CN104115036B - Optical film and display equipment - Google Patents
Optical film and display equipment Download PDFInfo
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- CN104115036B CN104115036B CN201380008112.5A CN201380008112A CN104115036B CN 104115036 B CN104115036 B CN 104115036B CN 201380008112 A CN201380008112 A CN 201380008112A CN 104115036 B CN104115036 B CN 104115036B
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- optical film
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Abstract
Optical film, it for being provided with the optical film of the resin bed of the solidfied material that comprises hardening resin composition at least one face of base material, aforementioned hardening resin composition contains: the polymerizable compound (A) in a part with oxygen-freeization alkylidene unit in group shown in more than 2 general formula (1) and the remaining structure except this group, in a part, there is the polymerizable compound (B) of group shown in more than 3 general formula (2), and polymerization initiator (C), and (A) composition and (B) mass ratio of composition ((A)/(B)) are 15/85 ~ 85/15, the adaptation of this optical film and printing material and excellent in adhesion with adhesive, case hardness is high simultaneously, therefore there is good damage-resistant energy, even if there is under hot and humid environment long-time placement and also can maintain the excellent durability of these characteristics.
Description
Technical field
The present invention relates to optical film and used the display equipment of this optical film.
Background technology
How to be situated between and to paste the HC film with hard painting (below also referred to as " HC ") layer by adhesive on the surface of the mobile devices such as mobile phone for the object of anti-damage. In addition, sometimes for improve mobile device surface appearance design object and implement decorating printing on the HC of this HC film layer surface.
HC layer forms by carry out to high-density crosslinked resin bed by the polymerization of multiple unsaturated bonds, therefore exists China ink to wait the printing material tendency low with respect to the adaptation of HC layer.
In addition, being used to form in the material of HC layer, for making formed HC layer surface become level and smooth object or the object of raising coating, the levelling agent such as compounding silicon-type or fluorine system sometimes. Conventionally, when the levelling agents such as compounding silicon-type or fluorine system, the HC layer surface forming becomes low polarity, therefore exists with the compatibility step-down of printing material, further reduces this problem with the adaptation of printing material.
Various motions have been carried out for the object addressing the above problem.
For example, in patent documentation 1, for provide have damage-resistant can and the object of the HC film of the HC layer of printing adaptability excellence, disclose the HC film with following HC layer, described HC layer contains Photoepolymerizationinitiater initiater, (methyl) acrylate monomer with specific mass ratio and has (methyl) acrylic monomer and/or phosphate (methyl) acrylate of alkylamidoalkyl.
In addition, in patent documentation 2, can, by having used the object of the HC film that the thermal transfer printing method of thermal transfer printer directly prints to HC layer, disclose and at least one face of base material, be provided with the HC film that surface tension is HC layer more than particular value for providing.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-161609 communique
Patent documentation 2: TOHKEMY 2011-110902 communique.
Summary of the invention
The problem that invention will solve
But as patent documentation 1, as the material that is used to form HC layer, even if used the special monomer such as (methyl) acrylate monomer with alkylamidoalkyl, the effect that the adaptation of formed HC layer and printing material is improved is still insufficient.
In addition, also unexposed for making the surface tension of HC aspect reach concrete means more than particular value in patent documentation 2.
In addition,, in the time that HC film is used for to liquid crystal display, liquid crystal display possesses the stepped construction that comprises multilayer for improving various optical parameters conventionally between substrate and liquid crystal. Therefore, be mostly situated between and be pasted on other layer (layer of being made by optical film) by the layer that comprises adhesive for the HC film of liquid crystal display.
But, the HC layer of general HC film for the low identical reason of adaptation of printing material, also poor with the cementability of adhesive, therefore seeking to possess the HC film that can improve with the HC layer of the cementability of adhesive.
The object of the invention is to, though provide with the adaptation of printing material and with the excellent in adhesion and case hardness of adhesive high thereby there is good damage-resistant energy, have under hot and humid environment long-time placement also can maintain these characteristics excellent durability optical film and used the display equipment of this optical film.
For the means of dealing with problems
The inventor etc. have repeated further investigation, found that, by using the resin combination that contains 2 kinds of polymerizable compounds with ad hoc structure with special ratios to be used as the hardening resin composition of the resin bed that forms the optical film of bearing the effect of HC layer, can solve above-mentioned problem, thereby realize the present invention.
, the invention provides following (1) ~ (8).
(1) optical film, it is the optical film that is provided with the resin bed of the solidfied material that comprises hardening resin composition at least one face of base material,
Aforementioned hardening resin composition contains: in a part, there is polymerizable compound (B) and the polymerization initiator (C) in the polymerizable compound (A), a part of oxygen-freeization alkylidene unit in group shown in 2 above following formulas (1) and the remaining structure except this group with group shown in 3 above following general formulas (2), (A) composition and (B) mass ratio of composition ((A)/(B)) be 15/85 ~ 85/15.
[changing 1]
(in above-mentioned formula (1), R represents hydrogen atom or methyl independently of one another, and * represents bonding part. ).
[changing 2]
(in above-mentioned formula (2), R1Represent independently of one another hydrogen atom or methyl, A represents the alkylidene of carbon number 1 ~ 5 independently of one another. N is more than 1 integer independently of one another. * represent bonding part. ).
(2), according to the optical film above-mentioned (1) Suo Shu, wherein, in a part of polymerizable compound (B), the aggregate value of the n in aforementioned formula (2) is 4 ~ 20.
(3), according to the optical film above-mentioned (1) or (2) Suo Shu, wherein, the A in aforementioned formula (2) is ethylidene or propylidene independently of one another.
(4) according to the optical film described in any one in above-mentioned (1) ~ (3), wherein, aforementioned hardening resin composition also contains levelling agent (D).
(5) according to the optical film described in any one in above-mentioned (1) ~ (4), wherein, the surface tension of aforementioned resin layer is more than 30mN/m.
(6) according to the optical film described in any one in above-mentioned (1) ~ (5), wherein, be provided with the resin bed of the solidfied material that comprises aforementioned hardening resin composition on the two sides of aforementioned substrates.
(7), according to the optical film described in any one in above-mentioned (1) ~ (6), wherein, be to possess the adhesive phase that comprises adhesive at least one face of opposition side and same side with the face that is provided with resin bed of aforementioned substrates.
(8) display equipment, it has used the optical film described in any one in above-mentioned (1) ~ (7).
Invention effect
The adaptation of optical film of the present invention and printing material and excellent in adhesion with adhesive, and case hardness is high thereby have good damage-resistant energy, even if there is under hot and humid environment long-time placement and also can maintain the excellent durability of these characteristics.
Brief description of the drawings
Fig. 1 is the profile that first method of optical film of the present invention is provided with the optical film of resin bed on a face of base material.
Fig. 2 is the profile that second method of optical film of the present invention is provided with the optical film of resin bed on the face on the two sides of base material.
Fig. 3 is the profile that Third Way of optical film of the present invention has the optical film of adhesive phase.
Fig. 4 is the profile that the cubic formula of optical film of the present invention has the optical film of adhesive phase.
Detailed description of the invention
[optical film]
Optical film of the present invention is that the resin bed that the solidfied material that comprises hardening resin composition is set at least one face of base material forms. Optical film of the present invention is not limited to optical film 1 as shown in Figure 1, be provided with resin bed 12 on a face of base material 11, also comprises optical film 2 as shown in Figure 2, be provided with resin bed 12a, the 12b of the solidfied material that comprises above-mentioned hardening resin composition on two faces of base material 11.
In addition, optical film of the present invention can be with the face that is provided with resin bed of base material be the optical film that possesses the adhesive phase that comprises adhesive at least one face of opposition side and same side.
In other words, on the face that it is opposition side that the position of adhesive phase can be arranged on the face that is provided with resin bed of base material, also can be arranged on the face of resin bed, can also be arranged on the opposition side of resin bed and the face of resin bed on the two.
Fig. 3 shows an example of the formation of the optical film of the present invention with adhesive phase. The optical film 1a of Fig. 3 (a) be with the face that is provided with resin bed 12 of base material 11 face that is opposition side on possess the optical film of adhesive phase 13. In addition, the optical film 1b of Fig. 3 (b) be with the face that is provided with resin bed 12 of base material 11 face that is same side on possess the optical film of adhesive phase 13, on the face of resin bed 12, possess adhesive phase 13. And, the optical film 1c of Fig. 3 (c) be with the face that is provided with resin bed 12 of base material 11 be the optical film that possesses adhesive phase 13a, 13b on the face of same side and opposition side on the two, on the face of resin bed 12, possess adhesive phase 13a, with the face of the face that is provided with resin bed 12 base material 11 that is opposition side on possess adhesive phase 13b.
It should be noted that, in the situation that exposing adhesive phase, can also be on adhesive phase stacked release liner.
It should be noted that, on the face about the both sides at base material, be provided with the optical film of resin bed, also can on the face of each resin bed, further possess adhesive phase. As the formation of such optical film that is provided with adhesive phase, for example, can list the optical film 2a shown in Fig. 4, the formation of 2b. Optical film 2a is provided with resin bed 12a, 12b on the face of the both sides of base material 11, and then only on the face of resin bed 12b, possesses adhesive phase 13. On the other hand, on the face of the resin bed 12a of optical film 2b on the two sides that is arranged at base material 11, these both sides of 12b, possess adhesive phase 13a, 13b.
Below, describe for the inscape of optical film of the present invention.
(base material)
The base material using in the present invention is as long as can, as the base material of optical film, being just not particularly limited.
As the material that forms such base material, for example can list PETG (PET), PEN, polyimides, PEI, poly-aramid fiber, polyether-ketone, polyether-ether-ketone, polyphenylene oxide, poly-(4-methylpentene-1), polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyurethane, ethylene-vinyl acetate copolymer, ionic cross-linked polymer resin, (methyl) acrylic acid ethyl copolymer, polystyrene, Merlon, fluororesin, low density polyethylene (LDPE), straight-chain low density polyethylene, the resin moldings such as tri acetyl cellulose etc.
Among these, from the viewpoint of the optical characteristics such as processability, the transparency, versatility and cost aspect, be preferably PETG.
In addition, can implement on the surface of base material the easy bonding processing such as prime treatment, sided corona treatment.
The thickness of base material is suitably selected according to purposes, is preferably 5 ~ 300 μ m, more preferably 10 ~ 200 μ m, 20 ~ 100 μ m more preferably.
(resin bed)
The resin bed that forms optical film of the present invention is the layer of the solidfied material that comprises hardening resin composition (following, also referred to as " resin combination "), and described hardening resin composition comprises (A) ~ (C) composition.
This resin bed also can comprise the resinous principle beyond the solidfied material of above-mentioned hardening resin composition etc.
The content of the solidfied material of the hardening resin composition in this resin bed with respect to the gross mass of resin bed be preferably 70 ~ 100 quality %, more preferably 80 ~ 100 quality %, more preferably 90 ~ 100 quality %, be further preferably 100 quality %.
The hardening resin composition using in the present invention contains: polymerizable compound (B) and the polymerization initiator (C) in the polymerizable compound (A) of oxygen-freeization alkylidene unit, a part in group and the remaining structure except this group shown in the above-mentioned general formulas (1) more than having 2 in a part with group shown in 3 above above-mentioned general formulas (2).
In addition, this resin combination can also contain levelling agent (D), other additive.
The resin combination using in the present invention is by containing in the lump polymerizable compound (B) with polymerizable compound (A), can improve case hardness, the raising durability of the resin bed being formed by resin combination, and make the adaptation of resin bed and printing material and become good with the cementability of adhesive.
((A) composition: the polymerizable compound (A) in a part with oxygen-freeization alkylidene unit in group shown in 2 above general formulas (1) and the remaining structure except this group)
The resin combination using in the present invention contains: the polymerizable compound (A) in a part with oxygen-freeization alkylidene unit in group shown in 2 above following general formulas (1) and the remaining structure except this group. By containing polymerizable compound (A), can improve the case hardness of the resin bed being formed by resin combination. In addition, also can improve the durability of this resin bed.
[changing 3]
(in above-mentioned formula (1), R represents hydrogen atom or methyl independently of one another, and * represents bonding part. ).
The quantity of group shown in the above-mentioned general formula (1) having in a part of polymerizable compound (A) be 2 above, be preferably 2 ~ 16, more preferably 2 ~ 12, more preferably 3 ~ 10, be further preferably 3 ~ 8.
The tendency that the case hardness of the resin bed that when 2 of the lazy weights of above-mentioned group, existence cannot form sufficient cross-linked structure, formed by resin combination reduces, thus not preferred.
On the other hand, the quantity of above-mentioned group is 16 when following, can suppress the printing characteristic of resin bed and the reduction of adaptation that are become too high and caused, formed by resin combination by crosslink density, thereby preferably. The curling generation that in addition, can also suppress to be caused by cure shrinkage.
In addition, polymerizable compound (A) is the compound of oxygen-freeization alkylidene unit in the remaining structure except group shown in above-mentioned general formula (1). Can think, the compound that comprises alkylidene oxide unit is because the chain length of alkylidene oxide structure is longer, therefore have that crosslinking points spacing extends, the structure of the resin bed entirety that formed by resin combination becomes thin tendency, its result, becomes the reason that the case hardness of resin bed reduces. Therefore can think, by using the polymerizable compound of oxygen-freeization alkylidene unit to be used as (A) composition, the case hardness of the resin bed being formed by resin combination is improved in the present invention.
As such polymerizable compound (A), for example can list trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerine three (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, 1, 3-butanediol two (methyl) acrylate, 1, 4-butanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, and in molecule, there is oligoester (methyl) esters of acrylic acid of oxygen-freeization alkylidene unit in group shown in 2 above above-mentioned general formulas (1) and the remaining structure except this group, oligo-ether (methyl) esters of acrylic acid, oligourethane (methyl) esters of acrylic acid, and oligomeric epoxy radicals (methyl) esters of acrylic acid etc.
It should be noted that, these (A) compositions can use separately or combine two or more uses.
Among these, be preferably pentaerythrite three (methyl) acrylate and dipentaerythritol six (methyl) acrylate, glycerine three (methyl) acrylate.
((B) composition: the polymerizable compound (B) in a part with group shown in 3 above general formulas (2))
The resin combination using in the present invention contains: the polymerizable compound (B) in a part with group shown in 3 above following general formulas (2).
Can think; by containing in the lump polymerizable compound (B) and (A) composition; can moderately reduce the crosslink density of the resin bed being formed by resin combination; therefore can keep case hardness to a certain degree; and resin bed is given polarity, improved the adaptation of itself and printing material and the cementability with adhesive, in a part of described polymerizable compound (B), there is group such, that formed by (methyl) acryloyl group and alkylidene oxide chain Direct Bonding shown in 3 above general formulas (2).
[changing 4]
In above-mentioned general formula (2), R1Represent independently of one another hydrogen atom or methyl. It should be noted that, * represents bonding part.
A represents the alkylidene of carbon number 1 ~ 5 independently of one another, is preferably ethylidene or propylidene, more preferably ethylidene. Be this alkylidene by making A, can moderately reduce the resin bed being formed by resin combination crosslink density, can improve the adaptation of itself and printing material and the cementability with adhesive.
It should be noted that, from improving the adaptation of itself and printing material and the viewpoint with the cementability of adhesive, the content of the oxidation ethylidene unit of the whole alkylidene oxides unit comprising in a part with respect to polymerizable compound (B) is preferably 60 ~ 100 % by mole, more preferably 75 ~ 100 % by mole, more preferably 85 ~ 100 % by mole, is further preferably 95 ~ 100 % by mole.
N represents the quantity of alkylidene oxide unit, is more than 1 integer independently of one another.
In addition, the aggregate value (the total quantity of the alkylidene oxide unit in a part of polymerizable compound (B)) of n in above-mentioned general formula (2) in a part of polymerizable compound (B) is more than 3, from improve the adaptation of gained optical film and printing material and with the cementability of adhesive, make case hardness become good viewpoint, be preferably 4 ~ 20, more preferably 6 ~ 16, more preferably 8 ~ 14.
This aggregate value is 4 when above, can moderately reduce the resin bed being formed by resin combination crosslink density, improve the adaptation of itself and printing material and the cementability with adhesive.
On the other hand, this aggregate value is below 20 time, owing to can exceedingly not reducing crosslink density, therefore can keep case hardness to a certain degree, so preferably.
The quantity of group shown in the above-mentioned general formula (2) having in a part of polymerizable compound (B) be 3 above, be preferably 3 ~ 16, more preferably 3 ~ 12, more preferably 3 ~ 10, more preferably 3 ~ 8, be further preferably 5 ~ 8.
When 3 of the lazy weights of this group, the crosslink density of the resin bed being formed by resin combination becomes reduction, case hardness reduces, so not preferred. And the durability of resin bed reduces.
On the other hand, be 16 and can suppress to be become by crosslink density the reduction of printing characteristic too high and that cause, adaptation when following, thereby preferably.
As such polymerizable compound (B), for example, can list alkylene oxide modified glycerol three (methyl) acrylate, alkylene oxide modification dipentaerythritol four (methyl) acrylate, alkylene oxide modification dipentaerythritol six (methyl) acrylate etc.
It should be noted that, these (B) compositions can use separately or combine two or more uses.
In the resin combination using in the present invention, (A) composition and (B) mass ratio of composition ((A)/(B)) are 15/85 ~ 85/15, are preferably 20/80 ~ 80/20, more preferably 28/72 ~ 72/28, more preferably 35/65 ~ 65/35, more preferably 41/59 ~ 59/41, are further preferably 46/54 ~ 54/46.
When this mass ratio less than 15/85, (B) amount of composition is too much, and the case hardness of the resin bed therefore being formed by resin combination reduces, so not preferred. And, the tendency that exists the durability of resin bed to reduce.
On the other hand, this mass ratio exceedes at 85/15 o'clock, and (A) amount of composition is too much, the resin bed therefore being formed by resin combination and the adaptation of printing material and poor with the cementability of adhesive.
The total content of (A) composition comprising in the resin combination using in the present invention and (B) composition is preferably 70 ~ 99.9 quality %, more preferably 80 ~ 99 quality %, 90 ~ 98 quality % more preferably with respect to whole compositions.
((C) composition: polymerization initiator)
As the polymerization initiator using in the present invention (C), as long as can promote (A) composition and (B) polymerisation of the polymerizable compound of composition, just be not particularly limited, can use any in Photoepolymerizationinitiater initiater or thermal polymerization, also they can be used in combination.
As optical polymerism initator, for example can list acetophenone system, benzophenone series, benzoin system, thioxanthones system and imidazoles is Photoepolymerizationinitiater initiater etc.
Be Photoepolymerizationinitiater initiater as acetophenone, for example can list diethoxy acetophenone, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-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, benzyl dimethyl ketal, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxyl-1-4-[4-(2-hydroxy-2-methyl-propiono) and-benzyl] phenyl }-2-methylpropane-1-ketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone etc.
As benzophenone series Photoepolymerizationinitiater initiater; for example can list benzophenone, 4-phenyl benzophenone, 4-benzoyl-4'-dimethyl diphenyl sulfide, 3; 3'; 4; 4'-tetra-(tert-butyl hydroperoxide carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone, 4,4'-Bis-dimethylamino benzophenone etc.
Be Photoepolymerizationinitiater initiater as benzoin, for example, can list the benzoin compounds such as benzoin, methylbenzene acyloin, ethylo benzene acyloin; The benzoin ether compounds such as benzoin methyl ether, benzoin ethylether, benzoin isobutyl ether, benzoin phenyl ether etc.
Be Photoepolymerizationinitiater initiater as thioxanthones, for example, can list ITX, ITX, 2,4-diethyl thioxanthone, the chloro-4-propoxyl group of 1-thioxanthones, 2,4-bis-clopenthixal ketones etc.
Be Photoepolymerizationinitiater initiater as imidazoles, for example, can list two (Chloro-O-Phenyl)-4 of 2,2'-, 4 ', 5,5 '-tetraphenyl double imidazole, 2, two (Chloro-O-Phenyl)-4 of 2'-, 4 ', 5,5 '-tetra--(p-methoxyphenyl) two imidazoles, 2, two (the 2-chlorphenyls)-4,4 ', 5 of 2'-, 5 '-tetraphenyl-1, the hexa-aryl bi-imidazole based compounds such as 2'-bisglyoxaline etc.
These Photoepolymerizationinitiater initiaters can use separately or combine two or more uses.
In addition, as thermal polymerization, for example can list benzoyl peroxide, peroxidized t-butyl perbenzoate, hydrogen phosphide cumene, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, peroxy dicarbonate two (2-ethoxyethyl group) ester, new peroxide tert-butyl caprate, the peroxidating valeric acid tert-butyl ester, the tertiary own ester of peroxidating valeric acid, peroxidating (3,5,5-trimethyl acetyl), the organic peroxide of dipropyonyl peroxide, lauroyl peroxide, diacetyl peroxide and so on; 2,2'-azobis isobutyronitrile, 2,2'-azo two (2-methylbutyronitrile), 1,1'-azo two (cyclohexane-1-phosphinylidyne), 2,2'-azo two (2,4-methyl pentane nitrile), 2,2'-azo two (2,4-dimethyl-4-methoxyl group valeronitrile), dimethyl 2,2'-azo two (2 Methylpropionic acid ester), 4,4'-azo two (4-cyanopentanoic acids), 2,2'-azo two (2-hydroxymethyl propionitrile), 2, the azo based compound of 2'-azo two [2-(2-imidazoline-2-yls) propane] and so on.
These thermal polymerizations can use separately or combine two or more uses.
Among these polymerization initiators, from reactive viewpoint, be preferably Photoepolymerizationinitiater initiater, more preferably acetophenone is Photoepolymerizationinitiater initiater.
The compounding amount of polymerization initiator (C) with respect to (A) composition and (B) total amount 100 mass parts of composition be preferably 0.1 ~ 30 mass parts, more preferably 1 ~ 20 mass parts, more preferably 3 ~ 15 mass parts, be further preferably 3.5 ~ 8 mass parts.
((D) composition: levelling agent)
From improving the flatness of gained HC layer and the viewpoint of coating, the resin combination using in the present invention is preferably gone back compounding levelling agent (D).
As levelling agent (D), for example can list acrylic compounds levelling agent, silicon-type levelling agent, fluorine is levelling agent, acrylic compounds levelling agent, ethene base system levelling agent and silicone-modified acrylic compounds levelling agent etc.
As silicon-type levelling agent, can use the copolymer of polyoxyalkylene and dimethyl silicone polymer etc. As the commercially available product of silicon-type levelling agent, can list FZ-2118, FZ-77, FZ-2161(trade name, DowCorningTorayCo., Ltd. system) etc.; KP321, KP323, KP324, KP326, KP340, KP341(trade name, Shin-Etsu Chemial Co., Ltd's system) etc.; TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460(trade name, MomentivePerformanceMaterialsInc. system) etc.; BYK-300, BYK-302, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-377, BYK-378, BYK-UV3500, BYK-3510, BYK-3570(BYK Amada Co., Ltd. system) etc. polyether modified silicon oil (polyoxyalkylene modified silicon oil) etc.
Be levelling agent as fluorine, can use the copolymer of polyoxyalkylene and fluorocarbons etc. Be the commercially available product of levelling agent as fluorine, can list MEGAFACSeries, the FCSeries of Sumitomo 3M Co., Ltd. system etc. of Dainippon Ink Chemicals's system.
As the commercially available product of acrylic compounds levelling agent, can list BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-381, BYK-392(trade name, BYK Amada Co., Ltd. system) etc.
In addition, as the commercially available product of silicone-modified acrylic compounds levelling agent, can list BYK-3550(trade name, BYK Amada Co., Ltd. system) etc.
These levelling agents can use separately or combine two or more uses.
Among these, from improving the flatness of resin bed and the viewpoint of coating that are formed by resin combination, be preferably acrylic compounds levelling agent or silicone-modified acrylic compounds levelling agent, silicone-modified acrylic compounds levelling agent more preferably.
The compounding amount of levelling agent (D) is preferably 0.01 ~ 10 mass parts, more preferably 0.03 ~ 5 mass parts, 0.06 ~ 3 mass parts more preferably with respect to (A) composition and (B) total amount 100 mass parts of composition.
(other additive)
In the resin combination using in the present invention, not damaging in the scope of effect of the present invention, can also compounding other additive except above-mentioned.
As such additive, for example can list defoamer, thickener, surfactant, organic system lubricant, organic system particulate, inorganic be particulate, antioxidant, ultra-violet absorber, blowing agent, dyestuff, pigment, antistatic additive etc.
The in the situation that of other additive of compounding, the total amount of the content of additive is preferably 0.01 ~ 10 quality %, more preferably 0.1 ~ 7 quality %, 0.3 ~ 3 quality % more preferably with respect to the whole compositions that comprise in resin combination.
(the formation method of resin bed)
For ease of be coated with, improve workability on base material, the resin combination using in the present invention can also and be prepared resin bed formation coating fluid with organic solvent diluting.
As organic solvent, for example, can list methyl ethyl ketone, acetone, ethyl acetate, oxolane, diox, cyclohexane, n-hexane, toluene, dimethylbenzene, normal propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether etc.
Form with the solid component concentration of coating fluid as resin bed, be preferably 10 ~ 60 quality %, more preferably 10 ~ 45 quality %, 15 ~ 30 quality % more preferably. Being 10 quality % when above, is fully as the consumption of solvent, is 60 quality % when following, and viscosity becomes appropriateness, coating operation becomes easy.
As above-mentioned resin bed formation is coated on to the method on base material with coating fluid, known method can be used, for example, intaglio plate cladding process, excellent painting method, spraying process, spin-coating method, rolling method, mould painting method, cutter painting method, air knife cladding process, curtain Tu Fa etc. can be listed.
It should be noted that, be coated with this coating fluid and form after coated film, from preventing the residual viewpoint of solvent, low boiling point component, preferably, with respect to formed coated film, with dry about 30 seconds ~ 5 minutes of the temperature of 80 DEG C ~ 150 DEG C of left and right.
Resin bed can be by making above-mentioned coated film solidify to form.
As curing method, in the situation that using Photoepolymerizationinitiater initiater to be used as (C) composition, can be undertaken by the irradiation of active energy beam, in addition, in the situation that using thermal polymerization to be used as (C) composition, can be undertaken by heating, also they can be used in combination.
As active energy beam, can list ultraviolet ray, electron beam, alpha ray, β ray etc., be preferably ultraviolet ray. For example, while curing reaction being carried out by ultraviolet irradiation, ultraviolet accumulated light is preferably 100mJ/cm2~2000mJ/cm2, 150mJ/cm more preferably2~1000mJ/cm2。
The thickness of the resin bed obtaining as such operation, from the viewpoint of hard painting and cost and reduce to shrink and suppress the viewpoint of curling generation, is preferably 1 ~ 20 μ m, more preferably 1 ~ 15 μ m, 1 ~ 10 μ m more preferably.
(physical property of resin bed)
Wait the viewpoint of repulsion (は じ I) of printing materials from suppressing China ink, the surface tension of resin bed be preferably 30mN/m above, more preferably 33mN/m above, more preferably more than 35mN/m.
It should be noted that, the capillary value of above-mentioned resin bed is the value obtaining according to the wetting tension determination of test method of " JISK6768:1999 ", particularly, is that the value obtaining is measured in the record based on embodiment.
As the pencil hardness of case hardness that represents resin bed, be preferably more than F hardness, more preferably hardness more than H, hardness more than 2H more preferably.
It should be noted that, the pencil hardness of above-mentioned resin bed is measured and is obtained according to JISK5600-5-4, particularly, is that the record mensuration based on embodiment obtains.
(adhesive phase)
In optical film of the present invention, the adhesive phase that comprises adhesive can be set.
InstituteThe adhesive using is not particularly limited, and can from conventionally usual adhesive, suitably select and use according to object.
As such adhesive, for example can list acrylic adhesives, polyurethane series adhesive, polyester is adhesive, rubber series adhesive, silicon-type adhesive etc. In addition, adhesive can be any in latex type, solvent-borne type, no-solvent type, can be also any in crosslinked class or non-crosslinked class.
The thickness of adhesive is suitably selected according to purposes, is preferably 3 ~ 100 μ m, 5 ~ 80 μ m more preferably.
[display equipment]
There is the optical film of the present invention of above formation and the adaptation of printing material and excellent in adhesion with adhesive, and case hardness is high, therefore has good damage-resistant energy, have excellent durability. As the purposes of optical film with such feature, can list and use this optical film as display equipments such as the liquid crystal displays of the guard block of image displaying part etc.
This display equipment has used optical film of the present invention to be used as the guard block of image displaying part, and therefore, the damage-resistant of image displaying part can be good, have excellent durability.
Embodiment
Further illustrate following embodiments of the invention, but the present invention is not limited to these embodiment.
(embodiment 1 ~ 12, comparative example 1 ~ 13)
Mix (A) ~ (D) composition with the compounding amount shown in table 1 and table 2 (being mass parts (solid constituent ratio)), prepare after hardening resin composition, dilute by propylene glycol monomethyl ether, obtaining solid component concentration is the resin bed formation coating fluid of 30 quality %.
And, using as base material, (mode that uses Meyer rod to reach 3 μ m with dried thickness on trade name " Le ミ ラ ー U48 ", Dongli Ltd.'s system, thickness 100 μ face m) is coated with prepared resin bed formation coating fluid, forms coated film for PETG (PET) film of the easy adhesive linkage of band that easy bonding processing has been implemented on two sides. ,, after coated film is dried to 1 minute with 80 DEG C, use high voltage mercury lamp radiation 300mJ/cm thereafter2The ultraviolet ray of (accumulated light), solidifies coated film, has made the optical film of the resin bed with thickness 3 μ m.
The compound using as the each composition in table 1 and table 2 is as follows.
((A) composition)
A-TMN-3L: the pentaerythritol triacrylate shown in following formula (A-1) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, there is the acrylate of group shown in 3 above-mentioned general formulas (1) (R: hydrogen atom)).
[changing 5]
A-DPH: the dipentaerythritol acrylate shown in following formula (A-2) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, there is the acrylate of group shown in 6 above-mentioned general formulas (1) (R: hydrogen atom)).
[changing 6]
。
((B) composition)
A-DPH-12E: the oxirane modification dipentaerythritol acrylate shown in following formula (B-1) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, has group (R shown in 6 above-mentioned general formulas (2)1: hydrogen atom, A: ethylidene) acrylate (aggregate value of n in a part, in above-mentioned general formula (2) is 12)).
[changing 7]
A-GLY-9E: the oxirane modified glycerol triacrylate shown in following formula (B-2) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, has group (R shown in 3 above-mentioned general formulas (2)1: hydrogen atom, A: ethylidene) acrylate (aggregate value of n in a part, in above-mentioned general formula (2) is 9)).
[changing 8]
。
(other polymerizable compound)
DMAA: DMAA.
A-200: the polyethyleneglycol diacrylate shown in following formula (b-1) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, has group (R shown in 2 above-mentioned general formulas (2)1: hydrogen atom, A: ethylidene) acrylate (aggregate value of n in a part, in above-mentioned general formula (2) is 4)).
[changing 9]
A-BPE-6: the oxirane modified bisphenol A diacrylate shown in following formula (b-2) (chemical industry Co., Ltd. of Xin Zhong village system, trade name, has group (R shown in 2 above-mentioned general formulas (2)1: hydrogen atom, A: ethylidene) acrylate (aggregate value of n in a part, in above-mentioned general formula (2) is 6)).
[changing 10]
。
((C) composition)
Irgacure184:1-hydroxycyclohexylphenylketone (BASF AG's system, trade name, acetophenone are Photoepolymerizationinitiater initiater).
((D) composition)
BYK-3550: silicone-modified acrylic compounds levelling agent (BYK Amada Co., Ltd. system, trade name).
About the optical film of made, carry out following test, the characteristic of optical film is evaluated. Evaluation result is shown in table 1 and table 2.
<surface tension>
According to the wetting tension test method of " JISK6768:1999 ", measure the surface tension (mN/m) of resin bed.
<with the adaptation of printing material>
At the surface coating ultraviolet curing type China ink (trade name " UVPAL911 China ink ", ink Co., Ltd. of kingdom system) of the resin bed of optical film, irradiation ultraviolet radiation and China ink is solidified, has obtained forming the optical film of the printed layers of thickness 1 μ m.
And, implement cross to cut on the surface of printed layers and form the wide chessboard trellis of 1mm, adhesive tape (NICHIBANCO. is pasted on the surface of being cut into tessellated printed layers at this cross, LTD. system, trade name " セ ロ テ ー プ (registration mark) "), according to the gridiron pattern adhesive tape method (cross cutting method) of " JISK5600-5-6 ", carry out the disbonded test of adhesive tape, carry out the adaptation of evaluating resin layer and printing material according to following benchmark.
AA: the surface of printed layers is carried out to cross is cut and the edge of the line of cut that forms is completely level and smooth, and the lattice of any grid all do not peel off.
A: to carrying out that cross is cut and the crossing of the line of cut that forms exists little peeling off in the surface of printed layers. The ratio that is judged as obvious affected part in part cut in cross is below 5% of entirety.
B: the edge of the line of cut forming along carry out cross to cut to the surface of printed layers and/or, exist and peel off at the crossing of line of cut. Cross cut the ratio that is judged as obvious affected part in part exceed entirety 5% and be below 15%.
C: the edge of the line of cut forming along carry out cross to cut to the surface of printed layers, generating portion or whole peel off greatly and/or, several lattice parts of forming or peel off by entire surface. Cross cut the ratio that is judged as obvious affected part in part exceed entirety 15% and be below 35%.
D: the edge of the line of cut forming along carry out cross to cut to the surface of printed layers, generating portion or whole peel off greatly and/or, several lattice parts of forming or peel off by entire surface. Cross cut the ratio that is judged as obvious affected part in part exceed entirety 35% and be below 65%.
E: cross is cut the ratio that is judged as obvious affected part in part and exceeded 65% of entirety.
The repulsion (は じ I) of<China ink>
The black repulsion of Visual Confirmation in the time of the surface coating ultraviolet curing type China ink (goods name " UVPAL911 China ink ", ink Co., Ltd. of kingdom system) of resin bed, evaluates by following benchmark.
A: do not observe repulsion.
B: only observe repulsion (part is not in addition observed repulsion) in end.
C: whole face is observed repulsion.
<with the cementability (mensuration of bonding force) of adhesive>
Use double faced adhesive tape (Lin get Ke company system, goods name " TL-85S-12 "), the optical film obtaining in embodiment and comparative example is attached to glass plate (エ ヌ エ ス ジ ー プ レ シ ジ ョ Application company system, goods name “ コ ー ニ Application グ ガ ラ ス イ ー グ Le XG ", size: 70mm × 150mm × 0.3mm) upper, has prepared to expose the adherend of resin bed.
And, by the adhesive tape for evaluating bonding force (Lin get Ke company system, goods name " PET25(A) P1069111LL ") be cut into the size of 25mm × 250mm, after the release liner of release adhesive sheet, be attached on the face of resin bed of above-mentioned adherend.
Thereafter, 23 DEG C, 50%RH(relative humidity) environment under place 24 hours, under equivalent environment, use cupping machine (ORIENTEC company system, goods name " テ Application シ ロ Application "), according to JISZ0237, measure bonding force (N/25mm) with the peeling rate of 300mm/ minute, the condition of peel angle of 180 °.
<pencil hardness>
According to JISK5600-5-4, use pencil eraser to draw hardness tester (peace field essence mechanism is made made, goods name " No.553-M "), measure the pencil hardness of resin layer surface. Wiping the speed of drawing is 1mm/ second.
<applicable coating>
In the manufacturing process of above-mentioned optical film, on the face of PET film, be coated with prepared resin bed and form while using coating fluid,, because producing pin hole, repulsion evaluates by following benchmark by visual being confirmed whether.
A: do not observe the generation of pin hole.
B: slightly observe the generation of pin hole.
C: obviously observe the generation of pin hole.
<endurancing>
In this test, use the optical film that make, that be formed with printed layers by the method identical with record in above-mentioned " with the adaptation of printing material ". By this optical film 60 DEG C, 90%RH(relative humidity) environment under place 240 hours and after promoting, the mode that forms the grid of 10 × 10 total 100 lattice with surface in printed layers is implemented cross and is cut, be cut into the chessboard trellis of 10 × 10 100 lattice of 1mm width, the surface of being cut into tessellated printed layers at this cross attaches adhesive tape (NICHIBANCO., LTD. system, trade name " セ ロ テ ー プ (registration mark) "). And, according to JISK5600-5-6(cross cutting method) gridiron pattern adhesive tape method peel off this adhesive tape, carry out disbonded test, evaluated the durability of resin bed. In table 1 and table 2, record: in sum 100 lattice of grid, the quantity of the unstripped and residual grid of printed layers after disbonded test.
[table 1]
[table 2]
As shown in Table 1, the surface tension of the resin bed of this film of the optical film of the present invention of embodiment 1 ~ 12 is high, with the adaptation of printing material and excellent in adhesion with adhesive, and case hardness is high, therefore damage-resistant can be excellent and durability is also good.
On the other hand, according to table 2, the optical film of comparative example 1 ~ 13 and adaptation printing material, present poor result with the arbitrary project in surface strength and the durability of the resin bed of the cementability of adhesive, this film.
Utilizability in industry
Optical film of the present invention and adaptation printing material and excellent in adhesion with adhesive, and case hardness is high, therefore has good damage-resistant energy, have excellent durability. Owing to having such characteristic, therefore, optical film of the present invention is applicable to as the parts of the display equipments such as such as liquid crystal display.
Description of reference numerals
1,1a, 1b, 1c, 2,2a, 2b optical film
11 base materials
12,12a, 12b resin bed
13,13a, 13b adhesive phase
Claims (10)
1. optical film, it for being provided with the resin bed of the solidfied material that comprises hardening resin composition at least one face of base materialOptical film,
Described hardening resin composition contains: in a part, have group shown in 2 above following formulas (1) and except this group withIn outer remaining structure, in the polymerizable compound of oxygen-freeization alkylidene unit (A), a part, there are 3 above following leading toThe polymerizable compound (B) of group shown in formula (2) and polymerization initiator (C), (A) composition and (B) matter of compositionAmount is 15/85～85/15 than ((A)/(B)), in a part of described polymerizable compound (B), and following general formula(2) aggregate value of the n in is 6～20,
[changing 1]
In above-mentioned formula (1), R represents hydrogen atom or methyl independently of one another, and * represents bonding part,
[changing 2]
In above-mentioned formula (2), R1Represent independently of one another hydrogen atom or methyl, A represents the alkylene of carbon number 1～5 independently of one anotherBase, n is more than 1 integer independently of one another, * represents bonding part.
2. optical film according to claim 1, wherein, the A in described general formula (2) is ethylidene or Asia independently of one anotherPropyl group.
3. optical film according to claim 1 and 2, wherein, described hardening resin composition also contains levelling agent(D)。
4. optical film according to claim 1 and 2, wherein, the surface tension of described resin bed is more than 30mN/m.
5. optical film according to claim 1 and 2, wherein, is provided with and comprises described curability on the two sides of described base materialThe resin bed of the solidfied material of resin combination.
6. optical film according to claim 4, wherein, is provided with and comprises described curable resin on the two sides of described base materialThe resin bed of the solidfied material of composition.
7. optical film according to claim 1 and 2 wherein, is being contrary with the face that is provided with resin bed of described base materialOn at least one face of side and same side, possesses the adhesive phase that comprises adhesive.
8. optical film according to claim 4, wherein, with the face that is provided with resin bed of described base material be opposition side andOn at least one face of same side, possesses the adhesive phase that comprises adhesive.
9. optical film according to claim 5, wherein, with the face that is provided with resin bed of described base material be opposition side andOn at least one face of same side, possesses the adhesive phase that comprises adhesive.
10. display equipment, it has used the optical film described in any one in claim 1～9.
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| JP2012-023453 | 2012-02-06 | ||
| JP2012023453A JP6074144B2 (en) | 2012-02-06 | 2012-02-06 | Optical film and display device |
| PCT/JP2013/052605 WO2013118720A1 (en) | 2012-02-06 | 2013-02-05 | Film for optical applications, and display device |
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| KR (1) | KR102148126B1 (en) |
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| JP6227321B2 (en) * | 2013-08-05 | 2017-11-08 | リンテック株式会社 | Transparent conductive film with protective film |
| JPWO2016006627A1 (en) * | 2014-07-11 | 2017-04-27 | 三菱レイヨン株式会社 | Fine uneven structure |
| KR101979200B1 (en) * | 2014-10-16 | 2019-05-17 | 주식회사 엘지화학 | Optical film coating composition and optical film including the same |
| JP6226104B1 (en) * | 2016-02-24 | 2017-11-08 | 東レ株式会社 | Colored resin composition |
| JP6291558B2 (en) * | 2016-11-08 | 2018-03-14 | リンテック株式会社 | Optical film and display device |
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| CN1611968A (en) * | 2003-10-31 | 2005-05-04 | 琳得科株式会社 | Paint composition, hard coating and CD |
| CN101104724A (en) * | 2002-02-01 | 2008-01-16 | 纳托科株式会社 | Composition curable with actinic energy ray and use thereof |
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| JP2006007434A (en) * | 2004-06-22 | 2006-01-12 | Daikin Ind Ltd | Antireflection film laminate and its manufacturing method |
| JP5355069B2 (en) * | 2007-12-28 | 2013-11-27 | 富士フイルム株式会社 | Colored curable composition, color filter, method for producing the same, and solid-state imaging device |
| JP2009161609A (en) | 2007-12-28 | 2009-07-23 | Three M Innovative Properties Co | Hard coat film and printed matter |
| JP2010032795A (en) * | 2008-07-29 | 2010-02-12 | Fujifilm Corp | Hard coat film, manufacturing method of hard coat film, antireflection film, polarizing plate, and display device |
| JP2011002759A (en) * | 2009-06-22 | 2011-01-06 | Dnp Fine Chemicals Co Ltd | Antireflection film |
| JP5381570B2 (en) * | 2009-09-29 | 2014-01-08 | 大日本印刷株式会社 | Method for producing hard coat film, hard coat film, polarizing plate and display panel |
| JP5414449B2 (en) * | 2009-10-16 | 2014-02-12 | 株式会社トクヤマ | Coating composition |
| JP2011110902A (en) | 2009-11-30 | 2011-06-09 | Fujicopian Co Ltd | Hard coat film and decorated hard coat film |
| KR101234851B1 (en) * | 2009-12-31 | 2013-02-19 | 제일모직주식회사 | Hard coating composition and larminate comrising hard coat layer |
| WO2011115162A1 (en) * | 2010-03-17 | 2011-09-22 | 三菱レイヨン株式会社 | Active energy ray curable resin composition and article having finely roughened structure on surface |
| JP5593848B2 (en) * | 2010-05-31 | 2014-09-24 | 大日本印刷株式会社 | Transparent conductive material |
| JP2012006321A (en) * | 2010-06-28 | 2012-01-12 | Sumitomo Chemical Co Ltd | Display-protecting resin plate |
| JP2012072269A (en) * | 2010-09-28 | 2012-04-12 | Fujifilm Corp | Microstructure |
| JP6128629B2 (en) * | 2011-04-22 | 2017-05-17 | 日東電工株式会社 | Optical laminate |
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| CN101104724A (en) * | 2002-02-01 | 2008-01-16 | 纳托科株式会社 | Composition curable with actinic energy ray and use thereof |
| CN1611968A (en) * | 2003-10-31 | 2005-05-04 | 琳得科株式会社 | Paint composition, hard coating and CD |
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| CN104115036A (en) | 2014-10-22 |
| JP2013160954A (en) | 2013-08-19 |
| WO2013118720A1 (en) | 2013-08-15 |
| JP6074144B2 (en) | 2017-02-01 |
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| KR20140125779A (en) | 2014-10-29 |
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