroxyethyl acrylate (" PLACCEL FA2D " of 92 parts of polycaprolactone modifications isocyanate content:, trade(brand)name is produced by Daicel chemical industry company limited), 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture kept 5 hours down at 70 degrees centigrade.Then, add 82 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 2.
(synthesis example 3)
(" NAA-46 ", trade(brand)name are produced hydroxyl value by NOF company: 207) also that this mixture heating up is extremely the highest 40 degrees centigrade to add 4.2 parts of stearyl alcohol in 50 parts of toluene.After abundant dissolving stearyl alcohol, adds 50 parts through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATED-170N ") and with this mixture 70 degrees centigrade of maintenances 30 minutes down.Subsequently, add 0.02 part of dibutyl tin laurate and mixture kept 3 hours down at 70 degrees centigrade.In addition, the hydroxyethyl acrylate (" PLACCEL FA3 " that adds 114 parts of polycaprolactone modifications, trade(brand)name is produced by Daicel chemical industry company limited), 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether also keep mixture 3 hours down at 70 degrees centigrade.Then, add 118.2 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 3.
(synthesis example 4)
With 50 parts of toluene, 50 parts of hydroxyethyl acrylate (" PLACCEL FA5 " through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-17ON "), 179 parts of polycaprolactone modifications, trade(brand)name is produced by Daicel chemical industry company limited), 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture kept 5 hours down at 70 degrees centigrade.Then, add 179 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 5.
(synthesis example 5)
With 50 parts of toluene, 25 parts of hydroxyethyl acrylate (" PLACCEL PA1O " through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N "), 162.8 parts of polycaprolactone modifications, trade(brand)name is produced by Daicel chemical industry company limited) 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture kept 5 hours down at 70 degrees centigrade.Then, add 137.8 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 10.
(synthesis example 6)
With 25 parts of toluene, 25 parts through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N "), 32 parts of vinylformic acid 2-hydroxyethyl esters (" LIGHT ESTERHOA ", trade(brand)name is produced by KYOEISHA chemical industry company limited), 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture kept 5 hours down at 70 degrees centigrade.Then, add 32 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 0.
(synthesis example 7)
(" NONION P-208 ", trade(brand)name are produced hydroxyl value by NOF company: 95) and with mixture heating up to the highest 40 degrees centigrade to add 10.3 parts of polyether-modified hexadecanols in 60 parts of toluene.After the polyether-modified hexadecanol of abundant dissolving, adds 50 parts through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N ") and with this mixture 70 degrees centigrade of maintenances 30 minutes down.Subsequently, add 0.02 part of dibutyl tin laurate and mixture kept 3 hours down at 70 degrees centigrade.In addition, add the hydroxyethyl acrylate (" PLACCELFA 1 ") of 55.9 parts of polycaprolactone modifications, 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether and mixture kept 3 hours down at 70 degrees centigrade.Then, add 56.2 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each the acrylate monomer residue in the gained urethane acrylate is 1.
(synthesis example 8)
50 parts of toluene, 50 parts of hydroxyethyl acrylate (" PLACCELFA3 ") through the hydroxyethyl acrylate (" PLACCEL FA1 ") of the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N "), 47 parts of polycaprolactone modifications, 31 parts of polycaprolactone modifications, 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether are mixed and mixture was kept 5 hours down at 70 degrees centigrade.Then, add 78 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each acrylate monomer residue is 1.5 in the average per molecule urethane acrylate.In addition, the maximum difference on repetition values is 2 between two kinds of urethane acrylates.
(synthesis example 9)
50 parts of toluene, 25 parts of hydroxyethyl acrylate (" PLACCELFA5 ") through the hydroxyethyl acrylate (" PLACCEL FA1 ") of the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N "), 55 parts of polycaprolactone modifications, 24 parts of polycaprolactone modifications, 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether are mixed and mixture was kept 5 hours down at 70 degrees centigrade.Then, add 79 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each acrylate monomer residue is 1.5 in the average per molecule urethane acrylate.In addition, the maximum difference on repetition values is 4 between two kinds of urethane acrylates.
(synthesis example 10)
With 25 parts of toluene, 50 parts of hexamethylene diisocyanates (" BURNOCK DN-950 " through the modification of TriMethylolPropane(TMP) affixture, trade(brand)name, produce by Japanese ink and chemical company limited, non-volatile content: 75%, 12%), the hydroxyethyl acrylate (" PLACCEL FA10 ") of 13.3 parts of 2-hydroxyethyl acrylate (" LIGHT ESTER HOA "), 35.9 parts of polycaprolactone modifications, 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture was kept 5 hours down at 70 degrees centigrade isocyanate content:.Then, add 49.2 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each acrylate monomer residue is 2 in the average per molecule urethane acrylate.In addition, the maximum difference on repetition values is 10 between two kinds of urethane acrylates.
(synthesis example 11)
(" NAA-422 ", trade(brand)name are produced hydroxyl value by NOF company: 180) and with mixture heating up to the highest 40 degrees centigrade to add 5.8 parts of docosyl alcohol in 50 parts of toluene.After abundant dissolving docosyl alcohol, adds 50 parts through the ester modified hexamethylene diisocyanate of tricarbimide (" TAKENATE D-170N ") and with this mixture 70 degrees centigrade of maintenances 30 minutes down.Subsequently, add 0.02 part of dibutyl tin laurate and mixture kept 3 hours down at 70 degrees centigrade.In addition, add the hydroxyethyl acrylate (" PLACCEL FA5 ") of 2.8 parts of vinylformic acid 2-hydroxyethyl esters (LIGHT ESTER HOA), the hydroxyethyl acrylate (" PLACCEL FA1 ") of 36.1 parts of polycaprolactone modifications, 48.1 parts of polycaprolactone modifications, 0.02 part of dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether and mixture kept 5 hours down at 70 degrees centigrade.Then, add 92.8 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each acrylate monomer residue is 2 in the average per molecule urethane acrylate.In addition, the maximum difference on repetition values is 5 between two kinds of urethane acrylates.
(synthesis example 12)
With 50 parts of toluene, 87 parts through the ester modified isoflurane chalcone diisocyanate of tricarbimide (" BESTANATE T1890E ", trade(brand)name, produce by DegussaAG), non-volatile content: 70%, isocyanate content: 12%], 59.8 the hydroxyethyl acrylate (" PLACCEL FA1 ") of part polycaprolactone modification, 32.8 the hydroxyethyl acrylate (" PLACCELFA20 " of part polycaprolactone modification, trade(brand)name is produced by Daicel chemical industry company limited), 0.02 part dibutyl tin laurate and 0.02 part of hydroquinone monomethyl ether mix and mixture were kept 5 hours down at 70 degrees centigrade.Then, add 84.5 parts of toluene to obtain having the urethane acrylate of solids content 50% weight.The caprolactone units repetition values of each acrylate monomer residue is 2 in the average per molecule urethane acrylate.In addition, the maximum difference on repetition values is 19 between two kinds of urethane acrylates.
The caprolactone units repetition values and the hydroxyl value that are used for each molecule acrylate monomer of synthesis example 1 to 12 provide at table 1.
Table 1
| Acrylate monomer | HEA | FA1 | FA2D | FA3 | FA5 | FA10 | FA20 |
| The caprolactone units repetition values of each acrylate monomer molecule | 0 | 1 | 2 | 3 | 5 | 10 | 20 |
| Hydroxyl value | 484 | 244 | 163 | 122 | 82 | 45 | 23 |
(embodiment 1)
With 60 parts of urethane acrylates that in synthesis example 1, obtain, 20 parts of urethane acrylates that in synthesis example 3, obtain, 10 parts of vinylformic acid phthalic acid list hydroxyethyl esters (" M-5400 ", trade(brand)name, produce by Toagosei company limited), 10 parts of toluene and 3 parts of light triggers (" IRGACURE 184 ", trade(brand)name is produced by the CIBA speciality chemical) mix the composition that has the curable with actinic energy ray of solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the composition of curable with actinic energy ray is 1.5.In addition, be included in that the difference on repetition values is 2 between two kinds of urethane acrylates in the composition of this curable with actinic energy ray.
(embodiment 2)
With 73 parts of urethane acrylates that in synthesis example 1, obtain, 27 parts of urethane acrylates that in synthesis example 4, obtain, 0.5 part of silicone compounds (" BYK-371 " with curable with actinic energy ray functional group, trade(brand)name is produced by BYK K.K.) and 3 parts of light triggers (" IRGACURE 184 ") mixing have the composition of the curable with actinic energy ray of solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the composition of curable with actinic energy ray is 1.8.In addition, be included in that the difference on repetition values is 4 between two kinds of urethane acrylates in this curable with actinic energy ray composition.
(embodiment 3)
90 parts of urethane acrylates that obtain, 10 parts of urethane acrylates that obtain and 3 parts of light triggers (" IRGACURE 184 ") are mixed the curable with actinic energy ray composition that has solids content 50% weight with preparation in synthesis example 5 in synthesis example 7.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 2.In addition, be included in that the difference on repetition values is 9 between two kinds of urethane acrylates in the composition of this curable with actinic energy ray.
(embodiment 4)
With 63 parts of urethane acrylates that in synthesis example 6, obtain, 27 parts of urethane acrylates that in synthesis example 4, obtain, 5 parts of vinylformic acid phthalic acid list hydroxyethyl esters (" M-5400 "), 0.1 part of fluorine cpd (" NS-2104 " with curable with actinic energy ray functional group, trade(brand)name, produce by Daikin Ind Ltd), 5 parts of toluene and 3 parts of light triggers (" IRGACURE 184 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 1.5.In addition, be included in that the difference on repetition values is 5 between two kinds of urethane acrylates in this curable with actinic energy ray composition.
(embodiment 5)
80 parts of urethane acrylates that obtain in synthesis example 8,10 parts of vinylformic acid phthalic acid list hydroxyethyl esters (" M-5400 "), 10 parts of toluene and 3 parts of light triggers (" IRGACURE184 ") are mixed the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 1.5.In addition, be included in that the maximum difference on repetition values is 2 between the urethane acrylate in this curable with actinic energy ray composition.
(embodiment 6)
With 80 parts of urethane acrylates that in synthesis example 9, obtain, 10 parts of tetraethylene glycol diacrylate (" LIGHT-ACRYLATE 4EG-A ", trade(brand)name, produce by Kyoeisha chemical company limited), 0.3 part of polyether-modified stearyl alcohol (" S-2 ", trade(brand)name is produced by NOF company), 10 parts of toluene and 3 parts of light triggers (" IRGACURE " 184) mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 1.5.In addition, be included in that the maximum difference on repetition values is 4 between the urethane acrylate in this curable with actinic energy ray composition.
(embodiment 7)
With 100 parts of urethane acrylates that in synthesis example 10, obtain, 1 part of fluorine cpd (" NS-2103 " with curable with actinic energy ray functional group, trade(brand)name is produced by Daikin Ind Ltd) and 3 parts of light triggers (" IRGACURE 184 ") mixing curable with actinic energy ray composition of having solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 2.0.In addition, be included in that the maximum difference on repetition values is 10 between the urethane acrylate in this curable with actinic energy ray composition.
(embodiment 8)
90 parts of urethane acrylates that obtain in synthesis example 11,5 parts of vinylformic acid phthalic acid list hydroxyethyl esters (" M-5400 "), 5 parts of toluene and 3 parts of light triggers (" IRGACURE 184 ") are mixed the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 2.0.In addition, be included in that the maximum difference on repetition values is 5 between the urethane acrylate in this curable with actinic energy ray composition.
(embodiment 9)
With 70 parts of urethane acrylates that in synthesis example 12, obtain, 15 parts of triethylene omega-diol diacrylates (" 3EG-A ", trade(brand)name is produced by Kyoeisha chemical company limited), 15 parts of toluene and 3 parts of light triggers (" IRGACURE 184 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 2.In addition, be included in that the maximum difference on repetition values is 19 between the urethane acrylate in this curable with actinic energy ray composition.
(embodiment 10)
With 4 parts of urethane acrylates that in synthesis example 1, obtain, 46 parts of urethane acrylates that in synthesis example 4, obtain, 15 part of two phenoxyethyl alcohol fluorenes diacrylate (" BPEF-A ", trade(brand)name, produce by Osaka aerochemistry company limited), 10 parts of polyethyleneglycol diacrylates (" LIGHT-ACRYLATE 14EGA ", trade(brand)name is produced by Kyoeisha chemical company limited), 25 parts of toluene and 3 parts of light triggers (" IRGACURE 2959 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 4.5.In addition, be included in that the maximum difference on repetition values is 4 between the urethane acrylate in this curable with actinic energy ray composition.
(Comparative Examples 1)
In 100 parts of urethane acrylates that in synthesis example 2, obtain, sneak into 3 parts of light triggers (" IRGACURE 184 ") have solids content 50% weight with preparation curable with actinic energy ray composition.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 2.
(Comparative Examples 2)
In 100 parts of urethane acrylates that in synthesis example 6, obtain, sneak into 3 parts of light triggers (" IRGACURE 184 ") have solids content 50% weight with preparation curable with actinic energy ray composition.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 0.
(Comparative Examples 3)
With 35 parts of urethane acrylates (" M-1100 ", trade(brand)name is produced by Toagosei company limited), the vinylformic acid hydroxyethyl ester (" PLACCEL FA2D ") of 65 parts of polycaprolactone modifications, 100 parts of toluene and 6 parts of light triggers (" IRGACURE 184 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 0.
(Comparative Examples 4)
With 68 parts of urethane acrylates (" M-1200 ", trade(brand)name is produced by Toagosei company limited), the hydroxyethyl acrylate (" PLACCEL FA5 ") of 32 parts of polycaprolactone modifications, 100 parts of toluene and 6 parts of light triggers (" IRGACURE 184 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.The caprolactone units repetition values that is included in each acrylate monomer residue in the average per molecule urethane acrylate in the curable with actinic energy ray composition is 0.
(Comparative Examples 5)
With 80 parts of dipentaerythritol acrylates (" M-400 ", trade(brand)name, produce by Toagosei chemical industry company limited), 20 parts of tetrahydrofurfuryl acrylate (" LIGHT-ACRTYLATETHF-A ", trade(brand)name is produced by Kyocisha chemistry company limited), 100 parts of toluene and 4 parts of light triggers (" IRGACURE 184 ") mix the curable with actinic energy ray composition that has solids content 50% weight with preparation.
(Comparative Examples 6)
100 parts of acrylic polyols (" GAMERON 18-300 ", trade(brand)name, produce by Natoco company limited) and isocyanate curing agent (" GAMERON solidifying agent 18-001 ", trade(brand)name is produced by Natocc company limited) mix with preparation double pack type vinylformic acid-carbamate resins coating.
The composition of making in embodiment 1-10 and Comparative Examples 1-6 is assessed and measured according to following (1)-(14).Its result provides in following table 2.
(1) coating transparency
The every kind composition of visual observation before solidifying.Those that wherein do not find turbidity be assessed as and wherein find turbidity those be assessed as *.
(2) transparency of filming
Have on the surface of easy to be adherent poly terephthalic acid ethylene glycol film of thickness 100 μ m, provide the cured layer of making by every kind of composition to prepare test board with thickness 10 μ m.Use " TC-H3DPK " (trade(brand)name, electricity look Co., Ltd. produces by Tokyo), measure the transparence (%) of all light by each test board.
(3) adhesivity
Use each above-mentioned test board, carry out cross cutting stripping test according to JIS K5400.Wherein measured value is that 0/100 test board is assessed as ◎, wherein measured value is 1/100 to be assessed as to the test board that is lower than 5/100, wherein measured value is 5/100 to be assessed as to the test board that is lower than 10/100, wherein measured value be 10/100 to the test board that is lower than 20/200 be assessed as △ and wherein measured value be 20/100 or be higher than 20/100 test board and be assessed as *.
(4) wet fastness
Measure the haze value of each test board before and after handling, wherein above-mentioned test board was placed 50 hours under the atmosphere of 50 degrees centigrade and relative humidity 98%.Wherein by handling the mist degree of measuring before
Measure the haze value of each test board before and after handling, wherein will flood with 0.1N vitriolic velveteen and on each test board, place 24 hours under 25 degrees centigrade the atmosphere.Wherein deducting resulting value the haze value of measuring after handling by the haze value of measuring before will handling is lower than 5% test board and is assessed as ◎, wherein this value is that the test board of 5-10% is assessed as zero, wherein this value is that the test board of 10-20% is assessed as, wherein this value is that the test board of 20-30% is assessed as △, and wherein this value be 30% or be higher than 30% test board and be assessed as *.
(12) alkali resistance
Measure the haze value of each test board before and after handling, wherein will flood with the velveteen of 0.1N sodium hydroxide and on each test board, place 24 hours under 25 degrees centigrade the atmosphere.Wherein deducting resulting value the haze value of measuring after handling by the haze value of measuring before will handling is lower than 5% test board and is assessed as ◎, wherein this value is that the test board of 5-10% is assessed as zero, wherein this value is that the test board of 10-20% is assessed as, wherein this value be the test board of 20-30% be assessed as △ and wherein this value be 30% or be higher than 30% test board and be assessed as *.
(13) productivity
Productivity was assessed by the every kind of composition required time of curing that is coated in every kind of test board process of preparation on the easy adherent polyethylene terephthalate film.Wherein required time be lower than 1 minute test board be assessed as zero and wherein required time be 1 minute or be higher than 1 minute test board and be assessed as *.
(14) scratch test
The cured layer that every kind of composition making in forming by embodiment 1-10 and Comparative Examples 1-6 on the surface of easy the to be adherent polyethylene terephthalate film of thickness 100 μ m is made is with the preparation test board.The thickness of the cured layer that is formed by the composition of making in Comparative Examples 5 is 20 μ m, and the thickness of the cured layer except that this layer is 50 μ m (these are because the thickness of the cured layer that forms when the composition of being made by Comparative Examples 5 is when surpassing 20 μ m, and the test board generation of curling is ruptured).Maximum scratch load (normal load [mN]) utilizes the scratch tester of being produced by HEIDON Co. to measure, when wherein carrying out the scratch mark on using the cured layer of diamond indenter at test board with tip diameter 15 μ m, the self-reparing capability that this scratch mark can be by cured layer is repaired under the atmosphere of 25 degrees centigrade and relative humidity 50%.The unit that is shown in the measured value in the parenthesis of table 2 is gf.Deducting resulting value the haze value that value is measured after handling is lower than 5% test board and is assessed as ◎, wherein this value is that the test board of 5-10% is assessed as, wherein this value is that the test board of 10-20% is assessed as, wherein this value be the test board of 20-30% be assessed as △ and wherein this value be 30% or more test board be assessed as *.
(5) solvent resistance
Solvent resistance is passed through to use the cleaning piece (" KINWIPE ", trade(brand)name are produced by Crecia company) that floods with toluene to rub each test board 10 times back and forth and is assessed.Do not find that wherein scratch or the adherent test board of cleaning piece fiber are assessed as, wherein find slight scratch or the adherent test board of cleaning piece fiber be assessed as △ and wherein find obvious scratch or the adherent test board of cleaning piece fiber be assessed as *.
(6) erasibility
Erasibility is assessed by the haze value (%) that uses the #0000 steel wool to measure to rub back and forth each test board of 30 times under load 500g.
(7) self-reparing capability
Self-reparing capability was assessed by the test board of nail scraping is at room temperature placed in 30 minutes.Wherein the test board that is repaired of scratch be assessed as and wherein the test board that is not repaired of scratch be assessed as *.
(8) workability
Workability is assessed by cutting each test board.Test board with the cut surface that does not produce prickle is assessed as and test board with the cut surface that produces prickle is assessed as *.
(9) crimp property
The degree of depth (mm) of curling is by being cut into 10cm
2The center crosscut of the test board of size goes out 2cm
2Size and measuring.
(10) resistance to deflection
Resistance to deflection is measured by fastening in test board with the feasible one piece material with thickness identical with test board of crooked each test board of vice under 180 degree.The test board that wherein produces the cured layer of infringement as crack or fracture is assessed as and wherein produce the test board that damages as the cured layer of crack or fracture and be assessed as *.
(11) acid resistance
Table 2
| 1. coating transparency | 2. the transparency of filming | 3. adhesivity | 4. wet fastness | 5. solvent resistance | 6. erasibility | 7. self-reparing capability | 8. processibility | 9. crimp property | 10. resistance to deflection | 11. acid resistance | 12. alkali resistance | 13. productivity | 14. scratch test | |
| Embodiment 1 | ○ | 90.1 | ◎ | ◎ | ○ | 1.9 | ○ | ○ | 0.4 | ○ | ◎ | ◎ | ○ | 329(40) |
| Embodiment 2 | ○ | 89.8 | ○ | ◎ | ○ | 1.2 | ○ | ○ | 0.5 | ○ | ◎ | ◎ | ○ | 657(67) |
| Embodiment 3 | ○ | 89.6 | ○ | ◎ | ○ | 1.6 | ○ | ○ | 0.6 | ○ | ◎ | ◎ | ○ | 412(42) |
| Embodiment 4 | ○ | 90.5 | ◎ | ◎ | ○ | 1.4 | ○ | ○ | 0.5 | ○ | ◎ | ◎ | ○ | 529(54) |
| Embodiment 5 | ○ | 90.0 | ◎ | ◎ | ○ | 1.9 | ○ | ○ | 0.5 | ○ | ◎ | ◎ | ○ | 235(24) |
| Embodiment 6 | ○ | 89.9 | ◎ | ◎ | ○ | 1.2 | ○ | ○ | 0.7 | ○ | ◎ | ◎ | ○ | 696(71) |
| Embodiment 7 | ○ | 90.4 | ○ | ◎ | ○ | 1.4 | ○ | ○ | 0.6 | ○ | ◎ | ◎ | ○ | 490(50) |
| Embodiment 8 | ○ | 90.2 | ◎ | ◎ | ○ | 1.3 | ○ | ○ | 0.5 | ○ | ◎ | ◎ | ○ | 353(36) |
| Embodiment 9 | × | 85.4 | ◎ | ◎ | ○ | 1.8 | ○ | ○ | 0.8 | ○ | ◎ | ◎ | ○ | 235(24) |
| Embodiment 10 | ○ | 90.6 | ○ | ○ | ○ | 1.6 | ○ | ○ | 0.9 | ○ | ◎ | ◎ | ○ | 235(24) |
| Comparative Examples 1 | ○ | 90.0 | ○ | ◎ | ○ | 3.4 | ○ | ○ | 0.9 | ○ | ◎ | ◎ | ○ | 176(18) |
| Comparative Examples 2 | ○ | 90.7 | ○ | ◎ | ○ | 22 | × | ○ | 1.2 | ○ | ◎ | ◎ | ○ | 88(9) |
| Comparative Examples 3 | ○ | 89.8 | ◎ | ◎ | ○ | 27 | × | ○ | 0.7 | ○ | ◎ | ◎ | ○ | 78(8) |
| Comparative Examples 4 | ○ | 89.4 | ◎ | ◎ | ○ | 30 | × | ○ | 0.8 | ○ | ◎ | ◎ | ○ | 137(14) |
| Comparative Examples 5 | ○ | 90.5 | ○ | ◎ | ○ | 1.0 | × | × | 5.7 | × | ◎ | ◎ | ○ | 392(40) |
| Comparative Examples 6 | ○ | 90.5 | ◎ | ◎ | ○ | 8.8 | × | ○ | 0.6 | ○ | ◎ | ◎ | × | 118(12) |
As shown in table 2, embodiment 1-10 compares with Comparative Examples 6 with Comparative Examples 1-4 has excellent erasibility, has and the erasibility of Comparative Examples 5 in identical level with the general hard coating agent of conduct.In addition, for the value of the critical loading of measuring by scratch test, embodiment 1-10 is greater than Comparative Examples 1-4 and Comparative Examples 6, and is in identical level with Comparative Examples 5.In addition, exist a kind of like this tendency: embodiment 1,5,7,9 and 10 aspect erasibility, to be worse than other embodiment slightly, in the former, be included in the scope that the maximum difference on the caprolactone units repetition values of each acrylate monomer residue between two kinds of urethane acrylates in the curable with actinic energy ray composition has exceeded 4-9.
(embodiment 11: the preparation of optical reflection film (1))
7 parts of barium sulfate and 3 parts of titanium dioxide are dispersed in 60 parts of urethane polyesters polyol resins (" BURNOCK D6-439 ", trade(brand)name are produced by big Japanese ink chemical company limited) with the preparation coating liquid.This coating liquid is coated on the release treatment face of release treatment polyester film (" DIAFOIL MRX ", trade(brand)name are produced by Diafoil Hoechst company limited), obtains build 50 μ m and solidify to form the white resin layer with thickness 75 μ m.Then, 10 parts of titanium dioxide are dispersed in the curable with actinic energy ray composition of 50 parts of embodiment 1 with the preparation coating liquid.This coating liquid is coated on the white resin layer, obtains build 100 μ m and solidify to form the reflection resin layer.
(embodiment 12: the preparation of optical reflection film (2))
Curable with actinic energy ray composition among the embodiment 1 is coated to polyethylene terephthalate film (" LUMIRROR T-60 " with thickness 50 μ m, trade(brand)name, produce by Toray industrial) one side on, obtain build 50 μ m and solidify to form the reflection resin layer.Then, 7 parts of barium sulfate and 3 parts of titanium dioxide are dispersed in 60 parts of urethane polyesters-polyol resins (" BURNOCK D6-439 ") with the preparation coating liquid.This coating liquid is coated on the white resin layer, obtains build 100 μ m and solidify to form the reflection resin layer.
(embodiment 13: the preparation of anti-reflective film (1))
Curable with actinic energy ray composition among the embodiment 2 is coated to has thickness 100 μ m on the one side of the polyethylene terephthalate film of Cement Composite Treated by Plasma, the low resin layer that obtains build 100 μ m and solidify to form.Then, 0.3 part of light trigger (" IRGACURE 184 ") is sneaked in 100 parts " OPSTAR JM5010 " (trade(brand)name is produced by JSR company limited) with the preparation coating liquid.By spin coating this coating liquid is coated on the described low resin layer, obtains build 0.1 μ m and solidify to form layer with low refractive index.
(embodiment 14: the preparation of anti-reflective film (2))
The curable with actinic energy ray composition of embodiment 1 is coated on the one side of the polycarbonate membrane with thickness 380 μ m, obtains build 100 μ m and solidify to form low resin layer.Then, prepare the coating liquid that comprises 10 parts of dipentaerythritol acrylates (" M-400 "), 200 parts of titanium oxide dispersion bodies (200 part of 15% toluene solution) and 0.3 part of light trigger (" IRGACURE 184 ").In addition, this coating liquid is coated on the described low resin layer, obtains build 0.1 μ m and solidify to form layer with high index by spin coating.Subsequently, 0.3 part of light trigger (" IRGACURE 184 ") is sneaked among 100 parts of OPSTAR JN5010 with the preparation coating liquid.By spin coating this coating liquid is coated on the layer with high index, and solidify to form layer with low refractive index.
(embodiment 15: the preparation of polarizing coating (1))
Curable with actinic energy ray composition among the embodiment 3 is coated on the tri acetyl cellulose film (" FUJI TACK F-T-UV80 ", trade(brand)name are produced by description film company limited of Fuji) with thickness 80 μ m, obtains build 60 μ m and curing.
(embodiment 16: the preparation of polarizing coating (2))
10 parts of ultra-fine grain ZnO are dispersed in the curable with actinic energy ray composition of 90 parts of embodiment 3 with the preparation coating liquid.Coating liquid is coated to by the tri acetyl cellulose film, also solidifies on the existing polarization plates that the three-decker of polarizer and tri acetyl cellulose film is formed.
(embodiment 17: the preparation of light-diffusing films (1))
35 parts of beads of being made by polymethylmethacrylate (" GN-0630H ", trade(brand)name are produced by Ganz chemistry company limited) are dispersed in the curable with actinic energy ray composition of 100 parts of embodiment 4 with the preparation coating liquid.This coating liquid is coated on the polyethylene terephthalate film (" Lumirror T-60 ") with thickness 50 μ m, obtains build 15 μ m and curing.
(embodiment 18: the preparation of light-diffusing films (2))
Be coated on the existing light-diffusing films curable with actinic energy ray composition of embodiment 4 and curing.
(embodiment 19: the preparation of phase lining form)
The curable with actinic energy ray composition of embodiment 6 is coated to by uniaxial extension has on the film that the highest 1.15-1.25 of polycarbonate membrane of thickness 100 μ m doubly makes and solidify.
(embodiment 20: be used for the preparation of the film (the last teleblem of touch sensor) of touch sensor)
The curable with actinic energy ray composition of embodiment 7 is coated on the polyethylene terephthalate film (" A4100 ", trade(brand)name are spun company limited by Japan and produced) with thickness 188 μ m, obtains build 60 μ m and curing.
Any function element among the embodiment 11-20 has excellent erasibility.
Industrial applicibility
The composition of curable with actinic energy ray of the present invention can be used as the product that coating or coating agent wherein needing to be used for erasibility.
Claims (8)
1. the composition of a curable with actinic energy ray comprises:
(methyl) alkyl acrylate of organic isocyanate by will in a molecule, having two or three isocyanate groups and the expression of the following general formula (4) of polycaprolactone modification and have carbamate (methyl) acrylate that the alcohol reaction of 13 to 25 carbon atoms obtains and (methyl) vinylformic acid hydroxyalkyl acrylate of the organic isocyanate by will having two or three isocyanate groups in a molecule and following general formula (5) expression reacts carbamate (methyl) acrylate that obtains;
In the general formula (4), R represents H or CH
3, n is that integer 1-10 and m are integer 1-25;
In the general formula (5), R represents H or CH
3, the 1st, integer 1-10;
If (methyl) alkyl acrylate of wherein described polycaprolactone modification and described (methyl) vinylformic acid hydroxyalkyl acrylate are referred to as (methyl) acrylate monomer, the caprolactone units repetition values of each (methyl) acrylate monomer residue is 1-5 in the described carbamate of average per molecule (methyl) acrylate so, and the maximum difference on the caprolactone units repetition values of each (methyl) acrylate monomer residue is 9 or is lower than 9 between two kinds of carbamates (methyl) acrylate.
2. the composition of a curable with actinic energy ray comprises:
By will in a molecule, having the organic isocyanate of two or three isocyanate groups and the following general formula of polycaprolactone modification, (4) represent, (methyl) alkyl acrylate reaction and the carbamate that obtains, (methyl) acrylate and by will in a molecule, having the organic isocyanate and the following general formula of two or three isocyanate groups, (5) represent, the carbamate that (methyl) vinylformic acid hydroxyalkyl acrylate obtains with the alcohol reaction with 13 to 25 carbon atoms, (methyl) acrylate;
In the general formula (4), R represents H or CH
3, n is that integer 1-10 and m are integer 1-25;
In the general formula (5), R represents H or CH
3, the 1st, integer 1-10;
If (methyl) alkyl acrylate of wherein described polycaprolactone modification and described (methyl) vinylformic acid hydroxyalkyl acrylate are referred to as (methyl) acrylate monomer, the caprolactone units repetition values of each (methyl) acrylate monomer residue is 1-5 in the described carbamate of average per molecule (methyl) acrylate so, and the maximum difference on the caprolactone units repetition values of each (methyl) acrylate monomer residue is 9 or is lower than 9 between two kinds of carbamates (methyl) acrylate.
3. the composition of a curable with actinic energy ray comprises:
(methyl) vinylformic acid hydroxyalkyl acrylate of carbamate (methyl) acrylate that (methyl) alkyl acrylate of organic isocyanate by will having two or three isocyanate groups in a molecule and the expression of the following general formula (4) of polycaprolactone modification and long-chain alcohol reaction obtain and the organic isocyanate by will having two or three isocyanate groups in a molecule and following general formula (5) expression and the alcohol with 13 to 25 carbon atoms react carbamate (methyl) acrylate that obtains;
In the general formula (1), R represents H or CH
3, n is that integer 1-10 and m are integer 1-25;
In the general formula (2), R represents H or CH
3, the 1st, integer 1-10;
If (methyl) alkyl acrylate of wherein described polycaprolactone modification and described (methyl) vinylformic acid hydroxyalkyl acrylate are referred to as (methyl) acrylate monomer, the caprolactone units repetition values of each (methyl) acrylate monomer residue is 1-5 in the described carbamate of average per molecule (methyl) acrylate so, and the maximum difference on the caprolactone units repetition values of each (methyl) acrylate monomer residue is 9 or is lower than 9 between two kinds of carbamates (methyl) acrylate.
4. according to the composition of any one described curable with actinic energy ray of claim 1-3, wherein the caprolactone units repetition values of each (methyl) acrylate monomer residue is 1-2.5 in the described carbamate of average per molecule (methyl) acrylate.
5. according to the composition of any one described curable with actinic energy ray of claim 1-3, wherein the maximum difference on the caprolactone units repetition values of each (methyl) acrylate monomer residue is 4-9 between two kinds of carbamates (methyl) acrylate.
6. according to the composition of any one described curable with actinic energy ray of claim 1-3, wherein said organic isocyanate has three isocyanate groups in a molecule.
7. according to the composition of any one described curable with actinic energy ray of claim 1-3, its carbonatoms that further comprises alkyl group is any in the compound that contains alkyl group, silicone compounds and the fluorine cpd of 13-25.
8. the composition of curable with actinic energy ray according to claim 7, the wherein said compound of alkyl group, described silicone compounds and the described fluorine cpd of containing have (methyl) acryl group respectively.
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| CN2007101085399A Division CN101104704B (en) | 2002-02-01 | 2003-01-31 | Composition curable with actinic energy ray and use thereof |
| CN2007101085401A Division CN101104724B (en) | 2002-02-01 | 2003-01-31 | Composition curable with actinic energy ray and use thereof |
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| CN2007101085401A Expired - Lifetime CN101104724B (en) | 2002-02-01 | 2003-01-31 | Composition curable with actinic energy ray and use thereof |
| CN2007101085399A Expired - Lifetime CN101104704B (en) | 2002-02-01 | 2003-01-31 | Composition curable with actinic energy ray and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106164121A (en) * | 2014-03-31 | 2016-11-23 | 日本合成化学工业株式会社 | Carbamate (methyl) acrylate based compound, actinic energy ray curable resion composition and smears |
| CN106554468A (en) * | 2015-09-29 | 2017-04-05 | 北京佰禄士科技有限公司 | A kind of active polyurethane macromolecular compound |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671477B (en) * | 2008-09-10 | 2012-07-04 | 比亚迪股份有限公司 | Reversible repair composition, preparation method thereof, varnish composition and self-repairing coating material |
| CN102666737B (en) * | 2009-11-25 | 2015-10-14 | 关西涂料株式会社 | The method of coating composition, coated article and formation multilayer film |
| JP5884988B2 (en) * | 2011-01-19 | 2016-03-15 | 日産化学工業株式会社 | High scratch-resistant imprint material containing urethane compound |
| JP6074144B2 (en) * | 2012-02-06 | 2017-02-01 | リンテック株式会社 | Optical film and display device |
| CN105116686A (en) * | 2015-08-28 | 2015-12-02 | 江门市恒光新材料有限公司 | Photosensitive resin for 3D printing |
| KR101947594B1 (en) * | 2017-04-13 | 2019-02-14 | 주식회사 쎄코 | Self-healing polyvinyl and method for preparing the same |
| SG11202003456VA (en) | 2017-12-13 | 2020-07-29 | Alcon Inc | Method for producing mps-compatible water gradient contact lenses |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11286531A (en) * | 1998-04-03 | 1999-10-19 | Daicel Ucb Kk | Noncrystalline urethane (meth)acrylate and its composition |
| JP2001002744A (en) * | 1999-06-21 | 2001-01-09 | Natoko Kk | Ultraviolet-curable composition and surface-functional material |
| JP2002256053A (en) * | 2000-12-28 | 2002-09-11 | Natoko Kk | Active energy ray-curable urethane (meth)acrylate, active energy ray-curable composition and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780487A (en) * | 1986-10-22 | 1988-10-25 | Thomas Kurpiewski | Radiation curable coating compositions |
| US5322861A (en) * | 1991-10-01 | 1994-06-21 | Mitsubishi Kasei Corporation | Ultraviolet-hardening urethane acrylate oligomer |
-
2003
- 2003-01-31 CN CN2007101085384A patent/CN101104670B/en not_active Expired - Lifetime
- 2003-01-31 CN CNB038029790A patent/CN100451045C/en not_active Expired - Lifetime
- 2003-01-31 CN CN2007101085401A patent/CN101104724B/en not_active Expired - Lifetime
- 2003-01-31 CN CN2007101085399A patent/CN101104704B/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11286531A (en) * | 1998-04-03 | 1999-10-19 | Daicel Ucb Kk | Noncrystalline urethane (meth)acrylate and its composition |
| JP2001002744A (en) * | 1999-06-21 | 2001-01-09 | Natoko Kk | Ultraviolet-curable composition and surface-functional material |
| JP2002256053A (en) * | 2000-12-28 | 2002-09-11 | Natoko Kk | Active energy ray-curable urethane (meth)acrylate, active energy ray-curable composition and their use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106164121A (en) * | 2014-03-31 | 2016-11-23 | 日本合成化学工业株式会社 | Carbamate (methyl) acrylate based compound, actinic energy ray curable resion composition and smears |
| CN106164121B (en) * | 2014-03-31 | 2019-12-20 | 三菱化学株式会社 | Urethane (meth) acrylate compound, active energy ray-curable resin composition, and coating agent |
| CN106554468A (en) * | 2015-09-29 | 2017-04-05 | 北京佰禄士科技有限公司 | A kind of active polyurethane macromolecular compound |
| CN106554468B (en) * | 2015-09-29 | 2019-11-12 | 常州领景新材料科技有限公司 | A kind of active polyurethane high-molecular compound |
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| Publication number | Publication date |
|---|---|
| CN101104724A (en) | 2008-01-16 |
| CN101104670B (en) | 2010-07-21 |
| CN101104670A (en) | 2008-01-16 |
| CN1703435A (en) | 2005-11-30 |
| CN101104704A (en) | 2008-01-16 |
| CN101104704B (en) | 2013-04-17 |
| CN101104724B (en) | 2010-09-08 |
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