CN101676310B - Fingerprint resistance photo-curing combination and coating article having fingerprint resistance coating layer - Google Patents
Fingerprint resistance photo-curing combination and coating article having fingerprint resistance coating layer Download PDFInfo
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- CN101676310B CN101676310B CN200910174603.2A CN200910174603A CN101676310B CN 101676310 B CN101676310 B CN 101676310B CN 200910174603 A CN200910174603 A CN 200910174603A CN 101676310 B CN101676310 B CN 101676310B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention provides a fingerprint resistance photo-curing combination, capable of improving fingerprint resistance of optical display device surface or an object whose mirror is polished by a simple process such as coating. The fingerprint resistance photo-curing combination contains polyurethane (methyl) acrylic ester (A) having at least one (methyl) acrylic ester group on its two rear ends separately and containing polyether cage, optical polymerism polyfunctional compound (B) and optical polymerization initiator (C), wherein the polyurethane (methyl) acrylic ester (A) has a structure represented by formula (1), the water resisting property of the polyurethane (methyl) acrylic ester (A) is less than 6.0 ml, and solubilization parameter is less than 12 (in the formula, X represents a residue group obtained by removing hydroxyl groups on the two rear ends of polyatomic alcohol compound containing polyether cage).
Description
Technical field
The present invention relates to give the fingerprint resistant light-cured combination of the anti-finger printing coating of the transparency and anti-finger printing excellence, and be provided with anti-finger printing film and the painting application of the anti-finger printing coating being formed by this fingerprint resistant light-cured combination.
Background technology
Liquid crystal indicator (liquid-crystal display) is in recent years for various fields such as computer, word processor, televisor, mobile telephone, portable information terminal, pocket game machines.In addition, touch-screen display is universal just rapidly, and so-called touch-screen display is to have the indicating meter of giving as security the structure that the demonstration on picture operates machines by pressing.In watching device of the guide display device that this touch-screen display is just being widely used in arranging in the facility such as bank ATM, vending machine, palm PC (PDA), duplicating machine, facsimile recorder, game machine, museum and department store etc., satellite navigation system, multi-media station (being arranged at the multi-functional terminal end machine of convenience store), mobile telephone, rail vehicle etc.
Optical display for this liquid crystal indicator, touch-screen display etc., require it to there is anti-finger printing, so-called anti-finger printing refers on the surface of these optical displays not can fingerprints, even or fingerprints also can wipe away simply.For these optical displays, so also require scuff resistance, described scuff resistance to refer to can be because use remains scuff mark.Especially for touch-screen display, due to by operating with finger touch display surface, therefore there is following problems,, on this surface, adhere in a large number the fingerprint that the lipid composition by sebum etc. causes, this fingerprint adhere to visuality and the operability that has hindered machine terminal.
And then in recent years, the field except display surface, also requires the raising of anti-finger printing.Such as for mobile telephone etc., from improving the angle of aesthetic appearance and designability, consider there is the bright finished tendency of preferred enforcement, described mirror polish has been utilized metal-plated processing or has been utilized the coating of carrying out metal-plated processing.Even and then for household electronic products, furniture, indoor articles for daily use or minaudiere etc., from improving the angle of aesthetic appearance and designability, consider, also have the bright finished tendency of preferred enforcement, described mirror polish has been utilized metal-plated processing or has been utilized the coating of carrying out metal-plated processing.These article have high designability, have on the other hand very obvious such shortcoming of adhering to of fingerprint.Therefore for these, implement bright finished article, also required to improve its anti-finger printing.
For optical display surface or implemented bright finished article, as the method that improves the didirtresistances such as its anti-finger printing, the method that surperficial didirtresistance (water and oil-resistant) is increased by coating silicone oil or fluoropolymer has been proposed.But the method at surface coated stain control agent, therefore has stain control agent to be erased very soon due to only, and the effect of didirtresistance can not continue, i.e. the poor shortcoming of antifouling persistence.On the other hand, also there is the coating composition that contains the additives such as these silicone oil or fluoropolymer by use that coating is set, and the method that the didirtresistance of anti-finger printing etc. is improved.But these additives are generally the additives that is referred to as magma (ソ Off ト Block mouth Star Network), also have the flexual character of the resin of giving simultaneously.There is the shortcoming reducing owing to adding these additives and make the physical strength of the surface hardness etc. of coating.
In TOHKEMY 2004-230562 communique (patent documentation 1), described hard coat film, it is characterized in that, transparent substrate film at least one side on be provided with hard coat, the cured article that described hard coat contains ionizing radiation induction type resin combination, and carry out surface treatment so that the water contact angle on surface is 70 ° following (claims 1) with alkaline aqueous solution.For this hard coat film, adopted the composition one-step solidification that makes coating by uviolizing etc., then use alkaline aqueous solution to carry out surface treatment so that the contact angle of the water on surface is 70 ° of following methods, but be below 70 ° in order to make the contact angle of water, the process management of requirement height or a large amount of examinations are poor, numerous and diverse thereby operation increases.The problem of the processing cost of a large amount of alkali wasteliquids that produce in addition in addition etc. also has problem aspect industrialization.
In TOHKEMY 2006-43919 communique (patent documentation 2), described the preparation method of hard coat film, it is characterized in that, being formed at average surface roughness Ra, be on the hard coating combination layer of energy ray-curable on the stripping film below 0.1 μ m, laminating base material film, irradiation energy ray after heating, make thus the hard coating combination layer of above-mentioned energy ray-curable solidify, on above-mentioned base material film, form hard coat (claim 1) closely sealedly.The base material film that this hard coat film has smooth-flat-surface by use is sought the raising of the fingerprint property wiped away.This hard coat film is characterised in that hard coat is arranged to be clipped in the state between stripping film and base material film in addition.Therefore also to need to be used to form the ，Gai manufacturing process of manufacturing process of the state that hard coat is clamped be numerous and diverse to this preparation method.Patent documentation 2 is the invention that consideration improves the property wiped away of fingerprint in addition, different from the application's technical background.
In TOHKEMY 2007-34027 communique (patent documentation 3), described the surfacing for indicating meter (claim 1) with convex-concave surface.This indicating meter is fine concavo-convex owing to having with surfacing, thereby form and to be attached to indicating meter and can to enter rapidly the concavo-convex recess of fine formation with lipid composition fingerprint, that derive from organism on surfacing surface, result makes fingerprint almost illegible ([0010] paragraph etc.).The convex-concave surface of this surfacing can be by being coated with alumina sol liquid, then flooding and form (claim 2) in hot water.That is,, according to the disclosed method of patent documentation 3, need on film, form several layers with other function.The surfacing forming so also needs the postprocessing working procedures ，Qi manufacturing process of impregnating numerous and diverse in addition, aspect industrialization, also has problem.
[patent documentation 1] TOHKEMY 2004-230562 communique
[patent documentation 2] TOHKEMY 2006-43919 communique
[patent documentation 3] TOHKEMY 2007-34027 communique
Summary of the invention
The present invention is the invention of making in order to solve above-mentioned existing problem, its object is to provide fingerprint resistant light-cured combination, and the anti-finger printing that said composition can make optical display surface by the very simple operation of coating etc. or implement bright finished article improves.
The invention provides fingerprint resistant light-cured combination, it contains:
Two ends have respectively at least 1 (methyl) urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A),
Optical polymerism polyfunctional compound (B) and
Photoepolymerizationinitiater initiater (C),
This urethane that contains polyether skeleton (methyl) acrylate (A) has the structure that following formula (1) represents,
[changing 1]
[in formula, X represents the residue that the removing hydroxyl removal with polyol compound two ends of polyether skeleton is obtained.]
And the water tolerance of this urethane that contains polyether skeleton (methyl) acrylate (A) (water ト レ ラ Application ス) is for below 6.0ml, solubility parameter is below 12, and above-mentioned purpose is achieved thus.
Above-mentioned fingerprint resistant light-cured combination can also contain polyethers or polyethers (methyl) acrylate (D).
In addition, (methyl) acrylate monomer (c) that the above-mentioned urethane that contains polyether skeleton (methyl) acrylate (A) is preferably polyol compound (a), the polyisocyanates (b) by making to have polyether skeleton and contains hydroxyl reacts the prepared urethane that contains polyether skeleton (methyl) acrylate.
Above-mentioned fingerprint resistant light-cured combination preferably contains:
The urethane that contains polyether skeleton (methyl) acrylate (A) 0.5～40 % by weight,
Optical polymerism polyfunctional compound (B) 30～99.5 % by weight,
Polyethers or polyethers (methyl) acrylate (D) 0～30 % by weight,
(wherein, usining mentioned component (A), (B) and gross weight (D) as 100 % by weight are as condition), and
Photoepolymerizationinitiater initiater (C), this Photoepolymerizationinitiater initiater (C) is 0.1～20 weight part with respect to composition (A), (B) and 100 weight parts of gross weight (D).
The present invention and then anti-finger printing film is also provided, it has transparent substrate and coating, and this coating is the coating of utilizing above-mentioned fingerprint resistant light-cured combination to form.
The present invention and then the painting application that is provided with anti-finger printing coating is also provided, described anti-finger printing coating utilizes above-mentioned fingerprint resistant light-cured combination to form.
Above-mentioned painting application is touch-screen display, liquid-crystal display, light emitting diode indicator, electroluminescent display, fluorescence display, plasma display or implemented bright finished article preferably.
The fingerprint resistant light-cured combination of the application of the invention, can or implement on optical display surface, on bright finished article etc., the coating with excellent anti-finger printing is set more easily.The coating being obtained by fingerprint resistant light-cured combination of the present invention also has the excellent transparency, the surface etc. that is suitable for very much optical display surface or has implemented bright finished article.The coating being obtained by fingerprint resistant light-cured combination of the present invention and then there is excellent scuff resistance and surperficial film hardness.Even the coating individual layer being obtained by fingerprint resistant light-cured combination of the present invention, also has the film hardness on excellent anti-finger printing, high scuff resistance and surface.And then fingerprint resistant light-cured combination of the present invention is owing to being light solidified, therefore there is following advantage, that is, can or implement on optical display surface to form more easily on bright finished article the coating with this excellent properties.Therefore the fingerprint resistant light-cured combination of the application of the invention, can form the coating of production efficiency and manufacturing cost excellence and have the anti-finger printing film of this coating.And then this coating can long term maintenance anti-finger printing, have advantages of that anti-finger printing persistence is also excellent.
Accompanying drawing explanation
The schematic cross-section of [Fig. 1] anti-finger printing film of the present invention.
[nomenclature]
1 ... anti-finger printing film, 3 ... coating, 5 ... transparent substrate.
Embodiment
Fingerprint resistant light-cured combination of the present invention contains:
Two ends have respectively at least 1 (methyl) urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A),
Optical polymerism polyfunctional compound (B) and
Photoepolymerizationinitiater initiater (C).Fingerprint resistant light-cured combination of the present invention can also contain polyether resin or polyethers (methyl) acrylate (D).
the urethane that contains polyether skeleton (methyl) acrylate (A)
In fingerprint resistant light-cured combination of the present invention, the contained urethane that contains polyether skeleton (methyl) acrylate (A) is urethane (methyl) acrylate that meets following condition, that is,
(i) two ends of molecule have respectively at least 1 (methyl) acrylate-based,
(ii) there is the structure that following formula (1) represents,
[changing 2]
[in formula, X represents the residue that the removing hydroxyl removal with polyol compound two ends of polyether skeleton is obtained.]
And (iii) water tolerance is below 6.0ml, solubility parameter is below 12.
In the present invention, composition (A) has the polyether structure of accompanying shown in above formula (1) (Jie) urethane bond, can obtain excellent anti-finger printing thus.At two ends, to have respectively at least 1 (methyl) acrylate-based for composition (A) in addition, can obtain good scuff resistance thus.
Urethane (methyl) acrylate of composition (A) also can have branched structure.Now " two ends " refers to two ends when molecular chain is long status.When thering is this branched structure, at the end of branched chain, also can there is at least 1 (methyl) acrylate-based.
As have structure shown in above formula (1), at two ends, there is respectively at least 1 (methyl) the acrylate-based urethane that contains polyether skeleton (methyl) acrylate (A), can enumerate the reactant of polyol compound (a), the polyisocyanates (b) for example with polyether skeleton and (methyl) acrylate monomer (c) that contains hydroxyl.
The polyol compound (a) with polyether skeleton can be enumerated for example glycol ether, triglycol, Tetraglycol 99, polyoxyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, 1,6-hexylene glycol, polymer with bis phenol A oxyethyl group glycol, polycaprolactone and have the block of polyethylene oxide, poly(propylene oxide), ethylene oxide/propylene oxide or the polyether glycol of at least a kind of structure of random copolymerization; The polyvalent alcohols such as trimethylolethane, TriMethylolPropane(TMP), poly-TriMethylolPropane(TMP), tetramethylolmethane, polypentaerythritol, Sorbitol Powder, mannitol, glycerine, Polyglycerine, polytetramethylene glycol are carried out to polyether-modified form, the polyvalent alcohol that contains polyether skeleton; Polyester polyol as the condenses of the polyprotonic acids such as above-mentioned polyether glycol and maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acid; Polyether glycol is carried out to the caprolactone modification polyvalent alcohol that caprolactone modification forms; Deng.
Polyisocyanates (b) can be enumerated for example fragrant family, fat family, the polyisocyanates of ester ring type system etc., wherein can enumerate tolylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, polyphenylene methane polyisocyanates, modified diphenylmethane diisocyanate, hydrogenation xylylene diisocyanate, xylylene diisocyanate, 1, hexamethylene-diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl-xylylene diisocyanate, isophorone diisocyanate, norbornylene vulcabond, 1, two (isocyanic ester ylmethyl) hexanaphthenes of 3-, phenylene diisocyanate, lysinediisocyanate, Lysine triisocyanate, the tripolymer compound of the polyisocyanates of naphthalene diisocyanate etc. or these polyisocyanates, biuret type (PVC ユ mono-レ Star ト type) polyisocyanates, water dispersive polyisocyanate, or the reaction product of these polyisocyanates and polyvalent alcohol etc.
(methyl) acrylate monomer (c) that contains hydroxyl can be to have 1 monofunctional monomer that (methyl) is acrylate-based, can be also to have 2 or it is with last (methyl) acrylate-based polyfunctional monomer.Monofunctional monomer can be enumerated such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxyl butyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, 2-hydroxyethyl acryl phosphoric acid ester, 2-(methyl) acryloxy ethyl-2-hydroxypropyl phthalic ester, caprolactone modification (methyl) 2-Hydroxy ethyl acrylate etc.Polyfunctional monomer can be enumerated such as 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, caprolactone modification Dipentaerythritol five (methyl) acrylate, caprolactone modification tetramethylolmethane three (methyl) acrylate, oxyethane modification Dipentaerythritol five (methyl) acrylate, oxyethane modification tetramethylolmethane three (methyl) acrylate etc.
For there is respectively at least 1 (methyl) the acrylate-based urethane that contains polyether skeleton (methyl) acrylate (A) at two ends, can react to prepare by making to have polyol compound (a), the polyisocyanates (b) of polyether skeleton and (methyl) acrylate monomer (c) that contains hydroxyl.In this preparation, can for example make to have polyol compound (a), the polyisocyanates (b) of polyether skeleton and (methyl) acrylate monomer (c) that contains hydroxyl reacts simultaneously, or after the polyol compound (a) that also can for example make to have polyether skeleton reacts with polyisocyanates (b), (methyl) acrylate monomer (c) that contains hydroxyl is reacted with it.
In thering is the reacting of the polyol compound of polyether skeleton (a) and polyisocyanates (b), the isocyanate group that preferably makes polyisocyanates (b) is that 1.1～2.5 equivalents react like this with respect to hydroxyl 1 equivalent of polyol compound (a), is particularly preferably 1.3～2.0 equivalents and reacts like this.Temperature of reaction is preferably 70～100 ℃, and the reaction times was preferably about 1～20 hour.In the reacting of this polyol compound (a) and polyisocyanates (b), more preferably use the such amine series catalysts in the such metal series catalysts of two lauric acid butyl tin or 1,8-diaza-dicyclo [5.4.0] hendecene-7 etc. to promote reaction.
The situation of simultaneously reacting for (methyl) acrylate monomer (c) that makes to have polyol compound (a), the polyisocyanates (b) of polyether skeleton and contain hydroxyl, the amount that preferably contains (methyl) acrylate monomer (c) of hydroxyl is 1.0～1.5 equivalents with respect to polyisocyanates (b) 1 equivalent, more preferably 1.0～1.3 equivalents.Temperature of reaction is preferably 60～100 ℃, and the reaction times is preferably 1～20 hour.
In addition, after reacting with polyisocyanates (b) for the polyol compound (a) that makes to have polyether skeleton, the situation that (methyl) acrylate monomer (c) that makes to contain hydroxyl reacts with it, preferably with respect to isocyanate group 1 equivalent of the reactant of polyol compound (a) and polyisocyanates (b), the hydroxyl of (methyl) acrylate monomer (c) that makes to contain hydroxyl is that 0.95～1.5 equivalent reacts like this, and the hydroxyl of (methyl) acrylate monomer (c) that particularly preferably makes to contain hydroxyl is that 1.0～1.1 equivalents react like this.Temperature of reaction is preferably 60～100 ℃, and the reaction times is preferably 1～20 hour.
For have respectively at least 1 (methyl) the acrylate-based urethane that contains polyether skeleton (methyl) acrylate (A) at two ends, more preferably its weight-average molecular weight is 3000～50000.When the weight-average molecular weight of the urethane that contains polyether skeleton (methyl) acrylate (A) is less than 3000, there is following possibility,, owing to thering is the molecular weight of the polyol compound (a) of polyether skeleton, reduce, urethane groups containing ratio uprises relatively, thereby the viscosity rise in when preparation, cause thus productivity to decline.On the other hand, if surpass 50000, there is following possibility,, because causing the productivity of fingerprint resistant light-cured combination, the viscosity increased of gained fingerprint resistant light-cured combination reduces, or because acrylate-based containing ratio reduces relatively, the physical strength of the coating therefore finally obtaining declines, from rather than preferred.And so-called molecular-weight average is weight-average molecular weight here, can use polystyrene as standard, utilize the measurement result of gel permeation chromatography (GPC) to calculate.
In the present invention, the urethane that contains polyether skeleton (methyl) acrylate (A) is used water tolerance for 6.0ml is following, solubility parameter is the material below 12.By making the water tolerance of composition (A), be that 6.0ml is following, solubility parameter is below 12, can obtain good anti-finger printing.
Water tolerance is to evaluate the index of hydrophilic degree, and its value is higher, means that wetting ability is higher.The measuring method of above-mentioned water tolerance is as follows: under the condition of 23 ℃, in 100ml beaker, the above-mentioned urethane that contains polyether skeleton (methyl) acrylate (A) 0.5g is mixed in and in tetrahydrofuran (THF) 10ml, makes its dispersion, use dropper in this mixture, slowly to add ion exchanged water, measure the amount (ml) that this mixture produces the needed ion exchanged water of gonorrhoea (white Turbid).The amount of this ion exchanged water (ml) is defined as to water tolerance.
Solubility parameter (solubility parameter is also abbreviated as SP value) means deliquescent yardstick.The numerical value of SP value is larger, represents that polarity is higher, and numerical value is less, represents that polarity is lower.And the SP value of composition (A) when the mixture of more than two kinds is to using the weighted mean of solubility parameter of each composition as SP value.
SP value can utilize following method to carry out practical measurement [reference: SUH, CLARKE, J.P.S.A-1,5,1671-1681 (1967)].
Measure temperature: 20 ℃
Sample: take resin 0.5g in 100ml beaker, use and add good solvent 10ml without calibrated pipet, dissolve by magnetic stirrer.
Solvent:
Good solvent ... diox, acetone etc.
Poor solvent ... normal hexane, ion exchanged water etc.
Cloud point is measured: use 50ml dropper to drip poor solvent, using and produce muddy point as dripping quantity.
The SP value δ of composition (A) is drawn by following formula.
[several 1]
δ＝(V
ml 1/2δ
ml+V
mh 1/2δ
mh)/(V
ml 1/2+V
mh 1/2)
[several 2]
V
m＝V
1V
2/(φ
1V
2+φ
2V
1)
[several 3]
δ
m＝φ
1δ
1+φ
2δ
2
Vi: the molecular volume of solvent (ml/mol)
φ i: the volume fraction of each solvent of cloud point
δ i: the SP value of solvent
Ml: low SP poor solvent mixed stocker
Mh: high SP poor solvent mixed stocker
The water tolerance of composition (A) is below 6.0ml, and solubility parameter is below 12, can obtain good anti-finger printing thus, and its reason is not come to a conclusion in theory, but can consider as described below.Composition (A) is owing to having urethane groups, thereby part has the part-structure that polarity is high in molecule.On the other hand, because composition (A) water tolerance is below 6.0ml, so molecule integral body is the compound that polarity is low.Here, the lipid composition that forms fingerprint is considered to longer chain fatty acid, and longer chain fatty acid consists of the low part of the such polarity of alkyl and the high carboxyl of polarity.In order to improve anti-finger printing, as long as increase for the affinity that forms the lipid composition of fingerprint, therefore, by using the above-mentioned composition (A) with the position that local polarity is high in molecule (urethane groups) and the low character of molecule integral polarity, can give good anti-finger printing.For solubility parameter, be also same.By making solubility parameter, be below 12, the composition (A) with the urethane groups that polarity is high is the compound that polarity is low as molecule integral body.Thus, for the affinity that forms the lipid composition of fingerprint, increase, anti-finger printing improves.And water tolerance is below 6.0ml and solubility parameter is the low character of polarity that all represents molecule integral body below 12.On the other hand, the present invention utilizes above-mentioned theory to get across completely, by use, have the composition (A) of following whole character concurrently, can realize the raising of anti-finger printing, described character has water tolerance to be that 6.0ml is following, solubility parameter is below 12 and has owing to having urethane groups makes the structure that local polarity is high.The inventor found through experiments the above-mentioned fact, thereby has completed the present invention.
And the preferred example of composition in the present invention (A) can be enumerated the urethane that contains polyether skeleton (methyl) acrylate that example is shown below.
[changing 3]
[in formula, R
1that the polyol compound (a) with polyether skeleton is removed the residue after the hydroxyl of two ends, R
2that polyisocyanates (b) is removed the residue after the isocyanate group of two ends, R
3and R
4can be identical, also can be different, be that (methyl) acrylate monomer (c) that contains hydroxyl is removed the residue after hydroxyl, and the n integer that is 1～60.]
More preferably the weight-average molecular weight of this urethane that contains polyether skeleton (methyl) acrylate (A) is 3000～50000.Said n is preferably 1～60 integer in addition, more preferably 1～30 integer.
optical polymerism polyfunctional compound (B)
Fingerprint resistant light-cured combination of the present invention is characterised in that, comprises urethane (methyl) acrylate (A) that contains polyether skeleton.In fingerprint resistant light-cured composition of the present invention, also contain optical polymerism polyfunctional compound (B) as filming forming component.By containing optical polymerism polyfunctional compound (B), the light solidified of fingerprint resistant light-cured combination increases, and the physical strength of gained coating (scuff resistance etc.) improves in addition.Optical polymerism polyfunctional compound (B) is the compound in a part with more than 2 optical polymerism group.Optical polymerism polyfunctional compound (B) can use has more than 2 (methyl) acrylate-based compound in molecule.Optical polymerism polyfunctional compound (B) preferably has 3 above (methyl) acrylate-based compounds.Optical polymerism polyfunctional compound (B) so long as have 2 above (methyl) acrylate-based compounds, can be monomer, can be also oligopolymer.
Monomer can be enumerated aklylene glycol two (methyl) acrylate of ethylene glycol bisthioglycolate (methyl) acrylate, propylene glycol two (methyl) acrylate etc.; Lower molecular weight polyalkylene glycol two (methyl) acrylate or its alkylene oxide modification bodies such as glycol ether two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate; Many (methyl) acrylate of polyvalent alcohol or its alkylene oxide modification body of trimethylolpropane tris (methyl) acrylate, tetramethylolmethane two or three or four (methyl) acrylate, two-TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol five or six (methyl) acrylate etc.; Two or three (methyl) acrylate of isocyanuric acid alkylene oxide modification body etc.By the blending ratio that regulates these to there is 2 (methyl) acrylate-based compound in molecule and to there is more than 3 (methyl) acrylate-based compound in molecule, apply, can regulate the physical property of gained coating.In optical polymerism polyfunctional compound (B), in molecule, there are 3 above (methyl) acrylate-based shared containing ratios of compound and be preferably 50～100%, more preferably 70～100%.In molecule, have more than 3 when (methyl) acrylate-based shared containing ratio of optical polymerism polyfunctional compound (B) is less than 50%, final gained film take resistance to marring, solvent resistance, a sliding that the woolliness of resistance to steel wire is representative have decline may, from rather than preferred.
Oligopolymer can be enumerated the oligopolymer of polyester (methyl) acrylate, epoxy (methyl) acrylate, acryloyl (methyl) acrylate (ア Network リ Le (メ タ) ア Network リ レ mono-ト) etc.And these oligopolymer preferable weight-average molecular weight that can be used as optical polymerism polyfunctional compound (B) are 300～5000, more preferably 500～3000.When larger than 5000, there is viscosity high, operation becomes difficult possibility.
These optical polymerisms polyfunctional compound (B) can use separately a kind, and all right two or more are used.
As optical polymerism polyfunctional compound (B), preferably at least a portion is used and in a part, is had 3 or its monomer with last optical polymerism group ((methyl) is acrylate-based).By using this monomer, can further improve the physical strength of gained coating.Preferred optical polymerism polyfunctional compound (B) can enumerate such as pentaerythritol triacrylate, TriMethylolPropane(TMP) EO modification triacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate etc.
photoepolymerizationinitiater initiater (C)
Fingerprint resistant light-cured combination of the present invention preferably contains Photoepolymerizationinitiater initiater (C).By there is Photoepolymerizationinitiater initiater (C), can increase the polymerizability that fingerprint resistant light-cured combination irradiates for ultraviolet isoreactivity energy-ray.It is that Photoepolymerizationinitiater initiater, acylphosphine oxide are that (ア シ Le Off オ ス Off イ Application オ キ サ イ De) Photoepolymerizationinitiater initiater, two luxuriant titaniums are that Photoepolymerizationinitiater initiater, oxime ester are polymerization starter etc. that the example of Photoepolymerizationinitiater initiater (C) can be enumerated such as alkyl phenones (ア Le キ Le Off エ ノ Application).Alkyl phenones is that Photoepolymerizationinitiater initiater for example can enumerate 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propionyl) benzyl] phenyl }-2-methylpropane-1-ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone etc.Acylphosphine oxide is that Photoepolymerizationinitiater initiater for example can enumerate 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide etc.Two luxuriant titaniums are that Photoepolymerizationinitiater initiater for example can be enumerated two (η 5-2,4-cyclopentadiene-1-yl)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-yl) phenyl) titaniums etc.Oxime ester is that polymerization starter can be enumerated for example 1.2-acetyl caproyl; 1-[4-(phenyl sulfo-)-; 2-(O-benzoyl oximes)], ethyl ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(0-ethanoyl oxime), hydroxyphenyl acetic acid, 2-[2-oxo-2-phenylacetyl oxygen base oxethyl] ethyl ester, 2-(2-hydroxyl-oxethyl) ethyl ester etc.And then can also use benzophenone, 2,4,6-tri-methyl benzophenone, benzoyl methyl benzoate, 2, the dehydrogenation type initiator of 4-diethyl thioxanthone, 2-ethyl-anthraquinone, camphorquinone etc.These Photoepolymerizationinitiater initiaters can be used separately a kind, and all right two or more are used.
In above-mentioned Photoepolymerizationinitiater initiater (C), more preferably use 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 and 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.
polyethers or polyethers (methyl) acrylate (D)
Fingerprint resistant light-cured combination of the present invention also can contain polyethers or polyethers (methyl) acrylate (D) as required.By contain the composition (D) as polyether resin or polyethers (methyl) acrylate, the advantage that has anti-finger printing to improve in fingerprint resistant light-cured combination.Especially, by containing composition (D), can realize with the affinity of lipid more improve, the fingerprint property wiped away further improves special like this performance.
As the polyethers of composition (D), can enumerate and contain polyethers dialkyl ether, polyethers single methanol or the polyether glycol etc. that carbon number is more than 3 alkylidene oxide (ア Le キ レ Application オ キ シ De)." carbon number is more than 3 alkylidene oxide " can enumerate and for example comprise use-O-CH
2-CH (CH
3oxypropylene, use-O-(CH of the oxidation isopropylidene of)-represent
2)
4oxidation tetramethylene, the use-O-CH of-expression
2-CH (CH
2the alkylidene oxide that the 3-oxychlorination propylidene of C1)-expression etc., carbon number are 3～4 etc.Be somebody's turn to do " carbon number is more than 3 alkylidene oxide (d-1) " more preferably oxypropylene, further preferential oxidation isopropylidene.The alkylidene oxide (d-2) that can also use the carbon number of the moieties of polyethers to be less than 3, but anti-finger printing can be mainly " carbon number is more than 3 alkylidene oxide " to be given, therefore preferably carbon number is at least a portion of more than 3 alkylidene oxide constituents (D).
Polyethers or polyethers (methyl) acrylate (D) preferred molecular weight is more than 400, more preferably more than 700.The molecular weight here can utilize the measurement result of the hydroxyl value of being calculated by JIS K 1557 to calculate.
Polyethers or polyethers (methyl) acrylate (D) also can be used commercially available polyethers or polyethers (methyl) acrylate.As the polyethers that can preferably use or polyethers (methyl) acrylate, can enumerate such as chemical (strain) society in キ シ ダ chemistry (strain) society polypropylene series He Xinzhong processed village polyethers diacrylate processed series etc.
In fingerprint resistant light-cured combination of the present invention, each composition (A), (B) and amount (D) are preferably:
The urethane that contains polyether skeleton (methyl) acrylate (A) 0.5～40 % by weight,
Optical polymerism polyfunctional compound (B) 30～99.5 % by weight,
Polyethers or polyethers (methyl) acrylate (D) 0～30 % by weight.
In more detail, when not containing composition (D), and then preferably:
The urethane that contains polyether skeleton (methyl) acrylate (A) is 0.5～40 % by weight, more preferably 2～35 % by weight,
Optical polymerism polyfunctional compound (B) is 30～99.5 % by weight, more preferably 65～98 % by weight.And using mentioned component (A) and gross weight (B) as 100 % by weight are as condition.
In addition, when containing composition (D), and then preferably:
The urethane that contains polyether skeleton (methyl) acrylate (A) is 0.5～40 % by weight, more preferably 2～35 % by weight,
Optical polymerism polyfunctional compound (B) is 30～97 % by weight, more preferably 45～95 % by weight,
Polyethers or polyethers (methyl) acrylate (D) is 1～30 % by weight, more preferably 2～20 % by weight.And using mentioned component (A), (B) and gross weight (D) as 100 % by weight are as condition.When the composition (D) of further cooperation has carbon number simultaneously, be more than 3 alkylidene oxide (d-1) and carbon number while being less than 3 alkylidene oxide (d-2), preferably 25 quality % in this composition (D) contained (d-1) and total (d-2) are (d-1) above.When the composition of (d-1) is lower than above-mentioned preferred in limited time lower, the situation that has the anti-finger printing of gained hard coat to decline, from rather than preferred.In addition now, in composition (D) aforementioned proportion of contained (d-1) on be limited to 100 quality %.
In addition when the composition (D) coordinating is for coming from polyethers or polyethers (methyl) acrylate (D-1) of (d-1) and coming from the polyethers of (d-2) or during the mixture of polyethers (methyl) acrylate (D-2), 10 quality % in preferred (D-1) and total (D-2) are (D-1) above.When the mixing ratio of (D-1) is lower than above-mentioned preferred in limited time lower, the situation that has the anti-finger printing of gained hard coat to reduce, from rather than preferred.In addition now, in composition (D) aforementioned proportion of contained (D-1) on be limited to 100 quality %.
When the amount of the urethane that contains polyether skeleton (methyl) acrylate (A) is fewer than above-mentioned scope, there are the anti-finger printing decline of gained anti-finger printing coating or the possibility of the variation such as resistance to bend(ing) or crimp tendency (カ mono-Le).When the amount of the urethane that contains polyether skeleton (methyl) acrylate (A) surpasses above-mentioned scope, there is the possibility of the declines such as the woolliness of resistance to steel wire or solvent resistance in addition.When optical polymerism polyfunctional compound's (B) amount when few, has the possibility of the physical strength variation such as film hardness on scuff resistance, surface than 30 % by weight.
Preferred light polymerization starter (C) contains 0.1～20 weight part with respect to composition (A), (B) and 100 weight parts of gross weight (D) in addition.When the amount of Photoepolymerizationinitiater initiater (C) is outside above-mentioned scope, there is light solidified not enough, the possibility that physical strength is poor.
other composition
Fingerprint resistant light-cured combination of the present invention can also coordinate the compound with 1 ethene unsaturated group as required.By containing this compound, can regulate the viscosity of gained coating fluid, adaptation, hardness and the flexibility of gained coating.As the compound with 1 ethene unsaturated group, can enumerate (methyl) acrylic compound that (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) tetrahydrofurfuryl acrylate etc. have ring texture; (methyl) vinylformic acid hydroxyalkyl acrylate of (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate etc.; (methyl) acrylic compound of the alkoxyl group oxide compound affixture (ア Le コ キ シ オ キ シ De is paid and added thing) of the phenol such as (methyl) vinylformic acid phenoxy ethyl; List (methyl) acrylate of the glycol such as ethylene glycol list (methyl) acrylate, methoxyl group ethylene glycol list (methyl) acrylate, Tetraglycol 99 list (methyl) acrylate, tripropylene glycol list (methyl) acrylate; The vinyl compound of NVP, N-caprolactam etc. etc.
Fingerprint resistant light-cured combination of the present invention can also contain the weighting agent of inorganic particulate or organic filler etc. as required.By containing inorganic particulate or organic filler, can further improve the scuff resistance of coating and surperficial film hardness, or give antidazzle.More preferably the median size of these inorganic particulates or organic filler is 5nm～number μ m left and right.As spendable inorganic particulate, can enumerate the particulate of metal for example or metal oxide.Metal can be enumerated such as Si, Ti, Al, Zn, Zr, In, Sn, Sb etc.Concrete inorganic particulate can be enumerated such as silicon-dioxide, aluminum oxide, zirconium white, titanium dioxide etc.And then these inorganic particulates more preferably with the functional group of UV-curable, for example acrylate-based particle surface is carried out to modification.In addition, as spendable organic filler, can enumerate the organic filler such as acrylic acid or the like (ア Network リ Le), polyester etc.
And when using inorganic particulate or organic filler, preferably its consumption is 0.1～50 % by weight left and right with respect to the solid minute weight of fingerprint resistant light-cured combination.When the content of inorganic particulate or organic filler surpasses 50 % by weight, the possibility that has the film toughness of gained coating to die down.
Fingerprint resistant light-cured combination of the present invention and then also can contain the organic solvent as diluting solvent as required.As this organic solvent, such as the object lesson of spendable solvent, can enumerate the aromatic series series solvent such as toluene, dimethylbenzene etc.; The aliphatics series solvent of hexane, heptane, octane, mineral turpentine (mineral spirit) etc.; The ketone series solvent of methyl ethyl ketone, acetone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; The ether series solvent of Anaesthetie Ether, isopropyl ether, tetrahydrofuran (THF), diox, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, methyl-phenoxide, phenyl ethyl ether etc.; The ester series solvent of ethyl acetate, butylacetate, isopropyl acetate, glycol diacetate etc.; The acid amides series solvent of dimethyl formamide, diethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone etc.; The cellosolve series solvent of methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether etc.; The ether-ether series solvent of propylene glycol monomethyl ether, propylene glycol list ethyl ether acetic ester etc.; The alcohol series solvent of methyl alcohol, ethanol, propyl alcohol etc.; The halogen series solvent of methylene dichloride, ethylene dichloride, chloroform etc. etc.These solvents can be used alone, but also also mix together.
Fingerprint resistant light-cured combination of the present invention and then also can contain as required photopolymerization and cause the normally used additives such as auxiliary agent, static inhibitor, polymerization retarder, antioxidant, UV light absorber, photostabilizer, defoamer, flow agent, pigment.For example, as the photopolymerization that can preferably use, cause auxiliary agent, can enumerate 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, dibutyl thanomin, methyldiethanolamine etc.
fingerprint resistant light-cured combination
Fingerprint resistant light-cured combination of the present invention comprises: the urethane that contains polyether skeleton (methyl) acrylate (A), optical polymerism polyfunctional compound (B) and Photoepolymerizationinitiater initiater (C) and polyethers as required or polyethers (methyl) acrylate (D).The fingerprint resistant light-cured combination of the application of the invention, can form following such coating, even if described coating also has very excellent anti-finger printing for individual layer, and film hardness and the anti-finger printing persistence on scuff resistance, surface are also excellent.
In addition, fingerprint resistant light-cured combination of the present invention is light solidified.Therefore,, when forming coating, there is the advantage that does not need heating to make its polymerization.In optical display, contain such as the low material of the thermotolerances such as resin molding more.Fingerprint resistant light-cured combination of the present invention has following advantage, that is, even for this optical display that contains the material that thermotolerance is low, resin molding then, also can form well coating.
Fingerprint resistant light-cured combination of the present invention can be by mixing mentioned component to prepare.In addition, when preparing composition, also can use as required the organic solvent that can be used for dilution.And fingerprint resistant light-cured combination of the present invention can dilute to use, also can not dilute and use.
As the preparation method of fingerprint resistant light-cured combination, such as can be by the above-mentioned urethane that contains polyether skeleton (methyl) acrylate (A), optical polymerism polyfunctional compound (B) and Photoepolymerizationinitiater initiater (C) and polyethers as required or polyethers (methyl) acrylate (D) and additive, organic solvent etc. are mixed to prepare.
It is that additive (シ リ コ mono-Application system adds drug) and fluorine are any one of additive that preferred fingerprint resistant light-cured combination of the present invention does not contain silicon.This is because these additives have the effect that improves the water-repellancy of gained coating and grease proofness, increase didirtresistance on the one hand, there is on the other hand the raising due to this water-repellancy and grease proofness to cause the lubricant component to being attached in coating to produce repulsion, make on the contrary dirt significantly may.
The fingerprint resistant light-cured combination of the application of the invention, can easily prepare anti-finger printing film.This anti-finger printing film has transparent substrate and coating.This coating is the layer being formed by above-mentioned fingerprint resistant light-cured combination, due to the existence of this layer, can bring into play anti-finger printing.
As the transparent substrate using in the preparation at anti-finger printing film; can use various overlays, such as tri acetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetyl cellulose film, cellulose acetate butyrate film, poly (ether sulfone) film, polyacrylic ester resin film, polyurethane series resin film, polyester film, polycarbonate membrane, polysulfone membrane, polyester film, polymethylpentene film, polyetherketone film, (methyl) acrylonitril membrane etc.Transparent substrate is preferably used polyethylene terephthalate.And the thickness of transparent substrate can suitably be selected according to purposes, generally use the thickness of 25～1000 μ m left and right.
The coating with anti-finger printing can form by apply above-mentioned fingerprint resistant light-cured combination on transparent substrate.The coating method of fingerprint resistant light-cured combination can suitably be selected according to the situation of fingerprint resistant light-cured combination and working procedure of coating, for example can by dip coating, airblade coating method, curtain coating method, rolling method, coiling rod painting method, intaglio plate coating method or extrusion coated method, (the method is the known method being recorded in No. 2681294 specification sheetss of United States Patent (USP).) etc. apply.
The fingerprint resistant light-cured combination being coated on transparent substrate then can get off to be cured by being exposed to the irradiation of active energy beam, can form thus the coating of anti-finger printing.And in this specification sheets, the term of " light solidified " is representing the meaning of broad sense, refer to by irradiating the light such as far ultraviolet rays yue, ultraviolet ray, near-ultraviolet ray, infrared rays to also have in addition the hertzian wave such as X ray, gamma-rays, electron beam, proton ray, neutron line isoreactivity energy-ray and the character that is cured.Wherein, the easiness obtaining from the viewpoint of curing speed, irradiating unit, price etc., it is favourable utilizing uviolizing to be cured.As the method for carrying out ultraviolet curing, can enumerate use and can send the high pressure mercury vapour lamp of the light of 200～500nm wavelength region may, metal halide lamp, xenon lamp, chemical lamp etc., with 100～3000mJ/cm
2the method that the energy of left and right irradiates etc.
In addition, can, by apply fingerprint resistant light-cured combination of the present invention on the surface of optical display, on the surface of optical display, form coating.As can the optical display of coating being set with fingerprint resistant light-cured combination of the present invention, can enumerate touch-screen display, liquid-crystal display, light emitting diode indicator, electroluminescent display, fluorescence display, plasma display etc.By being coated with fingerprint resistant light-cured combination of the present invention on various overlays, transite plate and glass etc. for these optical display surfaces, can on the surface of optical display, form coating.
And then process or carried out the coating of metal-plated processing and fingerprint resistant light-cured combination of the present invention is coated on the surface of having implemented bright finished article by metal-plated, can on the surface of these article, form the coating of anti-finger printing thus.As having implemented bright finished article, can enumerate such as portable information end end, household electrical appliance goods, furniture, indoor articles for daily use or minaudiere etc.By implemented to arrange on the surface of bright finished article the coating of anti-finger printing at these, can prevent adhering to of fingerprint.
The coating method of fingerprint resistant light-cured combination can be enumerated such as spin-coating method, dip coating, intaglio plate coating method, spraying method, rolling method, spread coating etc.Can be according to the kind of optical display of coating, and select suitable coating method.In the coating of fingerprint resistant light-cured combination, preferably so that the thickness of gained coating is 0.1～20 μ m applies like this.The fingerprint resistant light-cured combination of coating same is cured by being exposed under the irradiation of active energy beam with above-mentioned like this, can form thus the coating of anti-finger printing.
Embodiment
By following embodiment, be described more specifically the present invention, but the present invention is not limited to this.In embodiment, " part " and " % ", as long as no special explanation, is all weight basis.
preparation example 1 two ends have respectively at least 1 (methyl) acrylate-based, contain
there is the preparation of urethane (methyl) acrylate (A1) of polyether skeleton
In reaction vessel, add mixture (mixed weight was than 60: 40) 900 weight parts of isophorone diisocyanate (IPDI) 666 weight parts, polypropylene glycol (polypropylene glycol 1000, キ シ ダ chemistry (strain) society system) 2000 weight parts, pentaerythritol triacrylate and tetramethylol methane tetraacrylate, and then add dibutyl tin laurate 1000ppm as catalyzer, as the quinhydrones 1000ppm of polymerization retarder with as the methyl iso-butyl ketone (MIBK) (MIBK of solvent, so that the amount that solid composition is 40% is used), while be blown into air, at 80 ℃, mix 3 hours.
Like this, obtain thering is urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A1) at two ends.Measure SP value and the water tolerance value of urethane (methyl) acrylate that gained contains polyether skeleton, result SP value be 10.8 and water tolerance value be 3.5.Weight-average molecular weight is 7000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
preparation example 2 two ends have respectively at least 1 (methyl) acrylate-based, contain
there is the preparation of urethane (methyl) acrylate (A2) of polyether skeleton
In reaction vessel, add isophorone diisocyanate (IPDI) 44 weight parts, polypropylene glycol (polypropylene glycol 4000, キ シ ダ chemistry (strain) society system) 800 weight parts, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (mixed weight was than 60: 40) 90 weight parts, and then add the dibutyl tin laurate 1000ppm as catalyzer, quinhydrones 1000ppm as polymerization retarder, with the methyl iso-butyl ketone (MIBK) (MIBK as solvent, so that the amount that solid composition is 40% is used), while being blown into air 80 ℃ of stirring reactions 3 hours.
Like this, obtain thering is urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A2) at two ends.Measure SP value and the water tolerance value of urethane (methyl) acrylate that gained contains polyether skeleton, result SP value be 10.7 and water tolerance value be 3.7.Weight-average molecular weight is 9000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
preparation example 3 two ends have respectively at least 1 (methyl) acrylate-based, contain
there is the preparation of urethane (methyl) acrylate (A3) of polyether skeleton
In reaction vessel, add isophorone diisocyanate (IPDI) 44 weight parts, polypropylene glycol (polypropylene glycol 2000, キ シ ダ chemistry (strain) society system) 400 weight parts, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (mixed weight was than 60: 40) 90 weight parts, and then add the dibutyl tin laurate 1000ppm as catalyzer, quinhydrones 1000ppm as polymerization retarder, with the methyl iso-butyl ketone (MIBK) (MIBK as solvent, so that the amount that solid composition is 40% is used), while being blown into air 80 ℃ of stirring reactions 3 hours.
Like this, obtain thering is urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A3) at two ends.Measure SP value and the water tolerance value of urethane (methyl) acrylate that gained contains polyether skeleton, result SP value be 11.1 and water tolerance value be 4.8.Weight-average molecular weight is 8000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
preparation example 4 two ends have respectively at least 1 (methyl) acrylate-based, contain
there is the preparation of urethane (methyl) acrylate (A4) of polyether skeleton
In reaction vessel, add isophorone diisocyanate (IPDI) 44 weight parts, polypropylene glycol (Pluronic PE3100, BASF ジ ヤ パ Application (strain) society system) 200 weight parts, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (mixed weight was than 60: 40) 90 weight parts, and then add the dibutyl tin laurate 1000ppm as catalyzer, quinhydrones 1000ppm as polymerization retarder, with the methyl iso-butyl ketone (MIBK) (MIBK as solvent, so that the amount that solid composition is 40% is used), while being blown into air 80 ℃ of stirring reactions 3 hours.
Like this, obtain thering is urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A4) at two ends.Measure SP value and the water tolerance value of urethane (methyl) acrylate that gained contains polyether skeleton, result SP value be 11.7 and water tolerance value be 5.6.Weight-average molecular weight is 7000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
the relatively preparation of preparation example 1 urethane acrylate (1)
In reaction vessel, add isophorone diisocyanate (IPDI) 222 weight parts, polypropylene glycol (polypropylene glycol 1000, キ シ ダ chemistry (strain) society system) 1000 weight parts, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (mixed weight was than 60: 40) 450 weight parts, and then add the dibutyl tin laurate 1000ppm as catalyzer, quinhydrones 1000ppm as polymerization retarder, with the methyl iso-butyl ketone (MIBK) (MIBK as solvent, so that the amount that solid composition is 40% is used), while being blown into air, at 80 ℃, mix 3 hours, obtain urethane acrylate (1).
The urethane acrylate obtaining has acrylate-based on an end.Measure in addition SP value and the water tolerance value of gained urethane acrylate, result SP value be 11.2 and water tolerance value be 5.2.Weight-average molecular weight is 3000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
the relatively preparation of preparation example 2 urethanes
In reaction vessel, add isophorone diisocyanate (IPDI) 222 weight parts, polypropylene glycol (polypropylene glycol 1000, キ シ ダ chemistry (strain) society system) 2000 weight parts, and then add dibutyl tin laurate 1000ppm as catalyzer, as the quinhydrones 1000ppm of polymerization retarder with as the methyl iso-butyl ketone (MIBK) (MIBK of solvent, so that the amount that solid composition is 40% is used), while being blown into air, at 80 ℃, mix 3 hours, obtain urethanes.
Then measure SP value and the water tolerance value of gained urethanes, result SP value be 11.0 and water tolerance value be 4.7.Weight-average molecular weight is 6000 in addition.And weight-average molecular weight represents by the polystyrene conversion value of having utilized GPC to measure.
the preparation of embodiment 1 fingerprint resistant light-cured combination
By the urethane that contains polyether skeleton (methyl) acrylate 20 weight parts that obtained by preparation example 1, ア mouth ニ Star Network ス M305, (mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate (mixed weight was than approximately 60: 40) 80 weight parts and イ Le ガ キ ユ ア 184D (1-hydroxyl-cyclohexyl-phenyl ketone) 3 weight parts mix, the MIBK of take makes nonvolatile component ratio as 40 % by weight as solvent, obtains fingerprint resistant light-cured combination.
At PET film (thickness is 100 μ m), above by the excellent doctor knife coater of coiling (N o.12), resulting composition is applied, making dry film thickness is 5 μ m, 80 ℃ of heating 1 minute, solvent is removed dry.Then use high pressure mercury vapour lamp (120W/cm) so that ultraviolet ray is 300mJ/cm
2energy expose like this, it is solidified, form thus coating, obtain anti-finger printing film.
the preparation of embodiment 2～17 fingerprint resistant light-cured combinations
Except the weight part with shown in table 1～3 is used the raw material shown in table 1～3, other obtain fingerprint resistant light-cured combination similarly to Example 1.Form similarly to Example 1 in addition coating, obtain anti-finger printing film.And only in embodiment 5, making dry film thickness is that 3 μ m apply like this.
the preparation of comparative example 1～14 Photocurable composition
Except the weight part with shown in table 4～5 is used the raw material shown in table 4～5, other obtain fingerprint resistant light-cured combination similarly to Example 1.Form similarly to Example 1 in addition coating, obtain anti-finger printing film.
The evaluation of the cated sample of gained tool is carried out as following.And what obtained by these evaluation methods the results are shown in following table.
anti-finger printing is evaluated (oleic acid wiping evaluation)
In the coating of gained sample, drip 1 oil dripping acid.Then use dust-free cleaning cloth wiping 10 times back and forth.Evaluation of measuring is tested the turbidity of the sample after front and evaluation test as described above, tries to achieve Δ turbidity value.According to the numerical value of gained Δ turbidity value, by following standard, carry out anti-finger printing evaluation.
5 points: Δ turbidity is less than 0.5
4 points: Δ turbidity is more than 0.5 and is less than 1.0
3 points: Δ turbidity is more than 1.0 and is less than 3.0
2 points: Δ turbidity is more than 3.0 and is less than 5.0
1 point: Δ turbidity is more than 5.0
Turbidity value is measured as following.Use the diffusion transmittance (T of turbidometer (スガ trier society system) working sample
d(%)) and above-mentioned total light transmittance (full light Line transmittance) (T
t(%)), calculate turbidity value.And the total light transmittance (%) shown in table and turbidity (%) are all that the thickness that uses as base material in the preparation of coating is the value of measuring under the condition that exists of the PET membrane portions of 100 μ m.
[several 4]
H: turbidity (mist degree) (%)
T
d: diffusion transmittance (%)
T
t: total light transmittance (%)
the evaluation of the woolliness of resistance to steel wire
In the coating of gained sample, make the steel wool of #0000 at 500g/cm
sload under come and go 100 times.Then, carry out the visual assessment on the cured film surface after evaluation test, according to following standard, carry out the woolliness of resistance to steel wire evaluation.
◎: almost there is no scar
Zero: 2 following scar
△: 3 above and 10 following scars
*: 11 above scars
the evaluation of solvent resistance
On cured film surface with impregnation the swab stick wiping gently of MEK (methyl ethyl ketone), come and go 100 times, after visual test, the state of film coated surface is evaluated as following.
Zero: there is no vestige
△: vestige slightly
*: albefaction
the evaluation of sliding
Pen (front end shape: apply the load of 200g 0.8mmR), carry out the linear slide test of 40,000 times (coming and going 20,000 times) on cured film surface in polyacetal system.Sliding distance is now 30mm, and sliding velocity is 300mm/ second.Visual observation sliding position after this slip endurance life test.
Zero: almost there is no vestige
△: vestige slightly
*: albefaction
the evaluation of resistance to bend(ing)
According to JIS K 5600, utilize round shape axle method to measure cured coating film film.Minimum diameter by the cylinder not cracking on filming is evaluated as following.
Zero: diameter is less than 13mm
△: diameter be 13mm above～be less than 18mm
*: diameter is more than 18mm
the evaluation of crimp tendency
Cured coating film film is cut into the square that the length of side is 10cm, and the mean value (mm) of its 4 jiaos of amounts that upwarp is evaluated when standing.
Zero: be less than 10mm
△: 10mm is above and be less than 30mm
*: more than 30mm
The cooperation of above-described embodiment 1～16 and comparative example 1～14 and evaluation result are gathered and be shown in following table.And the symbol in table represents following content.
UV-6100B: Japanese synthetic chemistry (strain) society system, at two ends, there is respectively at least 1 (methyl) acrylate-based urethane acrylate that contains polyether skeleton, weight-average molecular weight is 5000
UV-3700B: Japanese synthetic chemistry (strain) society system, at two ends, there is respectively at least 1 (methyl) acrylate-based urethane acrylate that contains polyether skeleton, weight-average molecular weight is 41000
UA-47: chemistry (strain) society of eastern nation system, at two ends, there is respectively at least 1 (methyl) acrylate-based urethane acrylate that contains polyether skeleton, weight-average molecular weight is 2000
U-324A: Xin Zhong village chemistry (strain) society system, urethane acrylate
DPHA-40H: Japanese chemical drug (strain) society system, urethane acrylate
ア mouth ニ Star Network ス M305: the mixture (mixed weight is than about 60:40) of synthetic (strain) society in East Asia system, pentaerythritol triacrylate and tetramethylol methane tetraacrylate
ア mouth ニ Star Network ス M309: synthetic (strain) society in East Asia system, Viscoat 295
ア mouth ニ Star Network ス M350: synthetic (strain) society in East Asia system, TriMethylolPropane(TMP) 3EO modification triacrylate
ア mouth ニ Star Network ス M450: synthetic (strain) society in East Asia system, tetramethylol methane tetraacrylate
イ Le ガ キ ユ ア 184D:1-hydroxycyclohexylphenylketone
イ Le ガ キ ユ ア 907:2-methyl isophthalic acid [4-methylthio group phenyl]-2-morpholino propane-1-ketone
Polypropylene glycol 400: キ シ ダ chemistry (strain) society system, polypropylene glycol, molecular-weight average 400
Polypropylene glycol 700: キ シ ダ chemistry (strain) society system, polypropylene glycol, molecular-weight average 700
Polypropylene glycol 1000: キ シ ダ chemistry (strain) society system, polypropylene glycol, molecular-weight average is 1000
PE-3100:Pluronic PE3100, BASF ジ ヤ パ Application (strain) society system, the block polymer of polypropylene glycol 90%, polyoxyethylene glycol 10%, molecular weight is 1000
PE-61: Sanyo changes into industry (strain) society system, the block polymer of polypropylene glycol 86%, polyoxyethylene glycol 14%, molecular weight is 2000
APG-700: Xin Zhong village chemistry (strain) society system, polyethers diacrylate
UX-5000: Japanese chemical drug (strain) society system, polyester acrylate
UX-5001T: Japanese chemical drug (strain) society system, polyester acrylate
Epoxy ester 70PA: chemistry (strain) society of common prosperity society system, epoxy acrylate
Epoxy ester 80MFA: chemistry (strain) society of common prosperity society system, epoxy acrylate
BYK320: PVC Star グ ケ ミ mono-ジ ヤ パ Application (strain) society system, silicon is surface conditioner
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
* in above-mentioned table, relatively the urethane acrylate (1) of preparation example 1 only has on an end acrylate-basedly, and relatively preparation example 2 is that end does not have acrylate-based urethanes.
As shown in the above Table, can confirm that the anti-finger printing of the anti-finger printing film that the fingerprint resistant light-cured combination by embodiment obtains, the woolliness of resistance to steel wire, solvent resistance, a sliding, resistance to bend(ing), crimp tendency are all excellent.
Comparative example 1 is to have used 1 end to have the experimental example of acrylate-based urethane acrylate.Now, anti-finger printing is excellent, and the woolliness of resistance to steel wire and solvent resistance equal difference.
Comparative example 2 is to have used not have endways the experimental example of acrylate-based urethanes.Now, anti-finger printing is excellent, and the non-constants such as the woolliness of resistance to steel wire and solvent resistance.
Comparative example 3～4th, has been used the experimental example of SP value or the urethane acrylate of water tolerance value outside the scope of the invention.Now, can confirm that anti-finger printing is poor.
Comparative example 5 and 6 is the experimental examples that use urethane (methyl) acrylate (A) that polyethers or polyethers (methyl) acrylate (D) replace containing polyether skeleton.Now, can confirm that the woolliness of resistance to steel wire and a sliding are poor.
Comparative example 7 and 8 is experimental examples of urethane (methyl) acrylate (A) that replaces containing polyether skeleton with polyester acrylate.Now, can confirm not show anti-finger printing.
Comparative example 9 and 10 is experimental examples of urethane (methyl) acrylate (A) that replaces containing polyether skeleton with epoxy acrylate.Now also can confirm not show anti-finger printing.
Comparative example 11～14th, the experimental example of only using optical polymerism polyfunctional compound (B) to prepare.Now can confirm not show anti-finger printing.
Industrial applicability
The fingerprint resistant light-cured combination of the application of the invention can be more easily arranges the coating with excellent anti-finger printing on the surface of optical display etc.The coating being obtained by fingerprint resistant light-cured combination of the present invention also has the excellent transparency, is suitable for very much on the surface of optical display etc.The coating being obtained by fingerprint resistant light-cured combination of the present invention and then there is excellent scuff resistance and surperficial film hardness.And then fingerprint resistant light-cured combination of the present invention is light solidified, therefore can on the surface of optical display, form more easily the coating with this excellent properties.The fingerprint resistant light-cured combination of the application of the invention, has advantages of and can and be prepared in the such industry of original formation coating with excellent production efficiency.And then this coating can long term maintenance anti-finger printing, anti-finger printing persistence is also excellent.
Claims (7)
1. fingerprint resistant light-cured combination, it contains:
Two ends have respectively at least 1 (methyl) urethane acrylate-based, that contain polyether skeleton (methyl) acrylate (A),
Optical polymerism polyfunctional compound (B) and
Photoepolymerizationinitiater initiater (C),
This urethane that contains polyether skeleton (methyl) acrylate (A) has the structure shown in following formula (1), and the water tolerance of this urethane that contains polyether skeleton (methyl) acrylate (A) is below 6.0ml, solubility parameter is below 12
[changing 1]
In formula, X represents the residue that the removing hydroxyl removal with polyol compound two ends of polyether skeleton is obtained,
The measuring method of above-mentioned water tolerance is as follows: under the condition of 23 ℃, in 100ml beaker, the above-mentioned urethane that contains polyether skeleton (methyl) acrylate (A) 0.5g is mixed in and in tetrahydrofuran (THF) 10ml, makes its dispersion, use dropper in this mixture, slowly to add ion exchanged water, measure the amount that this mixture produces the needed ion exchanged water of gonorrhoea, the amount of this ion exchanged water is defined as to water tolerance, the unit of the amount of this ion exchanged water is ml
The urethane that contains polyether skeleton (methyl) acrylate (A) 0.5～40 % by weight,
Optical polymerism polyfunctional compound (B) 30～99.5 % by weight,
Polyethers or polyethers (methyl) acrylate (D) 0～30 % by weight,
Wherein, using mentioned component (A), (B) and gross weight (D) as 100 % by weight are as condition, and
Photoepolymerizationinitiater initiater (C) is 0.1～20 weight part with respect to composition (A), (B) and 100 weight parts of gross weight (D).
2. fingerprint resistant light-cured combination according to claim 1, wherein, the above-mentioned urethane that contains polyether skeleton (methyl) acrylate (A) is the urethane that contains polyether skeleton (methyl) acrylate prepared by polyol compound (a), the polyisocyanates (b) by making to have polyether skeleton and (methyl) acrylate monomer (c) reaction that contains hydroxyl.
3. fingerprint resistant light-cured combination according to claim 1 and 2, wherein, the polyol compound with polyether skeleton is selected from glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, dibutylene glycol, polytetramethylene glycol, 1,6-hexylene glycol, polymer with bis phenol A oxyethyl group glycol, has the polyether glycol of the block of polyethylene oxide, poly(propylene oxide), ethylene oxide/propylene oxide or at least a kind of structure of random copolymerization; Trimethylolethane, TriMethylolPropane(TMP), poly-TriMethylolPropane(TMP), tetramethylolmethane, polypentaerythritol, Sorbitol Powder, mannitol, glycerine, Polyglycerine, polytetramethylene glycol are carried out to polyether-modified form, the polyvalent alcohol that contains polyether skeleton; As above-mentioned polyether glycol and the polyester polyol of condenses that is selected from the polyprotonic acid of maleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, hexanodioic acid, m-phthalic acid; Polyether glycol is carried out to the caprolactone modification polyvalent alcohol that caprolactone modification forms.
4. fingerprint resistant light-cured combination according to claim 1 and 2, wherein, the polyol compound with polyether skeleton is selected from polyoxyethylene glycol, polypropylene glycol.
5. anti-finger printing film, it has transparent substrate and coating, and this coating is formed by the fingerprint resistant light-cured combination described in any one in claim 1～4.
6. be coated with application, it is provided with the anti-finger printing coating being formed by the fingerprint resistant light-cured combination described in any one in claim 1～4.
7. painting application according to claim 6, wherein, above-mentioned painting application is touch-screen display, liquid-crystal display, light emitting diode indicator, electroluminescent display, fluorescence display, plasma display or has implemented bright finished article.
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| JP2008236036 | 2008-09-16 | ||
| JP2008-236036 | 2008-09-16 | ||
| JP2008236036 | 2008-09-16 | ||
| JP2009194065A JP4638954B2 (en) | 2008-09-16 | 2009-08-25 | Fingerprint-resistant photocurable composition and painted product provided with fingerprint-resistant coating layer |
| JP2009194065 | 2009-08-25 | ||
| JP2009-194065 | 2009-08-25 |
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| CN104530331B (en) * | 2010-07-12 | 2017-01-11 | 大日本印刷株式会社 | Curable resin composition for antistatic layer, optical film, polarizing plate, and display panel |
| JP4816986B1 (en) * | 2010-09-06 | 2011-11-16 | Ｊｓｒ株式会社 | Curable composition and antireflection laminate |
| KR101223412B1 (en) * | 2010-10-08 | 2013-01-17 | 유림특수화학 주식회사 | Multilayer coating film with excellent anti-fingerprint property and product with the same |
| WO2012066924A1 (en) * | 2010-11-19 | 2012-05-24 | Dic株式会社 | Radical-curable resin composition, coating material and civil engineering building structure each using radical-curable resin composition, and method for constructing civil engineering building structure |
| WO2013077307A1 (en) * | 2011-11-22 | 2013-05-30 | 日本ペイント株式会社 | Hard coating composition |
| CN102675587B (en) * | 2012-05-22 | 2014-01-01 | 长春工业大学 | Preparation of environment pH-responsive polyurethane fluorescent light-emitting medical material |
| KR101528001B1 (en) * | 2012-06-22 | 2015-06-10 | 주식회사 엘지화학 | Electrode assembly, manufacture thereof, and secondary batteries including same |
| TWI655252B (en) * | 2014-09-26 | 2019-04-01 | 日商住友化學股份有限公司 | Ultraviolet-ray-curable coating composition, hard coat film and method for manufacturing same |
| KR102508672B1 (en) * | 2016-06-15 | 2023-03-13 | 삼성디스플레이 주식회사 | Display device |
| KR102351943B1 (en) * | 2016-06-20 | 2022-01-18 | 디아이씨 가부시끼가이샤 | Urethane (meth)acrylate resin and laminated film |
| JP6822792B2 (en) * | 2016-07-08 | 2021-01-27 | 中国塗料株式会社 | A method for producing a photocurable resin composition, a cured coating and a coated base material formed from the composition, and a cured coating and a coated base material. |
| KR102075027B1 (en) * | 2017-11-09 | 2020-03-12 | 주식회사 셀코스 | Deposition Method for Dark Titan Color |
| CN112423974B (en) * | 2018-07-05 | 2023-06-23 | 日产化学株式会社 | Method for producing scratch-resistant hard coating film |
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| JP5072241B2 (en) | 2006-03-06 | 2012-11-14 | 中国塗料株式会社 | Photocurable coating composition having excellent stain resistance and coating curing method |
| JP2008056789A (en) | 2006-08-31 | 2008-03-13 | Nippon Paint Co Ltd | Composition for antifouling hard coat |
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| CN1416443A (en) * | 2000-01-14 | 2003-05-07 | Dsm有限公司 | Photocurable resin compsn. and optical parts |
| CN1297974A (en) * | 2000-06-07 | 2001-06-06 | 湖南亚大化工建材有限公司 | Ultraviolet cured paint without yellowing |
| CN1347929A (en) * | 2000-10-10 | 2002-05-08 | 麦克德米德有限公司 | Photosensitive resin composition for producing printing board |
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