CN109791225A

CN109791225A - Antidazzle hard coating laminated body

Info

Publication number: CN109791225A
Application number: CN201780060909.8A
Authority: CN
Inventors: 松山元信
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2016-10-12
Filing date: 2017-10-11
Publication date: 2019-05-21
Anticipated expiration: 2037-10-11
Also published as: JP6799283B2; CN109791225B; TW201827535A; KR102507695B1; JPWO2018070426A1; WO2018070426A1; TWI735678B; KR20190060977A

Abstract

Anti-glare is excellent the subject of the invention is to provide having, and shows high marresistance, at the same time to the laminated body of the hard conating of the excellent adhesion of substrate.Solution is Antidazzle hard coating laminated body and its manufacturing method, above-mentioned Antidazzle hard coating laminated body is by substrate, square prime coat on the substrate, the Antidazzle hard coating laminated body constituted with the hard conating above the prime coat, above-mentioned prime coat is formed by the solidfied material of the prime coat formation composition comprising the siloxane oligomer specifically with free-radical polymerised double bond, above-mentioned hard conating is formed by the solidfied material of following solidification compounds, the solidification compound includes (a) polyfunctional monomer, (b) perfluoropolyether, it is combined with active energy beam polymerizable group via poly- (oxyalkylene) group in two ends of the strand comprising poly- (oxygen perfluorinated alkylidene) group, or active energy beam polymerizable group successively is combined with via poly- (oxyalkylene) group and 1 urethane bond base, (c ) organic fine particles and (d) polymerization initiator.

Description

Antidazzle hard coating laminated body

Technical field

The present invention relates to the Antidazzle hard coating laminated body for having the excellent hard conating of anti-glare (anti-glare function) and Its manufacturing method.

Background technique

Touch panel is equipped with to the flat-panel monitor of personal computer, portable phone, portable game devices, ATM etc. Product is commercialized mostly very much.In particular, with smart phone, the listing of tablet PC, the electrostatic with multi-touch function Capacity formula touch panel increases it without a break and carries number.

The reduction for mirroring caused visibility by exterior light to its picture in order to prevent, having used, which makes to have surface, forms The method that the Antidazzle hard coating tunic of the hard conating of indent and convex several μm of degree is fitted in these touch panel display surfaces.Make To form concave-convex method on surface, generally using the method for the particle for making hard conating contain the partial size with several μm of degree.

In addition, being operated for capacitive touch panel by the finger contact of employment.Therefore, it generates following Problem: it is operated all adhere to fingerprint, the visibility of the significant image for damaging display, or damage on the surface of touch panel every time The appearance of evil display.Fingerprint includes the oil from the moisture of sweat and from sebum, in order to make them all be not easy to adhere to, Strong expectation assigns waterproofness and grease proofness to the hard conating of display surface.

However, for capacitive touch panel, since people is contacted with finger daily, even if the soil resistance at initial stage The case where reaching high level, being damaged in use to which their function reduces is also more.Especially for Antidazzle hard coating Layer is prone to hook, is easy to damage due to having bumps on its surface.Therefore, the soil resistance in use process is resistance to Long property is project.

It discloses: as the hard conating with anti-glare and marresistance, being assigned as to hard coating surface so far The ingredient of soil resistance and marresistance has used intramolecular to have poly- (oxygen perfluorinated alkylidene) unit structure and (methyl) acryloyl The surface modifier of base is further used as assigning hard conating the ingredient of anti-glare, has used Methyl Methacrylate-Styrene The technology (patent document 1) of copolymer (MS) resin particle.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2013-257359 bulletin

Summary of the invention

Problems to be solved by the invention

In the method specifically recorded in patent document 1, there are following projects: intramolecular has poly- (oxygen perfluorinated alkylidene) base Unity structure is low with the fluorine content of surface modifier of (methyl) acryloyl group, cannot get sufficient soil resistance and marresistance.This Outside, there are following projects: the additive amount of MS resin particle is reduced if marresistance to be obtained, it cannot be adequately anti-dazzle Property, in the case where the degree can get sufficient anti-glare is added to MS resin particle, marresistance is significantly reduced.This Outside, the bad dispersibility of the resin particle in hard conating, the appearance for becoming agglutinator and damaging film is also project.

In addition, it is poor with the adaptation of glass baseplate to have used the hard conating of acrylic resin to be especially, it is easy from substrate Removing is also project.

In this way, it is desirable that anti-glare is excellent, and shows high marresistance, while the hard painting to the excellent adhesion of substrate Layer.

The method used for solving the problem

Further investigation has been repeated in the inventors of the present invention in order to achieve the above object, as a result, it has been found that, in order to improve and base Prime coat, the especially forming material of the prime coat are arranged between substrate and hard conating and uses with freely for the adaptation of material The siloxane oligomer of base polymeric double bond.Also, it was found that by using using comprising poly- (oxygen perfluorinated alkylidene) group knot Two ends of the strand of structure combine active energy beam polymerizable group via poly- (oxyalkylene) group or via poly- (oxyalkylene) group and 1 urethane bond base and combine active energy beam polymerizable group compound as fluorine system Surface modifier, further in the solidification compound for being wherein added to organic fine particles as hard conating forming material, to make At being provided with the hard conating with excellent anti-glare and high marresistance and excellent adhesion on above-mentioned prime coat Laminated body completes the present invention.

That is, as the 1st viewpoint, being related to a kind of Antidazzle hard coating laminated body, by substrate, on the substrate in the present invention The prime coat of side and the hard conating above the prime coat are constituted,

Above-mentioned prime coat is formed by the solidfied material of prime coat formation composition, above-mentioned prime coat formation composition packet Contain:

Ingredient (A) have free-radical polymerised double bond siloxane oligomer, the siloxane oligomer be by make to Include the alkoxy silane hydrolytic condensation of alkoxy silane B shown in alkoxy silane A shown in formula [1] and formula [2] less and obtains ,

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

(in formula, R¹Indicate the 1 valence organic group with free-radical polymerised double bond, R³Indicate the alkane of carbon atom number 1~10 Base (the ammonia that the alkyl can be substituted by phenyl by fluorine atom, at least by the alkyl-substituted amino of carbon atom number 1~6, at least Base or Carbamido substituted.) or phenyl, R²And R⁴Each independently represent methyl or ethyl, a indicate 1 or 2, b indicate 0~2 it is whole Number.)

Above-mentioned hard conating is formed by the solidfied material of solidification compound, and above-mentioned solidification compound includes:

(a) 100 mass parts of active energy ray-curable polyfunctional monomer,

(b) 0.1~10 mass parts of perfluoropolyether, the perfluoropolyether is in the molecule comprising poly- (oxygen perfluorinated alkylidene) group Two ends of chain are combined with active energy beam polymerizable group via poly- (oxyalkylene) group, or successively via poly- (oxyalkylene) group and 1 urethane bond group and be combined with active energy beam polymerizable group,

(c) there are 8~30 mass parts of organic fine particles of 1~10 μm of average grain diameter, and

(d) 1~20 mass parts of polymerization initiator generated free radicals using active energy beam.

As the 2nd viewpoint, it is related to Antidazzle hard coating laminated body described in the 1st viewpoint, the siloxane oligomer of mentioned component (A) Object is to have by alkoxy silane A shown in formula [1] with what alkoxy silane B hydrolytic condensation shown in formula [2] obtained The siloxane oligomer of free-radical polymerised double bond.

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

(in formula, R¹Indicate the 1 valence organic group with free-radical polymerised double bond, R³What expression can be replaced by fluorine atoms The alkyl or phenyl of carbon atom number 1~6, R²And R⁴Methyl or ethyl are each independently represented, a indicates 1 or 2, and b indicates 0~2 Integer.)

As the 3rd viewpoint, it is related to Antidazzle hard coating laminated body described in the 1st viewpoint or the 2nd viewpoint, in above-mentioned formula [1] R¹For the 1 valence organic group with vinyl or (methyl) acryloyl group.

As the 4th viewpoint, it is related to Antidazzle hard coating laminated body described in the 3rd viewpoint, above-mentioned alkoxy silane A is following formula [3] compound represented.

(in formula, R²Indicate meaning identical with the definition in above-mentioned formula [1], R⁵Indicate hydrogen atom or methyl, L¹Indicate carbon The alkylidene of atomicity 1~10.)

As the 5th viewpoint, be related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 4th viewpoint, it is above-mentioned at The siloxane oligomer with free-radical polymerised double bond for dividing (A) is to be originated from above-mentioned alkoxyl silicone comprising 10~99mol% The siloxane oligomer of the unit of alkane A.

As the 6th viewpoint, be related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 5th viewpoint, it is above-mentioned at Poly- (oxygen perfluorinated alkylidene) group for dividing the perfluoropolyether of (b) is with-[OCF₂]-and-[OCF₂CF₂]-as repetitive unit Group.

As the 7th viewpoint, be related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 6th viewpoint, it is above-mentioned at Poly- (oxyalkylene) group for dividing the perfluoropolyether of (b) is poly- (oxygen ethylidene) group.

As the 8th viewpoint, be related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 7th viewpoint, it is above-mentioned at The polyfunctional monomer for dividing (a) is selected from multifunctional (methyl) acrylate compounds and polyfunctional carbamate (methyl) propylene It is at least one kind of in ester compound.

As the 9th viewpoint, be related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 8th viewpoint, it is above-mentioned at The organic fine particles of point (c) are positive spherical particle.

As the 10th viewpoint, it is related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 9th viewpoint, it is above-mentioned The organic fine particles of ingredient (c) are polymethyl methacrylate particle.

As the 11st viewpoint, it is related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 10th viewpoint, it is above-mentioned The polymerization initiator of ingredient (d) is alkyl phenones Type of Collective initiator.

As the 12nd viewpoint, it is related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 11st viewpoint, it is above-mentioned 1~10/3 times of the average grain diameter of the organic fine particles with a thickness of mentioned component (c) of hard conating.

As the 13rd viewpoint, it is related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 12nd viewpoint, it is above-mentioned Hard conating has 1~20 μm of film thickness.

As the 14th viewpoint, it is related to Antidazzle hard coating laminated body described in the 13rd viewpoint, above-mentioned hard conating has 3~10 μm Film thickness.

As the 15th viewpoint, it is related to Antidazzle hard coating laminated body described in any one of the 1st viewpoint~the 14th viewpoint, it is above-mentioned Substrate is glass.

As the 16th viewpoint, it is related to a kind of manufacturing method of Antidazzle hard coating laminated body, the Antidazzle hard coating laminated body Have prime coat in at least one side of substrate, and have hard conating above the prime coat, the manufacturing method includes following Process:

The primer coating layer formation composition on substrate and the process for forming film；

The film of the prime coat formation composition is heated and makes the curing of coating, the process for forming prime coat；

The process for being coated with solidification compound on above-mentioned prime coat and forming film；And

Active energy beam is irradiated to the film of the solidification compound and makes the curing of coating, forms the work of hard conating Sequence,

Above-mentioned prime coat formation includes with composition:

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

Above-mentioned solidification compound includes:

(a) 100 mass parts of active energy ray-curable polyfunctional monomer,

(b) 0.1~10 mass parts of perfluoropolyether, the perfluoropolyether is in the molecule comprising poly- (oxygen perfluorinated alkylidene) group Two ends of chain are combined with active energy beam polymerizable group via poly- (oxyalkylene) base, or successively via poly- (oxygen Asia Alkyl) group and 1 urethane bond group and be combined with active energy beam polymerizable group,

Invention effect

In accordance with the invention it is possible to which providing, even there is 1~15 μm of thickness or so of film also to have excellent scratch resistance Property and high anti-glare and appearance also excellent hard conating laminated body, especially by substrate setting comprising having freely Above-mentioned hard conating is arranged, it may be said that is capable of providing in the prime coat of the siloxane oligomer of base polymeric double bond on the prime coat Laminated body with the adaptation with substrate also excellent hard conating.

Specific embodiment

Antidazzle hard coating laminated body of the invention by substrate, the substrate top prime coat and above the prime coat Hard conating constitute.

Moreover, above-mentioned prime coat is by comprising with free-radical polymerised double in Antidazzle hard coating laminated body of the invention The solidfied material of the prime coat formation composition of the siloxane oligomer of key is formed, and above-mentioned hard conating is by including active energy beam The solidfied material of the solidification compound of curability polyfunctional monomer etc. is formed.

Hereinafter, being described in detail to each layer for constituting Antidazzle hard coating laminated body of the invention.

" substrate "

Substrate in Antidazzle hard coating laminated body of the invention is not particularly limited, it can be cited for example that, plastics (poly- carbonic acid Ester, polymethacrylates, polystyrene, polyester, PET (polyethylene terephthalate), polyolefin, epoxy resin, three Cymel, triacetyl cellulose, ABS (acrylonitrile-butadiene-styrene copolymer), AS are (acrylonitrile-styrene copolymerized Object), norbornene resin etc.), metal, timber, paper, glass, silica, slate etc..The shape of these substrates can be Plate, membranaceous or 3 dimension formed bodys.

Wherein, in the present invention, as substrate, can be suitble to using glass.

The thickness of above-mentioned substrate is not particularly limited, can be such as 10~1,000 μm etc..

" prime coat "

Prime coat in Antidazzle hard coating laminated body of the invention is formed by the prime coat comprising following compositions (A) with combination The solidfied material of object is formed:

Ingredient (A) have free-radical polymerised double bond siloxane oligomer, the siloxane oligomer be by make to Include the alkoxy silane hydrolytic condensation of alkoxy silane B shown in alkoxy silane A shown in formula [1] and formula [2] less and obtains ?.

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

Hereinafter, being illustrated to mentioned component (A) and prime coat formation with each ingredient that composition may include.

[siloxane oligomer that (A) has free-radical polymerised double bond]

Above-mentioned (A) has the siloxane oligomer of free-radical polymerised double bond (hereinafter, also referred to as (A) siloxane oligomer Object) it is to include at least alkoxy silane B shown in alkoxy silane A shown in following formula [1] and following formula [2] as required Alkoxy silane unit, the siloxane oligomer obtained and making their hydrolytic condensations.

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

In above-mentioned formula [1], R¹Indicate the 1 valence organic group with free-radical polymerised double bond, R²Indicate methyl or ethyl, a Indicate 1 or 2.

In addition, in formula [2], R³(alkyl can be by fluorine atom, at least by carbon original for the alkyl of expression carbon atom number 1~10 The alkyl-substituted amino of subnumber 1~6, the amino or Carbamido substituted being at least substituted by phenyl.) or phenyl, preferably R³Expression can With the alkyl or phenyl for the carbon atom number 1~6 being replaced by fluorine atoms, R⁴Indicate that methyl or ethyl, b indicate 0~2 integer.

As the R in above-mentioned formula [1]¹The 1 valence organic group with free-radical polymerised double bond, it is however preferred to have ethylene 1 valence organic group of base or (methyl) acryloyl group.In addition, (methyl) acryloyl group so-called in the present invention, refers to acryloyl group Both with methacrylic acid group.

In addition, as the R in above-mentioned formula [2]³The carbon atom number 1~10 of expression alkyl (alkyl can by fluorine atom, The amino or Carbamido substituted being at least substituted by phenyl by the alkyl-substituted amino of carbon atom number 1~6, at least.), first can be enumerated Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, just oneself Base, cyclohexyl, n-octyl, positive decyl etc..

In addition, as the R in above-mentioned formula [2]³Indicate at least by the alkyl-substituted amino of carbon atom number 1~6, can lift Methylamino, dimethylamino, ethylamino, diethylamino, n-propyl amino, isopropylamino, n-butylamino, uncle out Butylamino, n-pentyl amino, n-hexyl amino, Cyclohexylamino, N- methyl-N-phenyl etc..

In turn, as the R in above-mentioned formula [2]³The amino being at least substituted by phenyl indicated, can enumerate phenyl amino, two Phenyl amino etc..

In alkoxy silane A shown in above-mentioned formula [1], preferably following formula [3] compound represented.

In formula, R²Indicate meaning identical with the definition in above-mentioned formula [1], R⁵Indicate hydrogen atom or methyl, L¹Indicate that carbon is former The alkylidene of subnumber 1~10, the preferably alkylidene of carbon atom number 1~8, the further preferably alkylene of carbon atom number 1~6 Base.

As above-mentioned L¹The alkylidene of the carbon atom number 1~10 of expression, can enumerate methylene, ethylidene, 1,3- propylidene, Methyl ethylidene, 1,4- butylidene, 1- methyl-1,3- propylidene, 1,5- pentylidene, 2,2- dimethyl -1,3- propylidene, 1,6- Hexylidene, 1,8- octamethylene, 1,10- decylene etc..Wherein, preferably 1,3- propylidene.

As the concrete example of such alkoxy silane A, trimethoxy (vinyl) silane, triethoxy (second can be enumerated Alkenyl) silane, 3- (methyl) acryloyloxypropyltrimethoxysilane, triethoxy (3- (methyl) acryloxypropyl) Silane, 8- (methyl) acryloxy octyl trimethoxy silane, triethoxy (8- (methyl) acryloxy octyl) silane, 3- (methyl) acryloxypropyl (dimethoxy) (methyl) silane, diethoxy (3- (methyl) acryloxypropyl) (methyl) silane, trimethoxy (4- ethenylphenyl) silane, triethoxy (4- ethenylphenyl) silane etc..

Wherein, preferably 3- (methyl) acryloyloxypropyltrimethoxysilane, triethoxy (3- (methyl) acryloyl Oxygroup propyl) silane.

In addition, the concrete example as alkoxy silane B shown in above-mentioned formula [2], can enumerate tetramethoxy-silicane, four ethoxies Base silane, trimethoxy (methyl) silane, triethoxy (methyl) silane, ethyl trimethoxy silane, triethoxy (ethyl) Silane, trimethoxy (propyl) silane, triethoxy (propyl) silane, trimethoxy (3,3,3- trifluoro propyl) silane, three second Oxygroup (3,3,3- trifluoro propyl) silane, butyl trimethoxy silane, butyl triethoxysilane, trimethoxy (amyl) silicon Alkane, triethoxy (amyl) silane, hexyl trimethoxysilane, triethoxy (hexyl) silane, trimethoxy (phenyl) silane, Triethoxy (phenyl) silane, dimethoxydimethylsilane, di ethoxy di methyl-monosilane, diethyldimethoxysilane, Diethoxy diethylsilane, dimethoxy dipropyl base silane, diethoxy dipropyl base silane, dibutyldimethoxysilane, Dibutyldiethoxysilane, dimethoxy diamyl base silane, diethoxy diamyl base silane, dihexyl dimethoxysilane, Diethoxy dihexyl silane, dimethoxydiphenyl silane, diethoxy diphenyl silane, trimethoxy ((phenyl amino) Methyl) silane, trimethoxy (3- (phenyl amino) propyl) silane, triethoxy (3- (phenyl amino) propyl) silane, diformazan Oxygroup (methyl) (3- (phenyl amino) propyl) silane etc..

Wherein, preferably tetramethoxy-silicane, tetraethoxysilane, trimethoxy (3- (phenyl amino) propyl) silane, Triethoxy (3- (phenyl amino) propyl) silane.

(A) siloxane oligomer is preferably to be originated from above-mentioned alkane comprising 10~99mol% among whole alkoxy silane units The siloxane oligomer of the unit of oxysilane A.

Especially (A) siloxane oligomer is preferably in entire infrastructure unit comprising at least following formula of 10~99mol% [4] siloxane oligomer of structural unit shown in.

In formula, R²、R⁵And L¹Indicate meaning identical with the definition in above-mentioned formula [3].

The method for obtaining above-mentioned (A) siloxane oligomer is not particularly limited.

For example, be condensed the alkoxy silane comprising above-mentioned alkoxy silane A and alkoxy silane B in organic solvent and It obtains.As by the method for alkoxy silane polycondensation, can enumerate for example, by alkoxy silane in alcohol or solvents such as glycols water Solution, the method for condensation.At this point, hydrolysis, condensation reaction can be any one of partial hydrolysis and complete hydrolysis.In complete hydrolysis In the case where, theoretically, if 0.5 times mole of water of the whole alkoxies being added in alkoxy silane, but it is preferably logical It is commonly incorporated into the water of the excess quantity compared with 0.5 times mole.In the present invention, the amount of water used in above-mentioned reaction can according to need Appropriate selection, but 0.5~2.5 times mole of whole alkoxies preferably generally in alkoxy silane.

In addition, in general, for promote hydrolysis, condensation reaction purpose, using formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oneself Acid, 2 ethyl hexanoic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, oxalic acid, Malonic acid, methylmalonic acid, succinic acid, tartaric acid, maleic acid, fumaric acid, adipic acid, decanedioic acid, citric acid, chloroacetic acid, Dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, p-aminobenzoic acid, salicylic acid, gallic acid, phthalic acid, benzene The organic acids such as pregnancy acid, benzene sulfonic acid, p-methyl benzenesulfonic acid；The inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and its metal Salt；The catalyst such as the alkali such as ammonia, methylamine, ethamine, ethanol amine, triethylamine.In addition, the solution usually by dissolving alkoxy silane It is heated, further promotes hydrolysis, condensation reaction.At this point, heating temperature and heating time can according to need appropriate selection. It can enumerate for example, heated at 50 DEG C, stir 24 hours methods, heat under reflux, method for stirring 1 hour etc..

In addition, can enumerate as another process for example, the mixture of alkoxy silane, solvent and oxalic acid is heated And the method for polycondensation.Specifically, being that oxalic acid is added in alcohol in advance after the alcoholic solution of oxalic acid is made, heated by the solution In the state of, by the method for alkoxy silane mixing.At this point, the amount of used oxalic acid is had preferably with respect to alkoxy silane 1 mole of the whole alkoxies having is 0.05~5 mole of %.Heating in this method can be at 50~180 DEG C of fluid temperature It carries out.In order not to evaporation, the volatilization etc. that liquid occurs, dozens of minutes~ten a few houres method is preferably heated under reflux.

Prime coat used in the present invention is formed with (A) siloxane oligomer used in composition by gel infiltration color The obtained weight average molecular weight (Mw) with polystyrene conversion measurement is composed as 100~10,000, preferably 500~5,000.

In the present invention, presumption uses above-mentioned siloxane oligomer by prime coat forming material, thus forming priming paint When layer, which mutually carries out partial hydrolysis condensation reaction, the alcohol volatilization generated at this time, so that being considered as prime coat formation has The structure in gap, as a result, the adaptation for facilitating whole prime coat and substrate and hard conating improves.

[solvent]

Prime coat formation composition used in the present invention can further include solvent, and the form of varnish is made.

As used solvent at this time, as long as by above-mentioned (A) ingredient and as needed by aftermentioned other ingredients The solvent of dissolution or dispersion, can be used for example, toluene, dimethylbenzene etc. are aromatic hydrocarbon；Ethyl acetate, butyl acetate, Isobutyl acetate, gamma-butyrolacton, methyl pyruvate, ethyl pyruvate, hydroxyl ethyl acetate, ethyl lactate, butyl lactate, 2- Hydroxy-2-methyl ethyl propionate, 2- hydroxy-3-methyl methyl butyrate, ethoxy ethyl acetate, 3- methoxy methyl propionate, 3- Methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, methylcellosolve acetate, ethyl cellosolve Esters or the ester ethers such as acetic acid esters, propylene glycol monomethyl ether (PGMEA), propylene glycol monopropyl ether acetic acid esters；Ethylene glycol Monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, carbiphene, propylene glycol monomethyl ether (PGME) etc. Ethers；The ketones such as methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, cyclohexanone；Methanol, ethyl alcohol, normal propyl alcohol, The alcohols such as 2- propyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, propylene glycol；N,N-dimethylformamide (DMF), N, N- bis- Amides such as methylacetamide, n-methyl-2-pyrrolidone (NMP) etc..These solvents can be used alone or with of more than two kinds It is applied in combination or to be used with the mixed solvent of water.

It is such as 0.01~70 mass % that prime coat used in the present invention, which is formed with the solid component concentration in composition, 0.1~50 mass % or 1~30 mass %.Here so-called solid component is the whole components from prime coat formation composition Ingredient after middle removing solvent composition.

[other additives]

In turn, prime coat used in the present invention, which is formed, uses in composition, as long as not damaging effect of the invention, so that it may Suitably cooperate the additive generally added as needed, for example, photosensitizer, polymerization inhibitor, polymerization initiator, levelling agent, surface Activating agent, adaptation imparting agent, plasticizer, ultraviolet absorbing agent, antioxidant, storage stabilizing agent, antistatic agent, inorganic fill Agent, pigment, dyestuff etc. and active energy ray-curable polyfunctional monomer etc..

[active energy ray-curable polyfunctional monomer]

Prime coat used in the present invention, which is formed, to be used in composition, in order to improve the adaptation of itself and the hard conating of top, Active energy ray-curable polyfunctional monomer can be further included.

As active energy ray-curable polyfunctional monomer used in prime coat formation composition, after can enumerating Multifunctional (methyl) acrylate compounds are selected from illustrated by < (a) the active energy ray-curable polyfunctional monomer > stated With monomer, multi-functional epoxy (methyl) acrylate chemical combination in polyfunctional carbamate (methyl) acrylate compounds Object, multifunctional polyester (methyl) acrylate compounds, unsaturated polyester (UP) etc..

In addition, in the present invention, so-called (methyl) acrylate compounds refer to acrylate compounds and metering system Both ester compounds.Such as (methyl) acrylic acid refers to acrylic acid and methacrylic acid.

In the prime coat formation composition being used in the present invention, the multifunctional list of active energy ray-curable is being used In the case where body, used relative to above-mentioned 100 mass parts of (A) siloxane oligomer with the amount of 1~300 mass parts, preferably with 1 The amount of~200 mass parts uses, and is particularly preferably used with the amount of 10~100 mass parts.

[polymerization initiator generated free radicals using active energy beam]

It include that above-mentioned < active energy ray-curable is multifunctional in prime coat formation used in the present invention composition In the case where monomer >, the polymerization that aftermentioned < (d) is generated free radicals using active energy beam can be further included and drawn Send out various polymerization initiators illustrated by agent >.

In prime coat formation composition used in the present invention, comprising above-mentioned polymerization initiator, phase For 100 mass parts of above-mentioned (A) siloxane oligomer, used with the amount of 0.1~25 mass parts, preferably with 0.1~20 mass The amount of part uses, and is particularly preferably used with the amount of 1~20 mass parts.

" hard conating "

< solidification compound >

Hard conating in Antidazzle hard coating laminated body of the invention is by the solidification compound comprising following (a)~(d) Solidfied material (i.e. cured film) formation.

(a) 100 mass parts of active energy ray-curable polyfunctional monomer,

Hereinafter, each ingredient to above-mentioned (a)~(d) is illustrated.

[(a) active energy ray-curable polyfunctional monomer]

So-called active energy ray-curable polyfunctional monomer, refer to by irradiation ultraviolet light isoreactivity energy-ray from And polymerization reaction carries out, and carries out cured monomer.

As the multifunctional list of (a) active energy ray-curable preferred in the solidification compound being used in the present invention Body is in multifunctional (methyl) acrylate compounds and polyfunctional carbamate (methyl) acrylate compounds Monomer.

As above-mentioned multifunctional (methyl) acrylate compounds, it can be cited for example that, trimethylolpropane tris (methyl) Acrylate, double trimethylolpropane four (methyl) acrylate, pentaerythrite two (methyl) acrylate, pentaerythrite three (methyl) acrylate, (methyl) acrylate of pentaerythrite two monostearate, pentaerythrite four (methyl) acrylate, two Pentaerythrite five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerol three (methyl) acrylate, the third oxygen Nitro three (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, three hydroxyl first of propoxylation Base propane three (methyl) acrylate, ethoxylation pentaerythrite four (methyl) acrylate, ethoxylated dipentaerythritol six (methyl) acrylate, ethoxylated glycerol three (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate, second Oxygroup Bisphenol F two (methyl) acrylate, 1,3- propylene glycol two (methyl) acrylate, 1,3 butylene glycol two (methyl) propylene Acid esters, 1,4- butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 2- methyl-1,8- ethohexadiol Two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylate, new penta Glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) Acrylate, bis- (2- hydroxyethyls) isocyanuric acid ester two (methyl) acrylate, three (2- hydroxyethyl) isocyanuric acid esters two (methyl) acrylate, three (2- hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, tricyclic [5.2.1.0^2,6] decane two Methanol two (methyl) acrylate, dioxane glycol two (methyl) acrylate, 2- hydroxyl -1- acryloxy -3- Bis- [4- (2- (methyl) acryloyls of methacryloxy propane, two (methyl) acryloxy propane of 2- hydroxyl -1,3-, 9,9- Oxygroup ethyoxyl) phenyl] fluorenes, bis- [4- (methyl) acryloyl group thio-phenyl] thioethers, bis- [thio second of 2- (methyl) acryloyl group Base] thioether, 1,3- adamantane glycol two (methyl) acrylate, 1,3- adamantane dimethanol two (methyl) acrylate, poly- second Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) phosphoric acid Modified three (2- hydroxyethyl) isocyanuric acid ester three (methyl) acrylate of ester, 6-caprolactone etc..

Wherein, as preferred compound, pentaerythrite three (methyl) acrylate, four (first of pentaerythrite can be enumerated Base) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..

Above-mentioned polyfunctional carbamate (methyl) acrylate compounds are that 1 intramolecular has multiple acryloyl groups or first Base acryloyl group and the compound with more than one urethane bond (- NHCOO-).

Such as it as above-mentioned polyfunctional carbamate (methyl) acrylate compounds, can enumerate through multifunctional isocyanide Acid esters and (methyl) the reacting for acrylate with hydroxyl and obtain compound, by polyfunctional isocyanate with there is hydroxyl The compound etc. that (methyl) acrylate of base is obtained with reacting for polyalcohol, but the multifunctional ammonia being able to use in the present invention Carbamate (methyl) acrylate compounds are not only limited to such illustration.

In addition, can enumerate as above-mentioned polyfunctional isocyanate for example, toluene di-isocyanate(TDI), two isocyanide of isophorone Acid esters, benzene dimethylene diisocyanate, hexamethylene diisocyanate etc..

In addition, can enumerate as above-mentioned (methyl) acrylate with hydroxyl for example, (methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 2- hydroxy propyl ester, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid Ester, tripentaerythritol seven (methyl) acrylate etc..

In turn, it as above-mentioned polyalcohol, can enumerate for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6- The glycols such as hexylene glycol, diethylene glycol (DEG), dipropylene glycol；As the aliphatic such as these glycols and succinic acid, maleic acid, adipic acid two The polyester polyol of carboxylic acids or the reaction product of dicarboxylic acids anhydride；Polyether polyol；Polycarbonate glycol etc..

In the present invention, as above-mentioned (a) active energy ray-curable polyfunctional monomer, it can be used alone by above-mentioned more Group composed by function (methyl) acrylate compounds and above-mentioned polyfunctional carbamate (methyl) acrylate compounds One of, or it is applied in combination two kinds or more.From the viewpoint of the marresistance of resulting solidfied material, it is preferably used in combination multifunctional (methyl) acrylate compounds and polyfunctional carbamate (methyl) acrylate compounds.In addition, as above-mentioned more officials Can (methyl) acrylate compounds, be preferably used in combination 5 functions or more multifunctional (methyl) acrylate compounds and 4 functions with Under multifunctional (methyl) acrylate compounds.

In addition, above-mentioned multifunctional (methyl) acrylate compounds and above-mentioned polyfunctional carbamate are applied in combination In the case where (methyl) acrylate compounds, relative to 100 mass parts of multifunctional (methyl) acrylate compounds, preferably make With 20~100 mass parts of polyfunctional carbamate (methyl) acrylate compounds, 30~70 mass parts are more preferably used.

Further, in above-mentioned multifunctional (methyl) acrylate compounds, the more of above-mentioned 5 function or more are being applied in combination In the case where function (methyl) acrylate compounds and above-mentioned 4 function multifunctional (methyl) acrylate compounds below, Relative to 100 mass parts of multifunctional (methyl) acrylate compounds more than 5 functions, it is preferable to use 4 functions more officials below Energy 10~100 mass parts of (methyl) acrylate compounds, more preferably use 20~60 mass parts.

Moreover it is preferred that: relative to 100 mass parts of multifunctional (methyl) acrylate compounds, with multifunctional amino 20~100 mass parts of formic acid esters (methyl) acrylate compounds use, and relative to multifunctional (methyl) more than 5 functions 100 mass parts of acrylate compounds, with 4 functions, 10~100 mass parts of multifunctional (methyl) acrylate compounds below It uses,

Relative to 100 mass parts of multifunctional (methyl) acrylate compounds, with polyfunctional carbamate (methyl) third 20~100 mass parts of enoic acid ester compounds use, and relative to multifunctional (methyl) acrylate compounds more than 5 functions 100 mass parts are used with 4 functions, 20~60 mass parts of multifunctional (methyl) acrylate compounds below,

Relative to 100 mass parts of multifunctional (methyl) acrylate compounds, with polyfunctional carbamate (methyl) third 30~70 mass parts of enoic acid ester compounds use, and relative to multifunctional (methyl) acrylate compounds more than 5 functions 100 mass parts are used with 4 functions, 10~100 mass parts of multifunctional (methyl) acrylate compounds below,

Relative to 100 mass parts of multifunctional (methyl) acrylate compounds, with polyfunctional carbamate (methyl) third 30~70 mass parts of enoic acid ester compounds use, and relative to multifunctional (methyl) acrylate compounds more than 5 functions 100 mass parts are used with 4 functions, 20~60 mass parts of multifunctional (methyl) acrylate compounds below.

[(b) perfluoropolyether, in two ends of the strand comprising poly- (oxygen perfluorinated alkylidene) group, via poly- (oxygen Asia Alkyl) group and be combined with active energy beam polymerizable group, or successively via poly- (oxyalkylene) group and 1 amino Formic acid ester linkage group and be combined with active energy beam polymerizable group]

In the present invention, as (b) ingredient, use following perfluoropolyether: it is comprising poly- (oxygen perfluorinated alkylidene) group Two ends of strand are combined with active energy beam polymerizable group via poly- (oxyalkylene) group, or successively via Poly- (oxyalkylene) group and 1 urethane bond base and combine active energy beam polymerizable group (hereinafter, also referred to as " (b) has the perfluoropolyether of polymerizable group in two ends ").(b) ingredient is played solidifies as used in the application present invention The effect of surface modifier in the hard conating of property composition.

The carbon atom number of alkylidene in above-mentioned poly- (oxygen perfluorinated alkylidene) group is not particularly limited, preferably carbon atom number It is 1~4.That is, above-mentioned poly- (oxygen perfluorinated alkylidene) group refers to that the divalent fluorocarbon radical with carbon atom number 1~4 replaces with oxygen atom The group for the structure being formed by connecting, oxygen perfluorinated alkylidene refer to that the divalent fluorocarbon radical with carbon atom number 1~4 is connect with oxygen atom Made of structure group.Specifically,-[OCF can be enumerated₂]-(oxygen perfluoromethylene) ,-[OCF₂CF₂]-(oxygen perfluor Asia second Base) ,-[OCF₂CF₂CF₂]-(oxygen perfluoropropane -1,3- diyl),-[OCF₂C(CF₃) F]-(oxygen perfluoropropane -1,2- diyl) etc. Group.

Above-mentioned oxygen perfluorinated alkylidene can be used alone, or can be applied in combination two kinds or more, in this case, more The combination of kind oxygen perfluorinated alkylidene can combine for block and randomly any one of combination.

Wherein, from the viewpoint of becoming good solidfied material (hard conating) from available marresistance, as poly- (oxygen perfluor Alkylidene) group, it is preferable to use have-[OCF₂]-(oxygen perfluoromethylene) and-[OCF₂CF₂Both]-(oxygen perfluor ethylidene) Group as repetitive unit.

Wherein, as above-mentioned poly- (oxygen perfluorinated alkylidene) group, preferably repetitive unit :-[OCF₂]-and-[OCF₂CF₂]- With terms of mole ratios to become [repetitive unit :-[OCF₂] -]: [repetitive unit :-[OCF₂CF₂] -]=2:1~1:2 ratio packet It more preferably include their group with the ratio for becoming about 1:1 containing their group.The combination of these repetitive units can be with Any one of combine for block and randomly combine.

The number of repeat unit of above-mentioned oxygen perfluorinated alkylidene, the range of the total preferably 5~30 as its number of repeat unit, More preferably 7~21 range.

In addition, above-mentioned poly- (oxygen perfluorinated alkylidene) group obtained by gel permeation chromatography, with polystyrene convert survey The weight average molecular weight (Mw) obtained is 1,000~5,000, preferably 1,500~2,000.

The carbon atom number of alkylidene in above-mentioned poly- (oxyalkylene) group is not particularly limited, and preferably carbon atom number is 1 ~4.It is formed by connecting that is, above-mentioned poly- (oxyalkylene) group refers to that the alkylidene with carbon atom number 1~4 replaces with oxygen atom The group of structure, oxyalkylene refer to the base for the structure that the divalent alkylidene with carbon atom number 1~4 is formed by connecting with oxygen atom Group.As above-mentioned alkylidene, ethylidene, 1- methyl ethylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene etc. can be enumerated.

Above-mentioned oxyalkylene can be used alone, or can be applied in combination two kinds or more, in this case, a variety of oxygen The combination of alkylidene can combine for block and randomly any one of combination.

Wherein, preferably poly- (oxygen ethylidene) group of above-mentioned poly- (oxyalkylene) group.

The number of repeat unit of oxyalkylene in above-mentioned poly- (oxyalkylene) group is, for example, 1~15 range, more preferably For such as 5~12 range, for example, 7~12 range.

As above-mentioned via poly- (oxyalkylene) group or successively via poly- (oxyalkylene) group and 1 carbamate Key base and the active energy beam polymerizable group combined, can enumerate (methyl) acryloyl group, carbamate (methyl) propylene Acyl group, vinyl etc..

Above-mentioned active energy beam polymerizable group is not limited to that there is 1 (methyl) acryl moieties isoreactivity energy to penetrate The group of line polymerism part, can be the group with 2 or more active energy beam polymerism parts, can enumerate for example, The structure of A1~A5 as shown below and the structure that the acryloyl group in these structures is replaced as to methylacryloyl.

There is the perfluoropolyether of polymerizable group in two ends as such (b), be easy in this way from industrial manufacture From the aspect of, compound shown below can be enumerated and the acryloyl group in these compounds is replaced as methacryl The compound of base is as preference.In addition, A indicates 1 among structure shown in above-mentioned formula [A1]~formula [A5] in structural formula A, PFPE indicates that above-mentioned poly- (oxygen perfluorinated alkylidene) group, n each independently represent the number of repeat unit of oxygen ethylidene, preferably It indicates 1~15 number, more preferably indicates 5~12 number, further preferably indicate 7~12 number.

Wherein, (b) used in the present invention has the perfluoropolyether of polymerizable group preferably comprising poly- in two ends Two ends of the strand of (oxygen perfluorinated alkylidene) group are successively via poly- (oxyalkylene) group and 1 urethane bond Base, that is, in two ends of the strand comprising poly- (oxygen perfluorinated alkylidene) group respectively in connection with poly- (oxyalkylene) group, at this Respectively in connection with 1 urethane bond base on each poly- (oxyalkylene) group at both ends, and then each carbamic acid at the both ends Perfluoropolyether of the ester bond respectively in connection with active energy beam polymerizable group.In turn, in above-mentioned perfluoropolyether, preferably active energy Measure the perfluoropolyether that ray polymerization group is the group at least two above active energy beam polymerism part.

In the present invention, it is expected that (b) having the perfluoropolyether of polymerizable group with living relative to above-mentioned (a) in two ends Property 100 mass parts of energy ray-curable polyfunctional monomer be that 0.1~10 mass parts, the ratio of preferably 0.2~5 mass parts make With.

Above-mentioned (b) in two ends there is the perfluoropolyether of polymerizable group for example to obtain by following methods: in poly- (oxygen Perfluorinated alkylidene) group two ends via poly- (oxyalkylene) group and with hydroxyl compound in, for the both ends Hydroxyl makes bis- ((methyl) acryloyloxymethyl) the ethyl isocyanic acids of 2- (methyl) acryloyloxyethyl isocyanate, 1,1- The method that there is ester etc. the isocyanate compound of polymerizable group to carry out urethane reaction, makes (methyl) acryloyl chloride Or the method that 1-chloro-4-methyl-benzene carries out the reaction of desalination acid, the method for making (methyl) acrylic acid carry out dehydration make itaconic acid The method etc. of acid anhydride progress esterification.

Wherein, the change with hydroxyl via poly- (oxyalkylene) group in two ends of poly- (oxygen perfluorinated alkylidene) group Close in object, be easy aspect from reacting, for the hydroxyl at the both ends, make 2- (methyl) acryloyloxyethyl isocyanate, There is bis- ((methyl) acryloyloxymethyl) ethyl isocyanates of 1,1- etc. the isocyanate compound of polymerizable group to carry out The method of urethane reaction, or (methyl) acryloyl chloride or 1-chloro-4-methyl-benzene for the hydroxyl, is made to carry out desalination acid The method of reaction is particularly preferred.

In addition, in solidification compound used in the present invention, in addition to (b) is including poly- (oxygen perfluorinated alkylidene) group Two ends of strand are via poly- (oxyalkylene) group or successively via poly- (oxyalkylene) group and 1 urethane bond Base and combine active energy beam polymerizable group perfluoropolyether other than, can also include following perfluoropolyether: comprising gather One end of the strand of (oxygen perfluorinated alkylidene) group is via poly- (oxyalkylene) group or successively via poly- (oxyalkylene) base It rolls into a ball with 1 urethane bond base and in conjunction with active energy beam polymerizable group, and in the other end via poly- (oxyalkylene) Group and with hydroxyl perfluoropolyether；At the both ends of the strand comprising poly- (oxygen perfluorinated alkylidene) group via poly- (oxygen Asia Alkyl) group and the perfluoropolyether compound of active energy beam polymerizable group [unbonded] with hydroxyl.

[organic fine particles of (c) with 1~10 μm of average grain diameter]

In the solidification compound being used in the present invention, organic fine particles with 1~10 μm of average grain diameter (hereinafter, Also referred to as " (c) organic fine particles ") make the surface concaveconvex shape of the hard conating formed by the solidification compound and assigns anti- Dizzy property.

In addition, refraction of the organic fine particles by its refractive index of control and the solidification compound as hard conating forming material The difference of rate, so that the effect of the haze value of control hard conating can also be undertaken.

The shape of above-mentioned organic fine particles is not particularly limited, for example, can be the approximately spherical of pearl, or powder Etc. unsetting shape, but preferably approximately spherical shape, more preferably aspect ratio are 1.5 approximately spherical grains below Son, be most preferably positive spherical particle.

As above-mentioned organic fine particles, can enumerate for example, polymethyl methacrylate particle (PMMA particle), organic silicon grain Son, polystyrene particle, polycarbonate particle, styrene particle, benzoguanamine particle, melamine particle, polyolefin Particle, polyester granules, polyamide particles, polyimide particle, polyvinyl fluoride particle etc..These organic fine particles can be used alone One kind also can be used together two kinds or more.

Wherein, as above-mentioned organic fine particles, can be suitble to using polymethyl methacrylate particle.

It is preferred that the range that the average grain diameter of above-mentioned organic fine particles used in the present invention is 1~10 μm, preferably 2~8 μm Range, more preferably 3~8 μm of range.Here so-called average grain diameter (μm), be by the laser diffraction based on Mie theory/ 50% volume diameter (median particle diameter) that scattering method obtains.If the average grain diameter of above-mentioned organic fine particles is greater than above-mentioned numerical value Range, then the image distinctiveness of display reduces, in addition, if being less than above-mentioned numberical range, then being prone to cannot be abundant Anti-glare, flash of light (ギラ Star キ) also become larger such problems.In addition, not special to the size distribution of above-mentioned organic fine particles It limits, preferably the consistent monodispersed particle of partial size.

Above-mentioned organic fine particles preferably have and the solidfied material of above-mentioned (a) active energy ray-curable polyfunctional monomer The organic fine particles for the refractive index that refringence is 0~0.20, further preferred above-mentioned refringence are 0~0.10.

In addition, the average grain diameter of above-mentioned organic fine particles is preferably relative to the curability group as used in the aftermentioned present invention The solidfied material of object acquisition, the i.e. film thickness of hard conating are closed, the range of average grain diameter b/ film thickness a=0.3~1.0 of organic fine particles is met Mode select.

Above-mentioned organic fine particles can be suitble to can be used using commercially available product for example, テ Network Port リマー (registered trademark) MBX Series, テ Network Port リマー SBX series, テ Network Port リマー MSX series, テ Network Port リマー SMX series, テ Network Port リマー SSX Series, テ Network Port リマー BMX series, テ Network Port リマー ABX series, テ Network Port リマー ARX series, テ Network Port リマー AFX Series, テ Network Port リマー MB series, テ Network Port リマー MBP series, テ Network Port リマー MB-C series, テ Network Port リマー ACX Serial, テ Network Port リマー ACP series [more than, ponding finished industrial (strain) system]；トスパー Le (registered trademark) series [モ (same) system of メ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application]；エ Port スター (registered trademark) Series, エ Port スター MA series, エ Port スター ST series, エ Port スター MX series [more than, (strain) Japan catalyst system]；オプトビーズ (registered trademark) series [Nissan Chemical Industries (strain) system]；フロービーズ series [refines (strain) in Sumitomo System]；トレパー Le (registered trademark) PPS, トレパー Le PAI, トレパー Le PES, トレパー Le EP [more than, eastern レ (strain) system]；3M (registered trademark) ダイニオ Application TF micro mist is serial [3M society system]；ケミスノー (registered trademark) MX series, ケミスノー MZ series, ケミスノー MR series, ケミスノー KMR series, ケミスノー KSR series, ケミスノー MP system Column, ケミスノー SX are serial, ケミスノー SGP is serial [more than, it is comprehensive to grind chemical (strain) system]；タ Off チッ Network (registered trademark) AR650 series, タ Off チッ Network AR-750 series, タ Off チッ Network FH-S series, タ Off チッ Network A-20, タ Off チッ Network YK system Column, タ Off チッ Network ASF series, タ Off チッ Network HU series, タ Off チッ Network F series, タ Off チッ Network C series, タ Off チッ Network WS Series [more than, (strain) system is spun by Japan]；アートパー Le (registered trademark) GR series, アートパー Le SE series, アートパー Le G series, アートパー Le GS series, アートパー Le J series, アートパー Le MF series, アートパー Le BE Series [more than, industrial (strain) system on root]；SHIN-ETSU HANTOTAI シリコー Application (registered trademark) KMP series [SHIN-ETSU HANTOTAI's chemical industry (strain) system] Deng.

In the present invention, it is expected that (c) organic fine particles are relative to above-mentioned (a) active energy ray-curable polyfunctional monomer 100 mass parts are preferably used with 8~30 mass parts with the ratio of 8~20 mass parts.

[polymerization initiator that (d) is generated free radicals using active energy beam]

It is preferred to utilize active energy beam and generate free radicals poly- in the solidification compound being used in the present invention Closing initiator (hereinafter, also referred to as " (d) polymerization initiator ") is, for example, to pass through electron ray, ultraviolet light, X-ray isoreactivity energy Ray is measured, the polymerization initiator generated free radicals especially by ultraviolet light irradiation.

As above-mentioned (d) polymerization initiator, can enumerate for example benzoin class, alkylbenzene ketone, thioxanthene ketone class, azo, Nitrine class, diazonium class, o-quinone diazonium class, acylphosphine oxide class, oxime esters, organic peroxide, benzophenone, bicoumarin Class, union II imidazoles, titanocenes class, thio-alcohol, halogenated hydrocarbon, trichloromethyl triazines or iodineSalt, sulfonium salt etc.Salt Deng.They can be used alone or be used in mixed way two kinds or more.

Wherein in the present invention, from the viewpoint of the transparency, surface cure, film hardening, it polymerize as (d) and causes Agent is, it is preferable to use alkyl phenones Type of Collective initiator.By using alkyl phenones Type of Collective initiator, marresistance can be obtained The solidfied material (hard conating) more improved.

As abovementioned alkyl benzophenone Type of Collective initiator, can enumerate for example, 1- hydroxy-cyclohexyl=phenyl=ketone, 2- hydroxyl Base-2- methyl-1-phenyl-propane-1- ketone, 2- hydroxyl-1- (4- (2- hydroxyl-oxethyl) phenyl)-2- methylpropane-1- ketone, 2- The Alpha-hydroxies alkyl phenones such as hydroxyl -1- (4- (4- (2- hydroxy-2-methyl propiono) benzyl) phenyl) -2- methylpropane -1- ketone Class；2- methyl-1-(4- (methyl mercapto) phenyl)-2- morpholino propane-1- ketone, 2- benzyl-2- dimethylamino-1- (4- morpholine For phenyl) the alpha-aminoalkyls benzophenone class such as butane -1- ketone；2,2- dimethoxy -1,2- diphenylethane -1- ketone；Benzoyl first Sour methyl esters etc..

In the present invention, it is expected that (d) polymerization initiator is relative to the above-mentioned multifunctional list of (a) active energy ray-curable 100 mass parts of body are preferably used with 1~20 mass parts with the ratio of 2~10 mass parts.

[(e) solvent]

Solidification compound used in the present invention can further include (e) solvent, that is, varnish is made, and (film forms material Material) form.

As above-mentioned solvent, as long as furthermore the dissolution of above-mentioned (a)~(d) ingredient, dispersion are considered that aftermentioned solidfied material is (hard Coating) operability when forming related coating, the drying property etc. that solidify front and back suitably select, can enumerate for example, benzene, Toluene, dimethylbenzene, ethylbenzene, tetrahydronaphthalene etc. are aromatic hydrocarbon；The aliphatic such as n-hexane, normal heptane, mineral spirits, hexamethylene or Ester ring type hydro carbons；Chloromethanes, bromomethane, iodomethane, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, perchloroethylene, neighbour two The halogenated species such as chlorobenzene；Ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetic acid esters, methylcellosolve acetate, The esters such as ethyl cellosolve acetate, propylene glycol monomethyl ether or ester ethers；Ether, tetrahydrofuran, 1,4- bis- Alkane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl, propylene glycol are mono- just The ethers such as propyl ether, propylene glycol monoisopropyl ether, the mono- n-butyl ether of propylene glycol；Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), The ketones such as di-n-butyl ketone, cyclohexanone；Methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, 2- ethyl The alcohols such as hexyl alcohol, benzylalcohol, ethylene glycol；The amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；Dimethyl sulfoxide etc. Sulfoxide type；The hetero ring type compounds such as n-methyl-2-pyrrolidone class and their mixed solvent of more than two kinds.

In addition, for control coating after drying when above-mentioned particle dispersibility purpose, higher boiling also can be used Solvent.

As such solvent, can enumerate for example, cyclohexyl acetate, propylene-glycol diacetate, 1,3-BDO oxalic acid Ester, 1,4- butanediol diacetate esters, 1,6-HD diacetate esters, ethylene glycol monobutyl ether acetic acid esters, carbiphene Acetic acid esters, diethylene glycol monobutyl ehter acetic acid esters, dipropylene glycol monomethyl ether acetate, 3- methoxybutyl acetic acid esters, ethylene glycol, It is diethylene glycol (DEG), propylene glycol, 1,3 butylene glycol, carbiphene, diethylene glycol monopropyl ether, diethylene glycol monobutyl ehter, double third sweet Alcohol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylether, tripropylene glycol list propyl ether, tripropylene glycol monobutyl base Ether, 3- methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol=methyl=propyl=ether etc..

The usage amount of these (e) solvent is not particularly limited, such as in solidification compound used in the present invention Solid component concentration becomes 1~70 mass %, preferably uses as the concentration of 5~50 mass %.Here so-called solid component is dense It spends (also referred to as nonvolatile component concentration), indicates the solid component of solidification compound used in the present invention (from whole components Ingredient after removing solvent composition) gross mass relative to above-mentioned (a)~(e) ingredient (and as needed other additives) The content of (total quality).

[other additives]

In addition, in solidification compound used in the present invention, as long as not damaging effect of the invention, so that it may according to need Suitably to cooperate the additive usually added, for example polymerization accelerant, polymerization inhibitor, photosensitizer, levelling agent, surfactant, Adaptation imparting agent, plasticizer, ultraviolet absorbing agent, antioxidant, storage stabilizing agent, antistatic agent, inorganic filler, face Material, dyestuff etc..

In addition, the purpose of the haze value for control solidfied material (hard conating), can cooperate the inorganic particles such as titanium oxide.

" Antidazzle hard coating laminated body "

As described above, Antidazzle hard coating laminated body of the invention is by the prime coat of the top of substrate, the substrate and at this 3 layers of the laminated body that hard conating above prime coat is constituted.

Antidazzle hard coating laminated body of the invention includes following processes and manufactures:

(i) primer coating layer formation composition and the process that forms film on substrate,

(ii) film of the prime coat formation composition is carried out heating makes its solidification, the process for forming prime coat,

(iii) process for being coated with solidification compound on above-mentioned prime coat and forming film, and

(iv) its solidification is made to the film irradiation active energy beam of the solidification compound, the process for forming hard conating.

Here prime coat formation composition and solidification compound can apply above-mentioned each composition.

The coating method of prime coat formation composition and solidification compound in above-mentioned (i) and (iii) process can be with Appropriate selection casting coating, method of spin coating, scraper coating method, Dipcoat method, rolling method, stick coating method, die coating method, spray coating method, Curtain coating, ink-jet method, print process (relief printing plate, intaglio plate, lithographic plate, screen painting etc.) etc., wherein from due to that can be coated with the short time, Even therefore the high solution of volatility also can use, being furthermore possible to the advantage that being easy to carry out uniform coating is examined Consider, it is expected that using method of spin coating.In addition, being formed from can simply be coated with, and without large area coating unevenness The advantage that smooth film, considers, it is expected that using rolling method, die coating method, spray coating method.Prime coat used herein, which is formed, to be used Composition and solidification compound can be suitble to the composition using the above-mentioned form in varnish.Additionally, it is preferred that making in advance For coating after prime coat formation composition and solidification compound are filtered for 2 μm or so filter etc. with aperture.

After the prime coat of above-mentioned (i) process forms the coating with composition, as (ii) process, with electric hot plate or baking oven Etc. being heated, by curing of coating, form prime coat.As heat treatment condition at this time, for example, it is preferable to for 40~ 150 DEG C, 30 seconds~10 minutes or so.

In addition, prime coat formation with composition include active energy ray-curable polyfunctional monomer, utilize active energy Amount ray and in the case where the polymerization initiator that generates free radicals, can be applicable in using the film of aftermentioned solidification compound Active energy beam irradiation process.

After the coating of the solidification compound of above-mentioned (iii) process, preferably then carried out with electric hot plate or baking oven etc. After predrying, as (iv) process, irradiating ultraviolet light isoreactivity energy-ray makes its photocuring, forms hard conating.As activity Energy-ray can enumerate ultraviolet light, electron ray, X-ray etc..Used light source is irradiated as ultraviolet light, can be used too Sunlight line, chemical lamp, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, metal halide lamp, xenon lamp, UV-LED etc..

Then, by toasting after carrying out, in particular by using electric hot plate, baking oven etc. to be heated, can make to polymerize Terminate with polycondensation.

In the laminated body of the invention that such operate obtains, the thickness of above-mentioned prime coat is not particularly limited, can be with For such as 0.01~1 μm of range.

In addition, hard conating is preferably set in such a way that it is with a thickness of 1~10/3 times of the average grain diameter of above-mentioned organic fine particles (c) It is fixed.Such as above-mentioned hard conating with a thickness of 1~30 μm of range, preferably 1~20 μm, more preferably 3~10 μm.

Embodiment

Hereinafter, enumerating embodiment further illustrates the present invention, but the present invention is not limited to following embodiments.

In addition, in embodiment, device used in the modulation of sample and the analysis of physical property and condition are as described below.

(1) rotary coating

Device: ズースマイ Network ロテッ Network society spin coater LabSpin6TT

(2) electric hot plate

Device: アズワ Application (strain) MH-180CS processed, MH-3CS

(3) UV irradiates

Device: アイグラ Off ィッ Network ス (strain) lamp of アイ ultra-violet curing device US5-0401 4kW × 1 processed

(4) scoring test

Device: reciprocal abrasiometer TRIBOGEAR TYPE:30S is made in new east scientific (strain)

Loading: 250g/cm²

Scanning speed: 3m/ minutes

(5) gel permeation chromatography (GPC)

Device: Dong ソー (strain) HLC-8220GPC processed

Column: Showa electrician (strain) Shodex processed (registered trademark) GPC KF-804L, GPC KF-805L

Column temperature: 40 DEG C

Eluent: tetrahydrofuran

Detector: RI

(6) film thickness

Device: (strain) ニ U Application number gauging machine デジマイ Network ロ MH-15M+ counter TC-101A

(7) glossiness

Device: U ニカミノ Le タ (strain) gloss meter GM-268Plus processed

Measurement angle: 60 degree

(8) full light transmittance, mist degree

Device: Japan electricity color industry (strain) haze meter NDH5000 processed

(9) contact angle

Device: consonance interface science (strain) DropMaster DM-501 processed

Measuring temperature: 20 DEG C

In addition, shorthand notation indicates following meanings.

PFPE1: have the perfluor of hydroxyl poly- via poly- (oxyalkylene) group (number of repeat unit 8~9) in two ends Ether [ソ Le ベイスペシャ Le ティ Port リマーズ society Fluorolink5147X]

Bis- (acryloyloxymethyl) ethyl isocyanates of BEI:1,1- [Showa electrician (strain) カレ Application ズ (registrar processed Mark) BEI]

DBTDL: dibutyl tin dilaurate [Tokyo chemical conversion industry (strain) system]

HTES: triethoxy (hexyl) silane [SHIN-ETSU HANTOTAI's chemical industry (strain) SHIN-ETSU HANTOTAI シリコー Application (registered trademark) KBE- processed 3063]

MPTES: triethoxy (3- methacryloxypropyl) silane [SHIN-ETSU HANTOTAI's chemical industry (strain) SHIN-ETSU HANTOTAI シリ U processed ー Application (registered trademark) KBE-503]

TEOS: tetraethoxysilane [モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application (same) TSL8124 processed]

DPHA: Dipentaerythritol Pentaacrylate/dipentaerythritol hexaacrylate mixture [Japanese chemical drug (strain) system KAYALAD DPHA]

PETA: the pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [village Xin Zhong chemical industry (strain) system NK ester A-TMM-3LM-N]

UA:6 functional aliphatic urethane acrylate oligomer [ダイセ Le オ Le ネ Network ス (strain) system EBECRYL (registered trademark) 5129]

SM2: UV response type fluorine system surface modifier [DIC (strain) the メガ Off ァッ Network processed (note with perfluoropolyether structures Volume trade mark) RS-75,40 mass %MEK/MIBK solution of effective component]

FP1: the positive spherical particle of crosslinked polymethylmethacrylaparticles [ponding finished industrial (strain) テ Network Port リマー processed (note Volume trade mark) SSX-105,5 μm of average grain diameter]

FP2: the positive spherical particle of crosslinked polymethylmethacrylaparticles [ponding finished industrial (strain) テ Network Port リマー processed (note Volume trade mark) SSX-103,3 μm of average grain diameter]

FP3: the positive spherical particle of crosslinked polymethylmethacrylaparticles [ponding finished industrial (strain) テ Network Port リマー processed (note Volume trade mark) SSX-102,2 μm of average grain diameter]

I2959:2- hydroxyl -1- (4- (2- hydroxyl-oxethyl) phenyl) -2- methylpropane -1- ketone [BASF ジャパ Application (strain) IRGACURE 2959 processed]

EPA: ESCAROL 507 ethyl ester [Japanese chemical drug (strain) KAYACURE EPA processed]

EtOH: ethyl alcohol

MEK: methyl ethyl ketone

MIBK: methyl iso-butyl ketone (MIBK)

PGME: propylene glycol monomethyl ether

[Production Example 1] has acryloyl group via poly- (oxyalkylene) group and 1 urethane bond in two ends Perfluoropolyether SM1 manufacture

BEI, 10mg of PFPE1, the 0.26g (1.0mmol) of 1.05g (0.5mmol) are added in screwed pipe The MEK of the DBTDL and 1.30g of (0.016mmol).The mixture is stirred 24 under room temperature (about 23 DEG C) using stirrer Hour.The reaction mixture MEK of 3.93g is diluted, the 20 mass %MEK for obtaining the SM1 as target compound are molten Liquid.

The weight average molecular weight Mw with polystyrene conversion measurement of resulting SM1 obtained by GPC is 3,400, dispersion degree: Mw (weight average molecular weight)/Mn (number-average molecular weight) is 1.2.

The modulation of [Production Example 2-1~2-3] paint base composition (prime coat, which is formed, uses composition)

Alkoxy silane and ethyl alcohol is added according to being documented in reaction flask for table 1, is stirred 5 minutes under stream of nitrogen gas, Modulate alkoxy silane/ethanol solution.The oxalic acid-separately modulated according to the record of table 1 was added dropwise through 10 minutes into the solution Water/ethanol solution.After the solution is stirred 30 minutes, heats and stir 1 hour until the reflux of interior liquid (about 80 DEG C).It will Reaction mixture is cooling until room temperature (about 23 DEG C), obtains the paint base composition of 40 mass % of siloxane oligomer concentration (PR1~PR3).

The weight average molecular weight Mw measured with polystyrene conversion of resulting siloxane oligomer obtained by GPC and dispersion Degree: Mw/Mn is respectively 1,400,1.1 (PR1), 1,500,1.1 (PR2), 1,500,1.1 (PR3).

Table 1

The modulation of [Production Example 3-1~3-4] hard coating composition (solidification compound)

Following ingredient is mixed according to the record of table 2, modulates the hard conating group that solid component concentration is 40 mass % It closes object (HC1~HC4).In addition, so-called solid component refers to the ingredient other than solvent here.In addition, so-called [part] indicates in table [mass parts].

(1) polyfunctional monomer: 50 mass parts of DPHA, 20 mass parts of 30 mass parts of UA and PETA

(2) surface modifier: 1 mass parts of surface modifier documented by table 2 (solid component or effective component conversion)

(3) organic fine particles: make amount documented by organic fine particles table 2 documented by table 2

(4) polymerization initiator: 5 mass parts of I2959

(5) polymerization accelerant: 0.1 mass parts of EPA

(6) solvent: amount documented by PGME table 2

Table 2

[Examples 1 to 8, comparative example 1~3]

It will be diluted in a manner of becoming solid component concentration (siloxane oligomer concentration) documented by table 3 with PGME Paint base composition, rotary coating (1,000rpm × 30 seconds) obtain on glass substrate (10cm × 10cm, thickness 0.7mm) Film.120 DEG C of electric hot plate of the film is heated 1 hour, so as to form the prime coat (solidification of thickness shown in table 3 Film).

On the prime coat, by hard coating composition rotary coating documented by table 3 (revolving speed × 30 second documented by table 3) And obtain film.It dries the film 3 minutes with 120 DEG C of electric hot plate and removes solvent.By resulting film in nitrogen gas Under atmosphere, irradiation exposure amount 500mJ/cm²UV light be exposed, thus produce with thickness shown in table 3 hard conating (Gu Change film) hard painting laminated body.

To it is resulting it is hard apply laminated body anti-glare, adaptation, marresistance, full light transmittance, mist degree and water and The contact angle of oleic acid is evaluated.The evaluation procedure of anti-glare, adaptation, marresistance and contact angle is shown below.This Outside, result is shown in Table 4 together.

[anti-glare]

The resulting hard laminated body that applies is placed on the black platform that (60 °) of glossiness Gs are 11.8, hard coating surface is measured Glossiness Gs (60 °), evaluated according to following benchmark.In addition, assuming actual use as hard painting laminated body In the case where, it is desirable that it is at least B, is desired for A.

A:Gs (60 °)≤120

B:120 < Gs (60 °)≤125

C:Gs (60 °) > 125

[adaptation]

Grid guide plate CCI-2 is drawn using guide plate [コーテッ Network (strain) system] 25 pieces are introduced (between 5 × 5,2mm to hard conating Every) right angle grid pattern notch, utilize oolemma [ニチバ Application (strain) the セロテープ processed for having used width 18mm (registered trademark) CT-18] draw square method (according to JIS5600-5-6), evaluated according to following benchmark.

A:25 block is not removed all

B:1~11 piece removing

It more than C:12 block removes

[marresistance]

By hard coating surface steel wool [ボ Application スター dealer Sales (strain) ボ Application ス processed for being installed on reciprocal abrasiometer ター (registered trademark) #0000 (super is thin)] apply 250g/cm²Loading wipe 1,000 back and forth, with permanent pen [ゼ Block ラ (strain) マッキー processed superfine (indigo plant), uses thin side] it draws lines in the part wiped across.Then the line nonwoven that will be drawn Fabric rag [Asahi Chemical Industry (strain) BEMCOT processed (registered trademark) M-1] is wiped, and confirms the degree of wound by visual observation and according to following Benchmark is evaluated.In addition, in the case where assuming actual use as hard painting laminated body, it is desirable that be at least B, be desired for A。

A: line that is not injured and being drawn with permanent pen is neatly wiped

B: it is slightly injured, but the line drawn with permanent pen is neatly wiped

C: the ink of permanent pen is entered in wound and cannot be wiped

[contact angle]

So that water or 1 μ L of oleic acid is attached to hard coating surface, its contact angle θ after 5 seconds is measured at 5 points, by its average value It is set as contact angle values.

Table 3

Table 4

As shown in 1~table of table 4, use in two ends in formation via poly- (oxyalkylene) group and 1 carbamic acid Ester bond base and when combining hard conating of the perfluoropolyether SM1 as surface modifier of acryloyl group, in the reality provided with prime coat When applying the 1~laminated body of laminated body 6, laminated body 10 and laminated body 11 of 1~embodiment of example 8, it is made that anti-glare is excellent actually to be made Used time be also can satisfy, adaptation and the quality of marresistance, furthermore transparent excellent laminated body.

On the other hand, used the siloxane oligomer without free-radical polymerised double bond (beyond this hair in prime coat Bright defined siloxane oligomer) in the case where (comparative example 1), and in the case where being not provided with prime coat (comparative example 2), at It is low for adaptation of the hard conating to glass substrate, the furthermore result of marresistance difference.

In addition, having used the UV response type fluorine system surface modifier SM2 with perfluoropolyether structures as table in hard conating In the case where the modifying agent of face (comparative example 3), although can get meet anti-glare, adaptation as a result, cannot get desired Marresistance.

More than, as shown in the result of embodiment, specific perfluoropolyether is used as the hard of surface modifier having In the laminated body of coating, by being arranged by the material comprising the specific siloxane oligomer with free-radical polymerised double bond The prime coat that solidfied material is formed can obtain and meet anti-glare, marresistance and to the over-all properties of the adaptation of substrate Laminated body.

Claims

1. a kind of Antidazzle hard coating laminated body, by substrate, square prime coat and above the prime coat on the substrate Hard conating is constituted,

The prime coat is formed by the solidfied material of prime coat formation composition, and the prime coat formation includes with composition:

Ingredient (A) has the siloxane oligomer of free-radical polymerised double bond, and the siloxane oligomer is by making at least to wrap Alkoxy silane hydrolytic condensation containing alkoxy silane B shown in alkoxy silane A shown in formula [1] and formula [2] and obtain,

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

In formula, R¹Indicate the 1 valence organic group with free-radical polymerised double bond, R³Indicate the alkyl or benzene of carbon atom number 1~10 Base, the ammonia which can be substituted by phenyl by fluorine atom, at least by the alkyl-substituted amino of carbon atom number 1~6, at least Base or Carbamido substituted, R²And R⁴Methyl or ethyl are each independently represented, a indicates 1 or 2, and b indicates 0~2 integer；

The hard conating is formed by the solidfied material of following solidification compounds, and the solidification compound includes:

100 mass parts of ingredient (a) active energy ray-curable polyfunctional monomer,

0.1~10 mass parts of ingredient (b) perfluoropolyether, the perfluoropolyether is in the molecule comprising poly- (oxygen perfluorinated alkylidene) group Two ends of chain are combined with active energy beam polymerizable group via poly- (oxyalkylene) group, or successively via poly- (oxyalkylene) group and 1 urethane bond group and be combined with active energy beam polymerizable group,

Organic fine particles 8~30 mass parts of the ingredient (c) with 1~10 μm of average grain diameter, and

1~20 mass parts of polymerization initiator that ingredient (d) is generated free radicals using active energy beam.

2. Antidazzle hard coating laminated body according to claim 1, the siloxane oligomer of the ingredient (A) is to pass through formula [1] alkoxy silane A shown in and alkoxy silane B hydrolytic condensation shown in formula [2] and having for obtaining is free-radical polymerised The siloxane oligomer of double bond,

R¹ _aSi(OR²)_4-A [1] R³ _bSi(OR⁴)_4-b [2]

In formula, R¹Indicate the 1 valence organic group with free-radical polymerised double bond, R³Indicate that the carbon that can be replaced by fluorine atoms is former The alkyl or phenyl of subnumber 1~6, R²And R⁴Each independently represent methyl or ethyl, a indicate 1 or 2, b indicate 0~2 it is whole Number.

R 3. Antidazzle hard coating laminated body according to claim 1 or 2, in the formula [1]¹For with vinyl or (first Base) acryloyl group 1 valence organic group.

4. Antidazzle hard coating laminated body according to claim 3, the alkoxy silane A is to change shown in following formula [3] Object is closed,

In formula, R²Indicate meaning identical with the definition in the formula [1], R⁵Indicate hydrogen atom or methyl, L¹Indicate carbon atom number 1~10 alkylidene.

5. Antidazzle hard coating laminated body according to any one of claims 1 to 4, the ingredient (A) has free radical The siloxane oligomer of polymeric double bond is the siloxanes of the unit from the alkoxy silane A comprising 10~99mol% Oligomer.

6. Antidazzle hard coating laminated body according to any one of claims 1 to 5, the perfluoropolyether of the ingredient (b) Poly- (oxygen perfluorinated alkylidene) group is with-[OCF₂]-and-[OCF₂CF₂The group of]-as repetitive unit.

7. Antidazzle hard coating laminated body described according to claim 1~any one of 6, the perfluoropolyether of the ingredient (b) Poly- (oxyalkylene) group is poly- (oxygen ethylidene) group.

8. Antidazzle hard coating laminated body according to any one of claims 1 to 7, the polyfunctional monomer of the ingredient (a) For in multifunctional (methyl) acrylate compounds and polyfunctional carbamate (methyl) acrylate compounds extremely It is a kind few.

9. Antidazzle hard coating laminated body described according to claim 1~any one of 8, the organic fine particles of the ingredient (c) are Positive spherical particle.

10. Antidazzle hard coating laminated body described according to claim 1~any one of 9, the organic fine particles of the ingredient (c) are Polymethyl methacrylate particle.

11. the polymerization of Antidazzle hard coating laminated body described according to claim 1~any one of 10, the ingredient (d) causes Agent is alkyl phenones Type of Collective initiator.

12. Antidazzle hard coating laminated body described according to claim 1~any one of 11, the hard conating with a thickness of described 1~10/3 times of the average grain diameter of the organic fine particles of ingredient (c).

13. Antidazzle hard coating laminated body described according to claim 1~any one of 12, the hard conating has 1~20 μm Film thickness.

14. Antidazzle hard coating laminated body according to claim 13, the hard conating has 3~10 μm of film thickness.

15. Antidazzle hard coating laminated body described according to claim 1~any one of 14, the substrate is glass.

16. a kind of manufacturing method of Antidazzle hard coating laminated body, the Antidazzle hard coating laminated body has in at least one side of substrate Standby prime coat, and have hard conating above the prime coat, the manufacturing method includes following processes:

The process for being coated with solidification compound on the prime coat and forming film；And

Active energy beam is irradiated to the film of the solidification compound and makes the curing of coating, the process for forming hard conating,

The prime coat formation includes with composition:

R¹ _aSi(OR²)_4-a [1] R³ _bSi(OR⁴)_4-b [2]

The solidification compound includes:

0.1~10 mass parts of ingredient (b) perfluoropolyether, the perfluoropolyether is in the molecule comprising poly- (oxygen perfluorinated alkylidene) group Two ends of chain are combined with active energy beam polymerizable group via poly- (oxyalkylene) base, or successively via poly- (oxygen Asia Alkyl) group and 1 urethane bond group and be combined with active energy beam polymerizable group,