CN106336803A - Compositon for hard coating, optical film and display device using the same - Google Patents
Compositon for hard coating, optical film and display device using the same Download PDFInfo
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- CN106336803A CN106336803A CN201610507553.5A CN201610507553A CN106336803A CN 106336803 A CN106336803 A CN 106336803A CN 201610507553 A CN201610507553 A CN 201610507553A CN 106336803 A CN106336803 A CN 106336803A
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- methyl
- acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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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
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Abstract
The invention provides a composition for a hard coating, an optical film and a display device using the same. The composition contains dendrimer compound (A), a photopolymerisable compound (B), a photopolymerisable initiator (C), and a solvent. The composition can reach a proper curing intensity, and ensures the hardness of the hard coating, and also greatly increases warping and flexibility.
Description
Technical field
The present invention relates to hard conating formation compositionss, the blooming employing it and image display device.
Background technology
In recent years, liquid crystal indicator (liquid crystal display) or organic light-emitting display device are employed
The thin-type display device of panel display apparatus such as (organic light emitting diode display) receives publicity.Special
Not, these thin-type display devices are realized in the form of touch panel (touch screen panel), are not only intelligent handss
Machine (smart phone), flat board (tablet) pc, and until various wearable devices (wearable device), so that
It is widely used in the various smart machines (smart device) that the property taken is characterized.
Display device based on these portable touch panels, in order to protect display pannel from cut,
Outside impact, possesses display protection window film, all using display in the case of nearly all on display pannel
With strengthens glass as window film.Display strengthens glass is than common glass thin, but has high intensity and damage resistant
Feature.
But, the weight of strengthens glass is big, is not only not suitable for the lighting of portable equipment, and rushes for from outside
Hit fragility, the property (unbreakable) therefore realizing being difficult to damage is difficult, in addition cannot bend to more than certain level.Cause
This, strengthens glass is not suitable as the flexibility with flexible (bendable) or foldable (foldable) function
(flexible) raw material of display.
Recently, for guaranteeing there is while flexibility and impact resistance intensity, the scratch-resistant being equivalent to strengthens glass
Optics plastic cover, carried out positive research.Usually, use as the optics compared with strengthens glass with flexibility
The raw material of the front cover of transparent plastic, has polyethylene terephthalate (pet), polyether sulfone (pes), poly- naphthalenedicarboxylic acid second two
Alcohol ester (pen), polyacrylate (par), Merlon (pc), polyimides (pi) etc..But, these high molecule plastic substrates
Compared with the strengthens glass as display protection window film, in terms of hardness and scratch-resistant, not only show insufficient thing
Property, and impact resistance is also insufficient.Therefore, carried out will by these plastic bases be coated with composite resin composition thus
Supplement the various trials of required physical property.
Thus, plastic basis material film arranges hard conating and ensure that high rigidity.For common hard conating, using by wrapping
The resin of the functional group containing light-cured type and the compositionss of firming agent or curing catalysts and other additives composition, especially
Ground, in the case of the composite resin of high functional group, is applied on optics plastic basis material film, can be used as hardness and scratch-resistant
The display protection form that trace improves uses.
But, the composite resin of general light-cured type, not only it is difficult to be equivalent to the high rigidity of strengthens glass, and
Significantly there is curling (curl) phenomenon that contraction during solidification causes, in addition flexibility is also insufficient, therefore has and is not suitable for
With the shortcoming acting on the protection window film being applied to flexible display.
Plastic base is disclosed in KR published patent 2013-74167 (patent documentation 1).
Prior art literature
Patent documentation
Patent documentation 1: KR published patent 2013-74167 publication
Content of the invention
Invention problem to be solved
Obtain it is an object of the invention to provide can manufacture and can realize high rigidity and flexibility and crimping simultaneously
The hard conating formation compositionss of the hard coat film of suppression.
It is further an object that being provided with being formed the light of the hard conating being formed with compositionss by above-mentioned hard conating
Learn film.
And then, it is an object of the invention to provide possessing the image display device of above-mentioned blooming.
Means for solving the problems
1. hard conating formation compositionss, dendrimer compound (a) that it comprises to be represented by following chemical formula 1,
Photopolymerizable compound (b), Photoepolymerizationinitiater initiater (c) and solvent (d).
[chemical formula 1]
(r1)4-nc(ch2or2)n
(in formula, n is 2～4 integer,
r1For the alkyl of carbon number 2～5,
r2For
M is 2 or 3,
r3It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular3Acrylate-based for (methyl).)
2. the hard conating formation compositionss of above-mentioned project 1, wherein, in above-mentioned chemical formula 1,
r3For hydrogen atom or
At least one r3For
X is 2 or 3,
r4It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular4Acrylate-based for (methyl).
3. the hard conating formation compositionss of above-mentioned project 1, wherein, with respect to the polymerizable component (mixing of (a) and (b)
Weight) total 100 weight portions, the dendrimer compound being represented by above-mentioned chemical formula 1 containing 10～50 weight portions
(a).
4. the hard conating formation compositionss of above-mentioned project 1, wherein, above-mentioned photopolymerizable compound (b) comprises selected from ammonia
Carbamate system (methyl) acrylate and comprise at least one of (methyl) acrylate of oxygen ethylidene.
5. the hard conating formation compositionss of above-mentioned project 4, wherein, above-mentioned carbamate system (methyl) acrylate is
The product being replaced by cyclohexyl.
6. the hard conating formation compositionss of above-mentioned project 1, wherein, above-mentioned Photoepolymerizationinitiater initiater (c) is selected from 1-Phenylethanone.
It is at least one of light trigger and amino ketones system light trigger.
7. the hard conating formation compositionss of above-mentioned project 1, wherein, also comprise inorganic nano-particle.
8. blooming, it possesses the hard conating shape described in any one of above-mentioned project 1～7 at least one side of base material film
The coating that one-tenth is formed with compositionss.
9. the blooming of above-mentioned project 8, wherein, above-mentioned blooming is window film.
10. image display device, it possesses the blooming described in above-mentioned project 8.
The effect of invention
The hard conating formation compositionss of the present invention are by comprising the dendrimer compound of ad hoc structure, Neng Goushi
Now suitable cured density.Thereby, it is possible to curl characteristics and flexibility are significantly increased while guaranteeing the hardness of hard conating.
In addition, the hard conating formation compositionss of the present invention, due to having excellent curl characteristics and flexibility, therefore can
Enough it is suitably applied flexible display
Specific embodiment
The present invention relates to hard conating formation compositionss, in more detail, it is related to the dendroid by comprising ad hoc structure
Macromolecular compound (a), photopolymerizable compound (b), Photoepolymerizationinitiater initiater (c) and solvent (d) are such that it is able to realize suitably
Cured density, the hard conating of curl characteristics and flexibility thus can be significantly increased while guaranteeing the hardness of hard conating
Formation compositionss, the blooming employing it and image display device.
Hereinafter the present invention is explained.
＜ hard conating forms and uses compositionss ＞
The hard conating formation compositionss of the present invention comprise the dendrimer compound (a) of ad hoc structure, photopolymerization
Property compound (b), Photoepolymerizationinitiater initiater (c) and solvent (d).
Dendrimer compound (a)
Comprise the dendritic macromole chemical combination being represented by following chemical formula 1 according to the hard conating formation compositionss of the present invention
Thing (a).
[chemical formula 1]
(r1)4-nc(ch2or2)n
(in formula, n is 2～4 integer,
r1For the alkyl of carbon number 2～5,
r2For
M is 2 or 3,
r3It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular3Acrylate-based for (methyl).
In this case, the dendrimer compound of chemical formula 1 becomes the dendrimer compound of 2nd generation,
By branches end comprise at least one (methyl) acrylate-based, thus in hard conating formation compositionss play polymerization
The effect of property compound.
According to another embodiment of the present invention, for dendrimer compound, the r in above-mentioned chemical formula 13For hydrogen
Atom or
At least one r3For
X is 2 or 3,
r4It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular4Can be acrylate-based for (methyl).
In this case, the dendrimer compound of chemical formula 1 becomes the dendrimer compound in the 3rd generation,
By branches end comprise at least one (methyl) acrylate-based, thus in hard conating formation compositionss play polymerization
The effect of property compound.
Dendritic macromole (dendrimer) compound is for strand according to certain rule from the outside portion in center regularly
The compound of polymerization." generation " in dendrimer compound means on the basis of central part, polymerizable functional group is carried out
Polyreaction and the number of times of branch that formed.In the case that the branches end of the 1st generation being formed carries out polyreaction again, become
2nd generation, polyreaction repeatedly is carried out.
In above-mentioned formula, n, m and x mean the generation number in per generation, it means that in each generation polyreaction can carry out poly-
The number of He Xing functional group.Total generation number of the dendrimer compound of synthesis means the generation number in each generation is multiplied.
In the present invention, it is that hard conating is formed with compositionss by the dendrimer compound that above-mentioned chemical formula 1 represents
During the polyreaction of polymerizable component ((a) and (b)), the molecular weight of polymer and crosslink density are adjusted to becoming of proper range
Point.Specifically, the dendrimer compound of above-mentioned chemical formula 1 is aggregated to tool on the basis of central part in polyreaction
There is the branch of lateral direction, form polymerizable functional group in each branches end.Thus, the polymerizable compound with common structure
Polyreaction compare, due to having more functional groups compared with the molecular weight of polymer, excellent hard therefore, it is possible to realize
Degree characteristic.
In addition, the dendrimer compound of chemical formula 1, due to only containing polymerizable functional group in end, is therefore polymerized
The central part of thing is able to ensure that suitable flexibility.Thus, curl characteristics can be improved while guaranteeing the hardness of hard conating
And flexibility.
The for example following institute of the polyreaction formula of the outline of the dendrimer compound that one embodiment of the present invention is related to
Show.
[reaction equation 1]
From above-mentioned reaction equation, the dendrimer compound that one embodiment of the present invention is related to is formed with tmp
Centered on, the dendritic macromole structure of 1st generation that dmpa is condensed.Then, dmpa is made repeatedly to be condensed as branched structure
It is polymerized and makes the algebraically of dendritic macromole continue to increase, after the 3rd generation, make the condensation polymerizations such as acrylic acid in terminal groups, can
It is formed at the dendrimer compound that end has multifunctional acryloyl group.
In the present invention, the aspect of the effect stated in realization, the dendrimer compound being represented by chemical formula 1 is preferred
There is 2nd generation or the structure in the 3rd generation.If it exceeds the 3rd generation ground reacted, then produce gelation problem.
In the present invention, the content of the dendrimer compound being represented by chemical formula 1 is not particularly limited, for example,
With respect to total 100 weight portions of polymerizable component (mixed weight of (a) and (b)), can be 10～50 weight portions, preferably
Can be 20～40 weight portions.If meeting above range, be capable of while guaranteeing excellent hardness curl characteristics and
Flexibility.If less than 10 weight portions, flexibility reduces sometimes, if it exceeds 50 weight portions, then because space steric effect produces
The presence of raw unreacted functional group is it is difficult to guarantee hardness property.
Photopolymerizable compound (b)
The photopolymerizable compound (b) of the present invention is the one-tenth for improving the mechanical properties of hard conating (particularly hardness)
Point.
The species of photopolymerizable compound (b) is not particularly limited, for example, it may be having polymerism unsaturated group
Monofunctional compound or polyfunctional compound.These can be used alone or are used in mixed way two or more.
Crosslink density will not be made to reduce when intramolecular has the compound of 1～3 polymerism unsaturated group in solidification,
The curl characteristics of solidfied material can be improved.In addition, have the multiple functionalized of the polymerism unsaturated group of more than 4 in intramolecular
Compound is so that crosslink density is increased in solidification, hard conating is given with the composition of excellent hardness.
As the concrete example of the photopolymerizable compound of the present invention, as comprising at least one (methyl) acrylate-functional
Group, as the monomer of polymerizable functional group, can include dipentaerythritol six (methyl) acrylate, dipentaerythritol five (first
Base) acrylate, tetramethylolmethane four (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, comprise oxygen
(methyl) acrylate of ethylidene, ester (methyl) acrylate, ether (methyl) acrylate, carbamate (methyl) propylene
Acid esters, epoxy (methyl) acrylate and melamine (methyl) acrylate.
As polymerism unsaturated group, preferably there is the compound of (methyl) acryloyl group or vinyl.As concrete
Example, can include (methyl) acrylate, n- vinyl compound, vinyl-substituted aromatic compound, vinyl ethers and
Vinyl esters.
As (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (first can be enumerated
Base) acrylate, glycerol three (methyl) acrylate, three (2- hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, second
Glycol two (methyl) acrylate, propylene glycol (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, Isosorbide-5-Nitrae-fourth two
Alcohol two (methyl) acrylate, 1,6- hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, diethylene glycol
Two (methyl) acrylate, 2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, double (2- hydroxyl second
Base) isocyanuric acid ester two (methyl) acrylate, add oxirane or expoxy propane in above-mentioned (methyl) acrylate
Poly- (methyl) acrylate；There is oligoester (methyl) acrylate of 1～3 (methyl) acryloyl group, oligomeric in the molecule
Ether (methyl) acrylate, oligomeric carbamate (methyl) acrylate, oligomeric epoxy (methyl) acrylate；(methyl) third
Olefin(e) acid hydroxy methacrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, in above-mentioned (methyl) acrylate
Add the product of oxirane or expoxy propane；Single (methyl) acrylate, (methyl) Isooctyl acrylate monomer, (methyl) propylene
Sour isodecyl ester, (methyl) stearyl acrylate ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylate.In addition,
As n- vinyl compound, n- vinyl pyrrolidone, n- caprolactam, n- vinyl O-phthalic can be included
Acid imide, n- vinylsuccinimide etc..As vinyl aromatic compound, styrene, divinyl can be included
Base benzene, 1-chloro-4-methyl-benzene, hydroxy styrenes, α-methyl styrene, bromometllylstyrene, trisbromomethyl styrene etc..As
Vinyl ethers, can include diethylene glycol monomethyl vinyl ethers, ethylene glycol divinyl ether, diethylene glycol divinyl ether, three sweet
Alcohol divinyl ether etc..As vinyl esters, vinylacetate, propionate, vinyl benzoate etc. can be included.
In above-mentioned photopolymerizable compound, from the viewpoint of hardness improves, carbamate system (methyl) third can be used
Olefin(e) acid ester.In addition, from the viewpoint of flexibility improves, can be using (methyl) acrylate comprising oxygen ethylidene.Most preferably
Carbamate system (methyl) acrylate and (methyl) that comprise oxygen ethylidene acrylate can be used together by ground.
In the present invention, above-mentioned carbamate system acrylate can be by diisocyanate cpd and have hydroxyl
Multifunctional (methyl) acrylate compounds carry out condensation reaction and manufacture.
The species of diisocyanate cpd is not particularly limited it is preferable that can be the compound being replaced with cyclohexyl.
Thus, urethane acrylate can have the substituent group of cyclohexyl.In this case, the structure being had due to cyclohexyl
Stability and there is both hardness and flexibility, at this point preferably.
As the concrete example of the diisocyanate cpd being replaced with cyclohexyl, Isosorbide-5-Nitrae-cyclohexyl two Carbimide. can be included
Ester, isophorone diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanate etc..But, it is not limited to these, specifically
Ground, can enumerate compound being represented by following chemical formula 2 and 3 etc..
[chemical formula 2]
[chemical formula 3]
As the concrete example of the polyfunctional acrylic ester with hydroxyl, trimethylolpropane two (methyl) acrylic acid can be enumerated
Ester, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate etc., but it is not limited to these.
In the present invention, the above-mentioned acrylate comprising oxygen ethylidene can carry out addition by making oxirane and polyhydric alcohol
Reaction and after having obtained having the polyfunctional alcohol of oxygen ethylidene, make (methyl) acrylic acid and above-mentioned polyfunctional alcohol carry out condensation reaction
And manufacture.As the concrete example of polyhydric alcohol, glycerol, trimethylolpropane, tetramethylolmethane, dipentaerythritol etc. can be included, but
It is not limited to these.
As the concrete example of the above-mentioned acrylate comprising oxygen ethylidene, trimethylolpropane (eo) can be included3Three (first
Base) acrylate, trimethylolpropane (eo)6Three (methyl) acrylate, trimethylolpropane (eo)9Three (methyl) acrylic acid
Ester, glycerol (eo)3Three (methyl) acrylate, glycerol (eo)6Three (methyl) acrylate, glycerol (eo)9Three (methyl) acrylic acid
Ester, tetramethylolmethane (eo)4Four (methyl) acrylate, tetramethylolmethane (eo)8Four (methyl) acrylate, tetramethylolmethane (eo)12
Four (methyl) acrylate, dipentaerythritol (eo)6Six (methyl) acrylate, dipentaerythritol (eo)12Six (methyl) propylene
Acid esters, dipentaerythritol (eo)18Six (methyl) acrylate etc..But, be not limited to these, specifically, can enumerate by under
Compound that the chemical formula 4 and 5 stated represents etc..
[chemical formula 4]
[chemical formula 5]
In the present invention, the content of photopolymerizable compound (b) is not particularly limited, for example, with respect to polymerizable component
Total 100 weight portions of (mixed weight of (a) and (b)), can be 65～95 weight portions, can preferably be 60～80 weight
Part.If meeting above range it can be ensured that excellent mechanical properties.
In the present invention, as photopolymerizable compound (b), by carbamate system (methyl) acrylate with to comprise oxygen sub-
In the case that the crylic acid ester mixture of ethyl uses, the content of carbamate system acrylate is not particularly limited, for example
With respect to total 100 weight portions of polymerizable component (mixed weight of (a) and (b)), can be 20～70 weight portions, preferably
Can be 40～50 weight portions.If meeting above range it can be ensured that excellent mechanical properties.If less than 20 weight portions,
Sometimes hardness reduces, if it exceeds 70 weight portions, then due to the excessive increase of contractility, the curling of coating occurs sometimes, breaks
Split, ftracture.
In addition, being not particularly limited to the content of above-mentioned (methyl) acrylate comprising oxygen ethylidene, for example with respect to
Total 100 weight portions of polymerizable component (mixed weight of (a) and (b)), can be 10～50 weight portions, can preferably be
30～40 weight portions.If meeting above range, while guaranteeing excellent mechanical properties, it is capable of flexibility.If no
To 10 weight portions, due to the minimizing of cured density, mechanical properties reduce sometimes, if it exceeds 50 weight portions, due to cured density
Rising, be sometimes difficult to ensure that flexibility.
Photoepolymerizationinitiater initiater (c)
As Photoepolymerizationinitiater initiater (c) according to the present invention, as long as free radical can be formed by light irradiation, then have no
Especially limit.
The decomposition of the molecule causing by the difference of chemical constitution or molecular bond energy is had to generate certainly in Photoepolymerizationinitiater initiater (c)
Coexist and take out the type type initiator of Hydrogen by the typei type initiator of base with tertiary amine.
As the concrete example of typei type initiator, 4- phenoxydichloroacetophenone, 4- tert-butyl dichloro-benzenes second can be enumerated
Ketone, 4- tert-butyl trichloroacetophenone, diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- (4- isopropyl
Base phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- (4- dodecylphenyl) -2- hydroxy-2-methyl propane -1- ketone, 4-
(2- hydroxyl-oxethyl)-phenyl (2- hydroxyl -2- propyl group) acetophenones such as ketone, 1- hydroxycyclohexylphenylketone, benzoin, benzene are even
The benzoin class such as relation by marriage methyl ether, benzoin ethyl ether, benzil dimethyl ketal, acylphosphine oxide class, titanocenes compound etc..
As the concrete example of type type initiator, benzophenone, benzoyl benzoic acid, Benzoylbenzene can be enumerated
Carboxylic acid methyl ether, 4- phenyl benzophenone, dihydroxy benaophenonel, 4- benzoyl -4'- dimethyl diphenyl sulfide, 3,3'- first
The benzophenones such as base -4- methoxy benzophenone, thiaxanthone, CTX, 2- methyl thiaxanthone, 2,4- dimethyl thioxanthene
Thiaxanthones such as ketone, isopropyl thioxanthone etc..
Photoepolymerizationinitiater initiater can use a kind, and also two or more may be used.In addition, can be by typei type and type type list
Solely use or be used in combination.
As the commercially available product of Photoepolymerizationinitiater initiater, there is irgacure 184 (manufacture of basf company) etc..
In the present invention, the content of Photoepolymerizationinitiater initiater (c) is not particularly limited, for example, total with respect to compositionss
100 weight portions, can be for 0.1～10 weight portion it is preferable that can be 1～5 weight portion.If meeting above range, Neng Goushi
Existing excellent mechanical properties and closing force.If less than 0.1 weight portion, sometimes solidifying and not being sufficiently carried out, final film
Mechanical properties, closing force reduce, if it exceeds 10 weight portions, sometimes there is cracking, curling that cure shrinkage causes etc..
Solvent (d)
As solvent (d) according to the present invention, as long as above-mentioned composition being dissolved or disperseing it becomes possible to no especially limit
System ground uses.
As concrete example, alcohol system (methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol etc.), ketone system (first can be enumerated
Base ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), metacetone, dipropyl ketone etc.), acetass system (methyl acetate, acetic acid
Ethyl ester, butyl acetate, propylene glycol methoxy acetass etc.), cellosolve system (methyl cellosolve, ethyl cellosolve, propyl cellosolve
Deng), hydrocarbon system (normal hexane, normal heptane, benzene,toluene,xylene etc.) etc..These can be used alone or mix two or more
Use.
In the present invention, the content of solvent is not particularly limited, for example, with respect to total 100 weight portions of compositionss, can
Think 5～90 weight portions it is preferable that can be 20～70 weight portions.In the range of above-mentioned content, it is capable of suitably
Coating, therefore preferably.On the other hand, if less than 5 weight portions, viscosity is high, and coating reduces, if it exceeds 90 weight
Part, the adjustment of the thickness of film is difficult sometimes, produces uneven drying, and bad order occurs.
Inorganic nano-particle (e)
Hard conating formation compositionss according to the present invention, in order to ensure the mechanical properties of hard conating, can further include
Inorganic nano-particle (e).
Above-mentioned inorganic nano-particle (e) is equably formed in film, it is possible to increase mar proof, scratch-resistant, pencil
The mechanical properties such as hardness.
The mean diameter of inorganic nano-particle (d) according to the present invention is not particularly limited, for example can for 1～
100nm, can preferably be 5～50nm.If in above range, being capable of excellent mechanical property.On the other hand, such as
Less than 1nm, then there is the cohesion of particle it is impossible to form homogeneous film in fruit mean diameter, if it exceeds 100nm, not only optics
Characteristic reduces, and mechanical property also reduces.
The species of above-mentioned inorganic nano-particle (d) is not particularly limited, for example, can be metal-oxide, can use
Selected from al2o3、sio2、zno、zro2、batio3、tio2、ta2o5、ti3o5、ito、izo、ato、zno-al、nb2o3、sno、mgo、
With a kind in combinations thereof it is preferable that al can be used2o3、sio2、zro2Deng.
In the present invention, the content of inorganic nano-particle (d) is not particularly limited, for example total with respect to compositionss
100 weight portions, can be 10～50 weight portions.In the range of above-mentioned content, mar proof, scratch-resistant, pencil are hard
The mechanical properties such as degree are excellent.On the other hand, if it exceeds 50 weight portions, sometimes hinder curable, so that mechanical property is reduced on the contrary,
The bad of outward appearance can occur.
Above-mentioned inorganic nano-particle can be diluted to the concentration of 10～80 weight % in organic solvent and use.
Additive (f)
Hard conating formation compositionss according to the present invention, in addition to aforesaid composition, can be wrapped as needed further
Containing additive, for example, can enumerate levelling agent, ultra-violet stabilizer, heat stabilizer etc..
Levelling agent is in order to improve the flatness of film and coating in coating composition and to add, and can use silicon
Levelling agent, fluorine system levelling agent, acrylic acid seriess levelling agent etc..As the commercially available product of above-mentioned levelling agent, byk chemie can be used
Byk-323, byk-331, byk-333, byk-337, byk-373, byk-375, byk-377, byk-378, tego of company is public
The tego glide 410 of department, tego glide 411, tego glide 415, tego glide 420, tego glide
432、tego glide 435、tego glide 440、tego glide 450、tego glide 455、tego rad
2100th, tego rad 2200n, tego rad 2250, tego rad 2300, tego rad 2500, the fc- of 3m company
4430th, fc-4432 etc..
Ultra-violet stabilizer is to prevent the variable color or easy damage because lasting ultraviolet irradiates of the surface of film
Badly add, the effect played masking or absorb ultraviolet.Above-mentioned ultra-violet stabilizer can be divided into according to the mechanism of action
Absorbent, delustering agent (quenchers), hindered amine as light stabilizer (hals, hindered amine light
Stabilizer), phenyl salicylate (phenyl salicylates, absorbent), benzophenone can for example be included
(benzophenone, absorbent), benzotriazole (benzotriazole, absorbent), nickel derivant (delustering agent), free radical
Agent for capturing (radical scavenger) etc..
As heat stabilizer, the heat stabilizer of polyphenol system, phosphite ester system and lactone system can be used.Above-mentioned ultraviolet is steady
Determine agent and heat stabilizer can be used in mixed way with suitable content on not affecting ultra-violet solidified level.
Above-mentioned additive, with respect to total 100 weight portions of all compositions, preferably uses 0.1～3 weight portion.
＜ blooming ＞
In addition, the present invention is provided with being formed the blooming of the hard conating being formed with compositionss by above-mentioned hard conating.
The blooming of the present invention is included in the base material film that at least one side possesses the hard conating being formed by above-mentioned composition.
As base material film, as long as transparent polymeric membrane, then can use with no particular limitation, for example can include by
Triacetyl cellulose, acetylcellulose butyrate, vinyl-vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, second
Acyl propionyl cellulose, polyester, polystyrene, polyamide, Polyetherimide, polyacrylic, polyimides, polyether sulfone, polysulfones,
Polyethylene, polypropylene, polymethylpentene, polrvinyl chloride, Vingon, polyvinyl alcohol, Pioloform, polyvinyl acetal, polyether-ketone, poly-
Ether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- naphthalene
The film that the macromolecules such as naphthalate, Merlon are formed.These macromolecules can be used alone or mix two or more
Close and use.
In base material film, it is difficult to after coating give the crystalline polymer base material film of closing force, engineering plastics base material, passes through water
Solution, saponification and in the case of so that surface is become and turn to hydrophilic polymer base material film, if formed using common hard conating used
Compositionss, the raising of closing force is difficult sometimes, or therefore mechanical properties reduce.But, the hard conating shape of the above-mentioned present invention
One-tenth compositionss also will not make mechanical properties reduce even for these base material films, is capable of excellent closing force.
For base material film, in order to improve the closing force with hard conating, can be to have passed through corona treatment, sided corona treatment
Base material film Deng surface treatment.
Hard conating passes through to be coated with hard conating formation compositionss on base material film, is solidified to form.In coating, can use
Slot coated method, scraper for coating method, spin-coating method, the tape casting, microgravure rubbing method, heliogravure rubbing method, stick coating method,
Rolling method, wire rod rubbing method, dip coating, spraying process, silk screen print method, woodburytype, aniline printing method, hectographic printing
The known method such as method, ink-jet application method, allotter print process, nozzle rubbing method, capillary rubbing method.
The thickness of hard conating is not particularly limited, can be such as 5～100 μm.If thickness is in above range, show
Show excellent hardness and flexibility, be prevented from crimp.
The blooming of the present invention due to having excellent hardness, flexibility and curl characteristics, therefore, it is possible to usefully apply
Window film in image display device.
＜ image display device ＞
In addition, the present invention is provided with the image display device of above-mentioned hard coating film.
The hardness of the hard coating film of the present invention and flexibility are excellent.Above-mentioned hard coating film for example can show dress as image
The outmost window film put uses, and especially, can be suitably applied flexible image display device.
Image display device can be common liquid crystal indicator, el display device, plasma display dress
Put, the various image display devices such as field-emission display device.
In order to contribute to the understanding of the present invention, preferred embodiment is shown below, but these embodiments are only to this
Invention is illustrated, and not limits appended Patent right requirement, in the range of scope of the invention and technological thought for
The change of embodiment is various and can be modified, this will be obvious to those skilled in the art that this
The change of sample and correction fall within appended Patent right requirement certainly.
Production Example-polymerizable component
[table 1]
The dendrimer compound in the a-1: the 3 generation
The dendrimer compound of a-2: 2nd generation
B-1:sou-1700b (shin-at＆c manufacture)
B-2:sou-1290 (shin-at＆c manufacture)
B-3:ua-306h (chemistry joint-stock company of common prosperity society manufactures)
B'-1:m4004 (manufacture of Mei Yuan Specialty Chemicals)
B'-2:dpea126 (Japanese chemical medicine company system is made)
B " -1:m300 trimethylolpropane trimethacrylate (manufacture of Mei Yuan Specialty Chemicals)
B " -2:m600 dipentaerythritol acrylate (manufacture of Mei Yuan Specialty Chemicals)
B " -3:m-340 (manufacture of Mei Yuan Specialty Chemicals)
Embodiment and comparative example
With respect to polymerizable component [embodiment 1～14 (group using Production Example 1～14 based on composition and content in table 1
Compound), comparative example 1～4 (using the compositionss of Production Example 15～18)] mixture 30 weight portion, put into nanopol 784
30 weight portions of (the 20nm Ludox that evonik company manufactures, pgema50% dilutes), the igacure184 of light trigger
5 weight portions of (manufacture of basf company), 3 weight portions of the byk-333 of levelling agent, 30 weight portions of methyl ethyl ketone, toluene
10 weight portions, manufacture hard conating formation compositionss.
Test method
Using rod coaters, the hard conating formation compositionss of embodiment and comparative example are coated 80 μm of optics polyamides
Imines film (manufacture of Rhizoma Sparganii gas chemical company, 100 μm, l-3430), is coated so that dried thickness becomes 20 μm,
It is dried 2 minutes in 80 DEG C of baking oven.Then, adopt high-pressure mercury-vapor lamp with 350mj/cm2Irradiate, manufacture hard coating film.
(1) pencil hardness
Using pencil scratching tester (pht, Korea S's sukbo scientific company manufacture), apply the load of 500g, determine lead
Hardness.Pencil uses Rhizoma Sparganii product, and each pencil hardness carries out the experiment of average 5 times, by cut be 1 time shown below
Maximum pencil hardness is as the pencil hardness of this hard conating.
(2) marresistance
Using steel wool testing machine (wt-lcm100, protech company of Korea S manufacture), past under 1kg/ (2cm × 2cm)
Move 10 times again, marresistance is tested.As steel wool, employ #0000.
＜ evaluation criterion ＞
S: cut is 0
A: cut is 1～10
B: cut is 11～20
C: cut is 21～30
D: cut is more than 31
(3) adaptation
In the coated face of film, the longitudinal and transverse cut channel forming 11 is spaced in 1mm, is made 100 squares.So
Afterwards, 3 disbonded tests, the number of the tetragon that record is peeled off are carried out using adhesive tape (ct-24, Japanese nichiban company manufacture)
Meansigma methodss.
Adaptation record as described below.
Adaptation=n/100
(n: the number of the tetragon not being stripped in whole tetragons, 100: the number of whole tetragons)
Should illustrate, in the case of not all being stripped, be recorded as 100/100.
(4) crimp
The sample being cut to a4 size (29.7 × 21.0cm) is placed on flat glass plate so that film coated
Face upper, measure under 25 DEG C, 50%rh 4 jiaos with glass plate distance, using meansigma methodss as measured value.
(5) plug
The coated film sample of the size of 1cm × 10cm in order to evaluate flexibility and the cracking behavior of film, will be cut into
It is placed on the iron rod of each diameter (2 φ～10 φ), make coating be upper, bent with record book in accordion form, it is shown in surface and do not produce out
The diameter of the minimum split.
[table 2]
| Distinguish | Pencil hardness | Marresistance | Adaptation | Curling | Plug |
| Embodiment 1 | 6h | s | 100/100 | 3mm | 2φ |
| Embodiment 2 | 5h | s | 100/100 | 3mm | 2φ |
| Embodiment 3 | 6h | s | 100/100 | 3mm | 3φ |
| Embodiment 4 | 5h | s | 100/100 | 3mm | 3φ |
| Embodiment 5 | 5h | s | 100/100 | 4mm | 3φ |
| Embodiment 6 | 5h | s | 100/100 | 5mm | 2φ |
| Embodiment 7 | 5h | s | 100/100 | 3mm | 3φ |
| Embodiment 8 | 6h | a | 100/100 | 4mm | 3φ |
| Embodiment 9 | 5h | a | 100/100 | 6mm | 5φ |
| Embodiment 10 | 4h | a | 100/100 | 6mm | 5φ |
| Embodiment 11 | 4h | a | 100/100 | 5mm | 5φ |
| Embodiment 12 | 3h | a | 100/100 | 7mm | 6φ |
| Embodiment 13 | 4h | a | 100/100 | 5mm | 4φ |
| Embodiment 14 | 4h | a | 100/100 | 5mm | 4φ |
| Comparative example 1 | hb | a | 97/100 | 15mm | 15φ |
| Comparative example 2 | f | a | 98/100 | 12mm | 12φ |
| Comparative example 3 | h | a | 97/100 | 10mm | 9φ |
| Comparative example 4 | f | a | 98/100 | 12mm | 12φ |
As understood by above-mentioned table 2, it is able to confirm that and the light being formed with compositionss is formed by hard conating according to the present invention
Film is all pencil hardness and flexibility is excellent.
And for not using the comparative example of dendrimer compound according to the present invention, be able to confirm that and cannot ensure
Both hardness and flexibility, are unsuitable for form substrate of flexible display etc..
Claims (10)
1. hard conating formation compositionss, the dendrimer compound (a) that it comprises to be represented by following chemical formula 1, light gather
Conjunction property compound (b), Photoepolymerizationinitiater initiater (c) and solvent (d),
[chemical formula 1]
(r1)4-nc(ch2or2)n
In formula, n is 2～4 integer,
r1For the alkyl of carbon number 2～5,
r2For
M is 2 or 3,
r3It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular3Acrylate-based for (methyl).
2. hard conating formation compositionss according to claim 1, wherein, in described chemical formula 1, r3For hydrogen atom or
At least one r3For
X is 2 or 3,
r4It is hydrogen atom or (methyl) is acrylate-based, at least one r intramolecular4Acrylate-based for (methyl).
3. hard conating formation compositionss according to claim 1, wherein, with respect to polymerizable component ((a) and (b)
Mixed weight) total 100 weight portions, the dendritic macromole being represented by described chemical formula 1 containing 10～50 weight portions
Compound (a).
4. hard conating formation compositionss according to claim 1, wherein, described photopolymerizable compound (b) comprises to select
From carbamate system (methyl) acrylate and comprise at least one of (methyl) acrylate of oxygen ethylidene.
5. hard conating formation compositionss according to claim 4, wherein, described carbamate system (methyl) acrylic acid
Ester is the product being replaced with cyclohexyl.
6. hard conating formation compositionss according to claim 1, wherein, described Photoepolymerizationinitiater initiater (c) is selected from benzene
At least one of ethyl ketone system light trigger and amino ketones system light trigger.
7. hard conating formation compositionss according to claim 1, wherein, also comprise inorganic nano-particle.
8. blooming, it possesses by the hard conating according to any one of claim 1～7 at least one side of base material film
The coating that formation is formed with compositionss.
9. blooming according to claim 8, wherein, described blooming is window film.
10. image display device, it possesses blooming according to claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150097222A KR101883721B1 (en) | 2015-07-08 | 2015-07-08 | Compositon for hard coating, optical film and display device using the same |
| KR10-2015-0097222 | 2015-07-08 |
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| CN106336803A true CN106336803A (en) | 2017-01-18 |
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| Country | Link |
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| JP (1) | JP6850081B2 (en) |
| KR (1) | KR101883721B1 (en) |
| CN (1) | CN106336803A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592629A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| CN112592507A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| CN112592506A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
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| KR102008320B1 (en) * | 2017-02-06 | 2019-08-07 | 동우 화인켐 주식회사 | Hard coating composition and hard coating film formed therefrom |
| KR102139525B1 (en) * | 2017-05-19 | 2020-07-30 | 동우 화인켐 주식회사 | Hard coating film and image display device using the same |
| KR102313741B1 (en) * | 2017-09-01 | 2021-10-18 | 동우 화인켐 주식회사 | Adhesive Film |
| KR102019961B1 (en) | 2018-06-08 | 2019-09-11 | 동우 화인켐 주식회사 | Hard coating film and image display device using the same |
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| JP2005076005A (en) * | 2003-09-03 | 2005-03-24 | Nippon Kayaku Co Ltd | Photosensitive resin composition for hard coat |
| JP2006010829A (en) * | 2004-06-23 | 2006-01-12 | Fuji Photo Film Co Ltd | Anti-reflection coating, anti-reflection film, polarizing plate, and image display device using same |
| JP5033454B2 (en) * | 2006-03-29 | 2012-09-26 | 富士フイルム株式会社 | Optical film, polarizing plate, image display device, and optical film manufacturing method |
| US7960018B2 (en) * | 2006-03-29 | 2011-06-14 | Fujifilm Corporation | Optical film, polarizing plate, image display, and manufacturing method of optical film |
| KR20080078407A (en) * | 2007-02-23 | 2008-08-27 | 동우 화인켐 주식회사 | Hard coating solution, and hard coating film and image display apparatus using the same |
| JP5201369B2 (en) * | 2007-09-26 | 2013-06-05 | デクセリアルズ株式会社 | Hard coat film |
| JP2009286924A (en) * | 2008-05-30 | 2009-12-10 | Jsr Corp | Curable composition |
| KR101862875B1 (en) * | 2011-12-23 | 2018-05-31 | 엘지이노텍 주식회사 | Light curable resin composition |
| KR101688173B1 (en) | 2011-12-26 | 2016-12-21 | 코오롱인더스트리 주식회사 | Plastic substrate |
| JP2013167837A (en) * | 2012-02-17 | 2013-08-29 | Nippon Kayaku Co Ltd | Energy beam curable resin composition for hard coat film, and hard coat film (2) |
| JP2014197119A (en) * | 2013-03-29 | 2014-10-16 | Ｊｘ日鉱日石エネルギー株式会社 | Optical film, polarizing plate, image display device, and manufacturing method for optical film |
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| JP5846251B2 (en) * | 2014-05-26 | 2016-01-20 | 大日本印刷株式会社 | Optical sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592629A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| CN112592507A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| CN112592506A (en) * | 2019-10-01 | 2021-04-02 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| CN112592507B (en) * | 2019-10-01 | 2023-01-20 | 东友精细化工有限公司 | Hard coat film, and window and image display device comprising same |
| US11613658B2 (en) | 2019-10-01 | 2023-03-28 | Dongwoo Fine-Chem Co., Ltd. | Hard coating film and window and image display device using same |
| US11760898B2 (en) | 2019-10-01 | 2023-09-19 | Dongwoo Fine-Chem Co., Ltd. | Hard coating film and window and image display device using same |
| CN112592506B (en) * | 2019-10-01 | 2023-09-29 | 东友精细化工有限公司 | Hard coating film, window comprising same, and image display device |
Also Published As
| Publication number | Publication date |
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| TW201708433A (en) | 2017-03-01 |
| JP6850081B2 (en) | 2021-03-31 |
| KR20170006515A (en) | 2017-01-18 |
| JP2017021336A (en) | 2017-01-26 |
| TWI696671B (en) | 2020-06-21 |
| KR101883721B1 (en) | 2018-08-29 |
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