CN109791225B

CN109791225B - Anti-glare hard-coated laminate

Info

Publication number: CN109791225B
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: 2021-02-19
Anticipated expiration: 2037-10-11
Also published as: CN109791225A; JP6799283B2; TW201827535A; KR102507695B1; JPWO2018070426A1; WO2018070426A1; TWI735678B; KR20190060977A

Abstract

The invention provides a laminate having a hard coat layer which has excellent anti-glare property, high scratch resistance and excellent adhesion to a substrate. The solution is an anti-glare hard-coated laminate comprising a substrate, a primer layer on the substrate, and a hard-coating layer on the primer layer, wherein the primer layer is formed from a cured product of a primer layer-forming composition containing a specific siloxane oligomer having a radical-polymerizable double bond, and the hard-coating layer is formed from a cured product of a curable composition containing (a) a polyfunctional monomer, (b) a perfluoropolyether having an active energy ray-polymerizable group bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, or having an active energy ray-polymerizable group bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group and 1 urethane bond in this order, (c) organic microparticles, and a method for producing the same, And (d) a polymerization initiator.

Description

Anti-glare hard-coated laminate

Technical Field

The present invention relates to an antiglare hard-coat laminate having a hard-coat layer excellent in antiglare properties (anti-glare function), and a method for producing the same.

Background

Products having touch panels mounted on flat panel displays such as personal computers, mobile phones, portable game devices, and ATMs are commercialized in a large number. In particular, with the advent of smartphones and tablet PCs, the number of capacitive touch panels having a multi-touch function has increased at a glance.

In order to prevent the reduction of visibility due to reflection of external light on the screen, a method of bonding an antiglare hard coat film having a hard coat layer of several μm with irregularities formed on the surface thereof to the surface of these touch panel displays has been used. As a method for forming irregularities on the surface, a method of incorporating fine particles having a particle diameter of about several μm into the hard coat layer is generally used.

In addition, the capacitance touch panel is operated by being touched with a human finger. Therefore, the following problems arise: fingerprints are attached to the surface of the touch panel each time an operation is performed, and visibility of an image of the display or appearance of the display is significantly impaired. Fingerprints include moisture derived from sweat and oil derived from sebum, and in order to make neither of them easily adhere, it is strongly desired to impart water repellency and oil repellency to a hard coat layer on the surface of a display.

However, since a person touches the capacitance type touch panel with a finger every day, even if the initial antifouling property reaches a high level, the capacitance type touch panel is often damaged during use and the functions thereof are often degraded. In particular, since the hard antiglare coating layer has irregularities on the surface thereof, the hard antiglare coating layer is liable to be caught and damaged. Therefore, durability of antifouling property during use is a problem.

Disclosed so far are: as a hard coat layer having antiglare properties and scratch resistance, a surface modifier having a poly (oxyperfluoroalkylene) group structure and a (meth) acryloyl group in a molecule is used as a component for imparting antifouling properties and scratch resistance to the surface of the hard coat layer, and a technique of using methyl methacrylate-styrene copolymer (MS) resin fine particles as a component for imparting antiglare properties to the hard coat layer is used (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-257359

Disclosure of Invention

Problems to be solved by the invention

The method described specifically in patent document 1 has the following problems: the surface modifier having a poly (oxyperfluoroalkylene) group structure and a (meth) acryloyl group in the molecule has a low fluorine content, and thus sufficient antifouling properties and scratch resistance cannot be obtained. Further, there is a problem that: if the amount of MS resin particles added is reduced in order to obtain scratch resistance, sufficient antiglare properties cannot be obtained, and if MS resin particles are added to such an extent that sufficient antiglare properties can be obtained, scratch resistance is significantly reduced. Further, the hard coat layer has poor dispersibility of the resin particles, and the resin particles become aggregates to impair the appearance of the coating film.

Further, a hard coat layer using an acrylic resin is also a problem that it has poor adhesion particularly to a glass substrate and is easily peeled off from the substrate.

Thus, a hard coat layer having excellent antiglare properties, high scratch resistance, and excellent adhesion to a substrate is required.

Means for solving the problems

The present inventors have made intensive studies to achieve the above object, and as a result, have found that a primer layer is provided between a substrate and a hard coat layer in order to improve adhesion to the substrate, and particularly that a siloxane oligomer having a radical polymerizable double bond is used as a material for forming the primer layer. Further, the inventors have found that a laminate having a hard coat layer provided on the primer layer and having excellent antiglare properties, high scratch resistance and excellent adhesion is obtained by using, as a fluorine-based surface modifier, a compound in which an active energy ray-polymerizable group is bonded to both ends of a molecular chain having a poly (oxyperfluoroalkylene) group structure via a poly (oxyalkylene) group or an active energy ray-polymerizable group is bonded via a poly (oxyalkylene) group and 1 urethane group, and further adding organic fine particles to the compound, and thereby have completed the present invention.

That is, the present invention relates, as a1 st aspect, to an antiglare hard-coated laminate composed of a substrate, a primer layer over the substrate, and a hard-coating layer over the primer layer,

the primer layer is formed from a cured product of a primer layer forming composition, the primer layer forming composition comprising:

a siloxane oligomer having a radical polymerizable double bond as component (A), which is obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by formula [1] and an alkoxysilane B represented by formula [2],

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

(in the formula, R¹Represents a 1-valent organic group having a radically polymerizable double bond, R³Represents an alkyl group having 1 to 10 carbon atoms (the alkyl group may be substituted with a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, an amino group substituted with at least a phenyl group, or a ureido group), or a phenyl group, R²And R⁴Each independently represents a methyl group or an ethyl group, a represents 1 or 2, and b represents an integer of 0 to 2. )

The hard coat layer is formed from a cured product of a curable composition containing:

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

(b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray-polymerizable group bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or an active energy ray-polymerizable group bonded to both ends of a molecular chain via a poly (oxyalkylene) group and 1 urethane bond group in this order,

(c) 8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm, and

(d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray.

As a second aspect, the present invention relates to the antiglare hard-coated laminate according to the first aspect 1, wherein the siloxane oligomer as the component (a) is a siloxane oligomer having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane a represented by the formula [1] and an alkoxysilane B represented by the formula [2 ].

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

(in the formula, R¹Represents a 1-valent organic group having a radically polymerizable double bond, R³Represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or a phenyl group, R²And R⁴Each independently represents a methyl group or an ethyl group, a represents 1 or 2, and b represents an integer of 0 to 2. )

As a 3 rd aspect, the present invention relates to the antiglare hard-coated laminate according to 1 st or 2 nd aspect, wherein the formula [1]R in (1)¹Is a 1-valent organic group having a vinyl group or a (meth) acryloyl group.

In a 4 th aspect, the present invention provides the antiglare hard-coated laminate according to the 3 rd aspect, wherein the alkoxysilane a is a compound represented by the following formula [3 ].

(in the formula, R²Is represented by the formula [1]Wherein R is as defined in⁵Represents a hydrogen atom or a methyl group, L¹Represents an alkylene group having 1 to 10 carbon atoms. )

An aspect 5 relates to the antiglare hard-coated laminate according to any one of aspects 1 to 4, wherein the siloxane oligomer having a radical polymerizable double bond of the component (a) is a siloxane oligomer containing 10 to 99 mol% of a unit derived from the alkoxysilane a.

The 6 th aspect of the present invention is the antiglare hard-coated laminate according to any one of the 1 st to 5 th aspects, wherein the perfluoropolyether of the component (b) has a poly (oxyperfluoroalkylene group) having- [ OCF ]₂]-and- [ OCF₂CF₂]-a group as a repeating unit.

An aspect 7 relates to the antiglare hard-coated laminate according to any one of aspects 1 to 6, wherein the perfluoropolyether of the component (b) has a poly (oxyalkylene) group as a poly (oxyethylene) group.

An 8 th aspect of the present invention is the antiglare hard-coated laminate according to any one of the 1 st to 7 th aspects, wherein the polyfunctional monomer of the component (a) is at least 1 selected from a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.

As a 9 th aspect, the hard-coated antiglare laminate according to any one of the 1 st to 8 th aspects is characterized in that the organic fine particles of the component (c) are spherical particles.

As a 10 th aspect, the present invention relates to the antiglare hard-coated laminate according to any one of the 1 st to 9 th aspects, wherein the organic fine particles of the component (c) are polymethyl methacrylate particles.

An 11 th aspect of the present invention is the antiglare hard-coated laminate according to any one of the 1 st to 10 th aspects, wherein the polymerization initiator of the component (d) is an alkylphenone-based polymerization initiator.

As a 12 th aspect, the present invention provides the antiglare hard-coated laminate according to any one of the 1 st to 11 th aspects, wherein the hard-coating layer has a thickness of 1 to 10/3 times an average particle diameter of the organic fine particles of the component (c).

An aspect 13 relates to the antiglare hard-coated laminate according to any one of aspects 1 to 12, wherein the hard-coating layer has a film thickness of 1 to 20 μm.

An aspect 14 relates to the antiglare hard-coated laminate according to aspect 13, wherein the hard-coating layer has a film thickness of 3 to 10 μm.

The 15 th aspect of the present invention relates to the antiglare hard-coated laminate according to any one of the 1 st to 14 th aspects, wherein the substrate is glass.

As a 16 th aspect, the present invention relates to a method for producing an antiglare hard-coated laminate, the method including a primer layer on at least one surface of a substrate and a hard-coating layer provided over the primer layer, the method including:

a step of applying a primer layer-forming composition to a substrate to form a coating film;

a step of forming a primer layer by heating the coating film of the primer layer-forming composition to cure the coating film;

a step of applying a curable composition on the primer layer to form a coating film; and

a step of irradiating the coating film of the curable composition with an active energy ray to cure the coating film to form a hard coat layer,

the primer layer forming composition includes:

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

The curable composition comprises:

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

Effects of the invention

According to the present invention, a laminate having a hard coat layer excellent in scratch resistance and high antiglare property even in a thin film having a thickness of about 1 to 15 μm and also excellent in appearance can be provided, and in particular, a laminate having a hard coat layer excellent in adhesion to a substrate can be provided by providing a primer layer containing a siloxane oligomer having a radical polymerizable double bond on a substrate and providing the hard coat layer on the primer layer.

Detailed Description

The antiglare hardcoat laminate of the present invention is composed of a substrate, a primer layer over the substrate, and a hardcoat layer over the primer layer.

In the antiglare hard-coat laminate of the present invention, the primer layer is formed from a cured product of a primer layer-forming composition containing a siloxane oligomer having a radical polymerizable double bond, and the hard-coat layer is formed from a cured product of a curable composition containing an active energy ray-curable polyfunctional monomer or the like.

Each layer constituting the antiglare hard-coated laminate of the present invention will be described in detail below.

Substrate

The substrate in the antiglare hardcoat laminate of the present invention is not particularly limited, and examples thereof include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, PET (polyethylene terephthalate), polyolefin, epoxy resin, melamine resin, triacetyl cellulose, ABS (acrylonitrile-butadiene-styrene copolymer), AS (acrylonitrile-styrene copolymer), norbornene resin, etc.), metals, woods, papers, glass, silica, slates, and the like. The shape of these substrates may be a plate, a film or a 3-dimensional molded body.

In the present invention, glass can be suitably used as the substrate.

The thickness of the substrate is not particularly limited, and may be, for example, 10 to 1,000 μm.

Primer layer

< composition for Forming primer layer >

The primer layer in the antiglare hard-coat laminate of the present invention is formed from a cured product of a primer layer-forming composition containing the following component (a):

a siloxane oligomer having a radical polymerizable double bond as component (A), which is obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by formula [1] and an alkoxysilane B represented by formula [2 ].

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

The components (a) and the components that can be contained in the primer layer-forming composition will be described below.

[ (A) siloxane oligomer having radically polymerizable double bond ]

The siloxane oligomer (a) having a radical polymerizable double bond (hereinafter, also simply referred to as "siloxane oligomer (a)") is a siloxane oligomer obtained by hydrolytic condensation of an alkoxysilane a represented by the following formula [1] and an alkoxysilane B represented by the following formula [2] which are contained at least as essential alkoxysilane units.

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

The above formula [1]In, R¹Represents a 1-valent organic group having a radically polymerizable double bond, R²Represents a methyl group or an ethyl group, and a represents 1 or 2.

Further, formula [2]In, R³Represents an alkyl group having 1 to 10 carbon atoms (the alkyl group may be substituted with a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, an amino group substituted with at least a phenyl group, or a ureido group), or a phenyl group, preferably R³Represents an alkyl group having 1 to 6 carbon atoms or a phenyl group which may be substituted with a fluorine atom, R⁴Represents a methyl group or an ethyl group, and b represents an integer of 0 to 2.

As the above formula[1]R in (1)¹The 1-valent organic group having a radical polymerizable double bond of (b) is preferably a 1-valent organic group having a vinyl group or a (meth) acryloyl group. In the present invention, the term "(meth) acryloyl group" refers to both an acryloyl group and a methacrylate group.

Further, the above formula [2]]R in (1)³Examples of the alkyl group having 1 to 10 carbon atoms (the alkyl group may be substituted with a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, an amino group substituted with at least a phenyl group, or a ureido group) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, a n-decyl group, and.

Further, the above formula [2]]R in (1)³Examples of the amino group substituted with at least an alkyl group having 1 to 6 carbon atoms include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a N-propylamino group, an isopropylamino group, a N-butylamino group, a tert-butylamino group, a N-pentylamino group, a N-hexylamino group, a cyclohexylamino group, and an N-methyl-N-phenylamino group.

Further, the formula [2]]R in (1)³Examples of the amino group substituted with at least a phenyl group include a phenylamino group and a diphenylamino group.

Among the alkoxysilane A represented by the above formula [1], a compound represented by the following formula [3] is preferable.

In the formula, R²Is represented by the formula [1]Wherein R is as defined in⁵Represents a hydrogen atom or a methyl group, L¹Represents an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms.

As the above-mentioned L¹Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, 1, 3-propylene, methylethylene, 1, 4-butylene, 1-methyl-1, 3-propylene, 1,5-Pentylene, 2-dimethyl-1, 3-propylene, 1, 6-hexylene, 1, 8-octylene, 1, 10-decylene, and the like. Among them, 1, 3-propylene is preferable.

Specific examples of the alkoxysilane A include trimethoxy (vinyl) silane, triethoxy (vinyl) silane, 3- (meth) acryloyloxypropyltrimethoxysilane, triethoxy (3- (meth) acryloyloxypropyl) silane, 8- (meth) acryloyloxyoctyltrimethoxysilane, triethoxy (8- (meth) acryloyloxyoctyl) silane, 3- (meth) acryloyloxypropyl (dimethoxy) (meth) silane, diethoxy (3- (meth) acryloyloxypropyl) (meth) silane, trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane and the like.

Among them, 3- (meth) acryloyloxypropyltrimethoxysilane and triethoxy (3- (meth) acryloyloxypropyl) silane are preferable.

Specific examples of the alkoxysilane B represented by the formula [2] include tetramethoxysilane, tetraethoxysilane, trimethoxy (methyl) silane, triethoxy (methyl) silane, ethyltrimethoxysilane, triethoxy (ethyl) silane, trimethoxy (propyl) silane, triethoxy (propyl) silane, trimethoxy (3,3, 3-trifluoropropyl) silane, triethoxy (3,3, 3-trifluoropropyl) silane, butyltrimethoxysilane, butyltriethoxysilane, trimethoxy (pentyl) silane, triethoxy (pentyl) silane, hexyltrimethoxysilane, triethoxy (hexyl) silane, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane, and the like, Diethoxydiethylsilane, dimethoxydipropylsilane, diethoxydipropylsilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dimethoxydipentylsilane, diethoxydipentylsilane, dihexyldimethoxysilane, diethoxydihexylsilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, trimethoxy ((phenylamino) methyl) silane, trimethoxy (3- (phenylamino) propyl) silane, triethoxy (3- (phenylamino) propyl) silane, dimethoxy (methyl) (3- (phenylamino) propyl) silane, etc.

Among them, tetramethoxysilane, tetraethoxysilane, trimethoxy (3- (phenylamino) propyl) silane, and triethoxy (3- (phenylamino) propyl) silane are preferable.

(A) The siloxane oligomer is preferably a siloxane oligomer containing 10 to 99 mol% of units derived from the above-mentioned alkoxysilane A among all alkoxysilane units.

In particular, the siloxane oligomer (A) is preferably a siloxane oligomer containing at least 10 to 99 mol% of a structural unit represented by the following formula [4] in all the structural units.

In the formula, R²、R⁵And L¹Is represented by the formula [3]]The same meanings as defined in (1) above.

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

For example, an alkoxysilane containing the above alkoxysilane a and alkoxysilane B is condensed in an organic solvent. Examples of the method of polycondensing the alkoxysilane include a method of hydrolyzing and condensing the alkoxysilane in a solvent such as alcohol or glycol. At this time, the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, water may be added in an amount of 0.5 times by mole of the total alkoxy groups in the alkoxysilane, but it is preferable to add water in an excess amount of 0.5 times by mole. In the present invention, the amount of water used in the above reaction may be appropriately selected as needed, but is preferably 0.5 to 2.5 times by mol based on the total alkoxy groups in the alkoxysilane.

In addition, for the purpose of promoting hydrolysis and condensation reactions, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, heptanoic acid, caprylic acid, pelargonic 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, sebacic acid, citric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, p-aminobenzoic acid, salicylic acid, gallic acid, phthalic acid, mellitic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and metal salts thereof; ammonia, methylamine, ethylamine, ethanolamine, triethylamine and other alkali catalysts. In addition, the hydrolysis and condensation reaction are further promoted by heating a solution in which the alkoxysilane is dissolved. In this case, the heating temperature and the heating time may be appropriately selected as necessary. Examples thereof include a method of heating at 50 ℃ and stirring for 24 hours, a method of heating under reflux and stirring for 1 hour, and the like.

In addition, another method includes, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent, and oxalic acid. Specifically, the method is a method of adding oxalic acid to an alcohol in advance to prepare an alcoholic solution of oxalic acid, and then mixing the solution with alkoxysilane in a heated state. In this case, the amount of oxalic acid used is preferably 0.05 to 5 mol% based on 1 mol of all alkoxy groups of the alkoxysilane. The heating in the method can be carried out at the liquid temperature of 50-180 ℃. In order to prevent evaporation, volatilization, and the like of the liquid, a method of heating under reflux for several tens of minutes to several tens of hours is preferable.

The silicone oligomer (A) used in the primer layer forming composition used in the present invention has a weight average molecular weight (Mw) of 100 to 10,000, preferably 500 to 5,000, as measured in terms of polystyrene by gel permeation chromatography.

In the present invention, it is presumed that the use of the siloxane oligomer as the primer layer forming material allows the oligomers to undergo a partial hydrolysis condensation reaction with each other when forming the primer layer, and the alcohol generated at this time volatilizes, so that the primer layer is considered to have a structure having a gap, which contributes to the improvement of the adhesion between the entire primer layer and the substrate and the hard coat layer.

[ solvent ]

The primer layer-forming composition used in the present invention may be in the form of a varnish by further including a solvent.

The solvent used in this case may be any solvent as long as it dissolves or disperses the component (a) and, if necessary, other components described later, and aromatic hydrocarbons such as toluene and xylene; esters or ester ethers such as ethyl acetate, butyl acetate, isobutyl acetate, γ -butyrolactone, methyl pyruvate, ethyl glycolate, ethyl lactate, butyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methylcellosolve acetate, ethylcellosolve acetate, Propylene Glycol Monomethyl Ether Acetate (PGMEA), and propylene glycol monopropyl ether acetate; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Propylene Glycol Monomethyl Ether (PGME); ketones such as Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, and propylene glycol; amides such as N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMF), and N-methyl-2-pyrrolidone (NMP). These solvents may be used alone or in combination of 2 or more, or in a mixed solvent with water.

The solid content concentration in the primer layer-forming composition used in the present invention is, for example, 0.01 to 70 mass%, 0.1 to 50 mass%, or 1 to 30 mass%. The solid content here is a component obtained by removing the solvent component from the entire components of the primer layer-forming composition.

[ other additives ]

Further, the primer layer-forming composition used in the present invention may be appropriately blended with commonly added additives such as a photosensitizer, a polymerization inhibitor, a polymerization initiator, a leveling agent, a surfactant, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like, and an active energy ray-curable polyfunctional monomer, if necessary, as long as the effects of the present invention are not impaired.

[ active energy ray-curable polyfunctional monomer ]

The primer layer forming composition used in the present invention may further contain an active energy ray-curable polyfunctional monomer in order to improve adhesion to an overlying hard coat layer.

Examples of the active energy ray-curable polyfunctional monomer used in the primer layer-forming composition include a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound, a polyfunctional epoxy (meth) acrylate compound, a polyfunctional polyester (meth) acrylate compound, and an unsaturated polyester, which are exemplified in the following equation (a) for the active energy ray-curable polyfunctional monomer.

In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

In the primer layer-forming composition used in the present invention, when an active energy ray-curable polyfunctional monomer is used, it is used in an amount of 1 to 300 parts by mass, preferably 1 to 200 parts by mass, and particularly preferably 10 to 100 parts by mass, based on 100 parts by mass of the above-mentioned (a) siloxane oligomer.

[ polymerization initiator generating free radicals by active energy ray ]

When the primer layer-forming composition used in the present invention contains the < active energy ray-curable polyfunctional monomer > described above, the composition may further contain various polymerization initiators exemplified below as < (d) a polymerization initiator that generates radicals by active energy rays.

In the primer layer-forming composition used in the present invention, when the polymerization initiator is contained, it is used in an amount of 0.1 to 25 parts by mass, preferably 0.1 to 20 parts by mass, and particularly preferably 1 to 20 parts by mass, based on 100 parts by mass of the siloxane oligomer (a).

Hard coating

< curable composition >

The hard coat layer in the antiglare hard coat laminate of the present invention is formed from a cured product (i.e., a cured film) of a curable composition containing the following (a) to (d).

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

The respective components (a) to (d) will be described below.

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

The active energy ray-curable polyfunctional monomer is a monomer which is cured by a polymerization reaction by irradiation with an active energy ray such as ultraviolet ray.

The active energy ray-curable polyfunctional monomer (a) in the curable composition used in the present invention is preferably a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate(meth) acrylate, propoxylated glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0^2,6]Decane dimethanol di (meth) acrylate, dioxane diol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl]Fluorene, bis [4- (meth) acryloyl-thiophenyl]Thioether, bis [2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) phosphate, epsilon-caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like.

Among these, preferred compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The polyfunctional urethane (meth) acrylate compound is a compound having 1 molecule thereof with a plurality of acryloyl groups or methacryloyl groups and one or more urethane bonds (-NHCOO-).

Examples of the polyfunctional urethane (meth) acrylate compound include a compound obtained by the reaction of a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, a compound obtained by the reaction of a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group and a polyol, and the like, but the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to these examples.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and 1, 6-hexamethylene diisocyanate.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate.

Further, examples of the polyhydric alcohol include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, and the like; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids such as succinic acid, maleic acid and adipic acid, or dicarboxylic anhydrides; a polyether polyol; polycarbonate diols, and the like.

In the present invention, as the active energy ray-curable polyfunctional monomer (a), one or more selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound may be used alone or in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Further, as the above-mentioned polyfunctional (meth) acrylate compound, it is preferable to use a polyfunctional (meth) acrylate compound having 5 or more functions in combination with a polyfunctional (meth) acrylate compound having 4 or less functions.

When the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound are used in combination, the polyfunctional urethane (meth) acrylate compound is preferably used in an amount of 20 to 100 parts by mass, more preferably 30 to 70 parts by mass, based on 100 parts by mass of the polyfunctional (meth) acrylate compound.

Further, in the case where the 5 or more functional polyfunctional (meth) acrylate compound and the 4 or less functional polyfunctional (meth) acrylate compound are used in combination in the polyfunctional (meth) acrylate compound, it is preferable to use 10 to 100 parts by mass, and more preferably 20 to 60 parts by mass of the 4 or less functional (meth) acrylate compound per 100 parts by mass of the 5 or more functional polyfunctional (meth) acrylate compound.

Further, it is preferable that: 20 to 100 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound, and 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functions per 100 parts by mass of a polyfunctional (meth) acrylate compound having 5 or more functions,

20 to 100 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound, and 20 to 60 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functions per 100 parts by mass of a polyfunctional (meth) acrylate compound having 5 or more functions,

30 to 70 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound, and 10 to 100 parts by mass of a polyfunctional (meth) acrylate compound having 4 or less functions per 100 parts by mass of a polyfunctional (meth) acrylate compound having 5 or more functions,

the amount of the polyfunctional urethane (meth) acrylate compound is 30 to 70 parts by mass per 100 parts by mass of the polyfunctional (meth) acrylate compound, and the amount of the polyfunctional (meth) acrylate compound having 4 or less functions is 20 to 60 parts by mass per 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functions.

[ (b) perfluoropolyether having active energy ray-polymerizable groups bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or having active energy ray-polymerizable groups bonded to both ends of a molecular chain via a poly (oxyalkylene) group and 1 urethane bond group in this order ]

In the present invention, as the component (b), the following perfluoropolyethers are used: active energy ray-polymerizable groups are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, or active energy ray-polymerizable groups are bonded to both ends of a molecular chain via a poly (oxyalkylene) group and 1 urethane bond in this order (hereinafter, also referred to simply as "(b) perfluoropolyether having polymerizable groups at both ends). (b) The component (b) functions as a surface modifier in a hard coat layer to which the curable composition used in the present invention is applied.

The number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, and the number of carbon atoms is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group is a group having a structure in which 2-valent fluorocarbon groups having 1 to 4 carbon atoms and oxygen atoms are alternately bonded, and the oxyperfluoroalkylene group is a group having a structure in which 2-valent fluorocarbon groups having 1 to 4 carbon atoms and oxygen atoms are bonded. Specifically, it includes- [ OCF ]₂]- (oxyperfluoromethylene), - [ OCF₂CF₂]- (oxyperfluoroethylene), - [ OCF₂CF₂CF₂]- (oxyperfluoropropane-1, 3-diyl), [ OCF₂C(CF₃)F]- (oxyperfluoropropane-1, 2-diyl) and the like.

One kind of the oxyperfluoroalkylene group may be used alone, or two or more kinds may be used in combination, and in this case, the combination of plural kinds of oxyperfluoroalkylene groups may be either of block combination and random combination.

Among them, from the viewpoint of obtaining a cured product (hard coat layer) having good abrasion resistance, it is preferable to use a poly (oxyperfluoroalkylene) group having- [ OCF ]₂]- (oxyperfluoromethylene) and- [ OCF₂CF₂]Both- (oxyperfluoroethylene) as the radical of the repeating unit.

Among them, the poly (oxyperfluoroalkylene) group is preferably a repeating unit: - [ OCF₂]And- [ OCF₂CF₂]-in molar ratio to become [ repeating unit: - [ OCF₂]-]: [ repeating unit: - [ OCF₂CF₂]-]2: 1-1: 2, more preferably so as to be in the range of about 1: the ratio of 1 contains their radicals. The combination of these repeating units may be either block combination or random combination.

The number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21 in total.

The poly (oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 2,000, in terms of polystyrene, as measured by gel permeation chromatography.

The number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, and is preferably 1 to 4. That is, the poly (oxyalkylene) group is a group having a structure in which alkylene groups having 1 to 4 carbon atoms and oxygen atoms are alternately bonded, and the oxyalkylene group is a group having a structure in which 2-valent alkylene groups having 1 to 4 carbon atoms and oxygen atoms are bonded. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a1, 3-propylene group, and a1, 4-butylene group.

One kind of the oxyalkylene group may be used alone, or two or more kinds may be used in combination, and in this case, the combination of plural kinds of oxyalkylene groups may be either of block combination and random combination.

Among them, the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.

The number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, more preferably, in the range of, for example, 5 to 12, and, for example, in the range of 7 to 12.

Examples of the active energy ray-polymerizable group bonded via a poly (oxyalkylene) group or via a poly (oxyalkylene) group and 1 urethane bond in this order include a (meth) acryloyl group, a urethane (meth) acryloyl group, a vinyl group and the like.

The active energy ray-polymerizable group is not limited to a group having 1 active energy ray-polymerizable moiety such as a (meth) acryloyl moiety, and may be a group having 2 or more active energy ray-polymerizable moieties, and examples thereof include structures of a1 to a5 shown below, and structures in which an acryloyl group in these structures is replaced with a methacryloyl group.

The perfluoropolyether (b) having polymerizable groups at both ends is preferably exemplified by the following compounds and compounds obtained by replacing acryloyl groups in these compounds with methacryloyl groups, from the viewpoint of ease of industrial production. In the structural formula, A represents 1 of the structures represented by the formulae [ A1] to [ A5], PFPE represents the poly (oxyperfluoroalkylene) group, and n represents the number of repeating units of oxyethylene groups independently of each other, preferably 1 to 15, more preferably 5 to 12, and still more preferably 7 to 12.

Among these, the perfluoropolyether (b) having polymerizable groups at both ends used in the present invention is preferably a perfluoropolyether having a poly (oxyperfluoroalkylene) group and 1 urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, that is, a perfluoropolyether having a poly (oxyperfluoroalkylene) group bonded to each of both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, 1 urethane bond bonded to each of the poly (oxyalkylene) groups at both ends, and an active energy ray polymerizable group bonded to each of the urethane bonds at both ends. Further, among the above perfluoropolyethers, those having an active energy ray-polymerizable group of at least 2 active energy ray-polymerizable moieties are preferable.

In the present invention, it is desirable that the perfluoropolyether (b) having polymerizable groups at both ends is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).

The perfluoropolyether (b) having polymerizable groups at both ends can be obtained, for example, by the following method: among compounds having a hydroxyl group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, a method of subjecting an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1, 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate to a carbamation reaction, a method of subjecting (meth) acryloyl chloride or chloromethylstyrene to a dehydrochlorination reaction, a method of subjecting (meth) acrylic acid to a dehydration reaction, a method of subjecting itaconic anhydride to an esterification reaction, and the like are given.

Among these, in the compounds having a hydroxyl group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group, a method of subjecting an isocyanate compound having a polymerizable group such as 2- (meth) acryloyloxyethyl isocyanate or 1, 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate to a urethanization reaction with respect to the hydroxyl group at both ends or a method of subjecting (meth) acryloyl chloride or chloromethyl styrene to a dehydrochlorination reaction with respect to the hydroxyl group is particularly preferable from the viewpoint of easiness of the reaction.

In addition, the curable composition used in the present invention may contain, in addition to (b) perfluoropolyether in which an active energy ray-polymerizable group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group or via a poly (oxyalkylene) group and 1 urethane bond in this order: a perfluoropolyether having an active energy ray-polymerizable group bonded via a poly (oxyalkylene) group or via a poly (oxyalkylene) group and 1 urethane bond in this order at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group, and having a hydroxyl group via a poly (oxyalkylene) group at the other end; perfluoropolyether having hydroxyl groups at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via the poly (oxyalkylene) group [ compound to which an active energy ray-polymerizable group is not bonded ].

[ (c) organic fine particles having an average particle diameter of 1 to 10 μm ]

In the curable composition used in the present invention, organic fine particles having an average particle diameter of 1 to 10 μm (hereinafter, also simply referred to as "(c) organic fine particles") impart antiglare properties to the surface of the hard coat layer formed from the curable composition in an uneven shape.

The organic fine particles can also play a role in controlling the haze value of the hard coat layer by controlling the difference between the refractive index of the organic fine particles and the refractive index of the curable composition as the hard coat layer forming material.

The shape of the organic fine particles is not particularly limited, and may be, for example, substantially spherical in the form of beads or may be an amorphous shape such as powder, but is preferably substantially spherical, more preferably substantially spherical particles having an aspect ratio of 1.5 or less, and most preferably spherical particles.

Examples of the organic fine particles include polymethyl methacrylate particles (PMMA particles), silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, polyvinyl fluoride particles, and the like. These organic fine particles may be used alone or in combination of two or more.

Among these, polymethyl methacrylate particles can be suitably used as the organic fine particles.

The organic fine particles used in the present invention preferably have an average particle diameter in the range of 1 to 10 μm, preferably 2 to 8 μm, and more preferably 3 to 8 μm. The average particle diameter (μm) here is a 50% volume diameter (median diameter) measured by a laser diffraction/scattering method based on Mie theory. If the average particle size of the organic fine particles is larger than the above numerical range, the image clarity of the display is lowered, and if the average particle size is smaller than the above numerical range, problems such as insufficient antiglare properties and increased glare (ギラツキ) tend to occur. The particle size distribution of the organic fine particles is not particularly limited, and monodisperse fine particles having uniform particle sizes are preferable.

The organic fine particles preferably have a refractive index difference of 0 to 0.20 from a cured product of the active energy ray-curable polyfunctional monomer (a), and more preferably have a refractive index difference of 0 to 0.10.

The average particle size of the organic fine particles is preferably selected so that the average particle size b/film thickness a of the organic fine particles is in the range of 0.3 to 1.0 relative to the film thickness of a hard coat layer, which is a cured product obtained from the curable composition used in the present invention described later.

The organic fine particles may be those commercially available, and examples thereof include テクポリマー (registered trademark) MBX series, テクポリマー SBX series, テクポリマー MSX series, テクポリマー SMX series, テクポリマー SSX series, テクポリマー BMX series, テクポリマー ABX series, テクポリマー ARX series, テクポリマー AFX series, テクポリマー MB series, テクポリマー MBP series, テクポリマー MB-C series, テクポリマー ACX series, and テクポリマー ACP series [ manufactured by hydroprocessment industries, Ltd. ]; トスパール (registered trademark) series [ モメンティブ, パフォーマンス, マテリアルズ, ジャパン (manufactured by same Co.) ]; エポスター series (registered trademark), エポスター MA series, エポスター ST series, エポスター MX series [ or more (strain) manufactured by japan catalyst) ]; オプトビーズ (registered trademark) series [ manufactured by Nissan chemical industry Co., Ltd ]; フロービーズ series [ manufactured by Sumitomo Seiko Co., Ltd ]; トレパール (registered trademark) PPS, トレパール PAI, トレパール PES, トレパール EP (manufactured by imperial arts レ, Inc.); 3M (registered trademark) ダイニオン TF Fine powder series [ manufactured by 3M Co. ]; 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 series, ケミスノー SX series, ケミスノー SGP series [ manufactured by Soken chemical Co., Ltd ]; タフチック (registered trademark) AR650 series, タフチック AR-750 series, タフチック FH-S series, タフチック A-20 series, タフチック YK series, タフチック ASF series, タフチック HU series, タフチック F series, タフチック C series, タフチック WS series [ supra, manufactured by Toyo Boseki Kaisha ]; アートパール (registered trademark) GR series, アートパール SE series, アートパール G series, アートパール GS series, アートパール J series, アートパール MF series, and アートパール BE series [ manufactured by Geneva industries, Ltd ]; shin-Yue シリコーン (registered trademark) KMP series (manufactured by shin-Yue chemical industry Co., Ltd.), and the like.

In the present invention, it is desirable that the organic fine particles (c) are used in an amount of 8 to 30 parts by mass, preferably 8 to 20 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).

[ (d) polymerization initiator generating free radical by active energy ray ]

In the curable composition used in the present invention, a polymerization initiator which generates radicals by active energy rays (hereinafter, also simply referred to as "(d) polymerization initiator") is preferably a polymerization initiator which generates radicals by irradiation with active energy rays such as electron rays, ultraviolet rays, and X-rays, particularly ultraviolet rays.

Examples of the polymerization initiator (d) include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones, biscoumarins, bisimidazolesMetallocenes, thiols, halogenated hydrocarbons, trichloromethyl triazines, or iodine

Onium salts, sulfonium salts and the like

Salts, and the like. These may be used singly or in combination of two or more.

Among them, in the present invention, from the viewpoint of transparency, surface curability, and film curability, it is preferable to use an alkylbenzene polymerization initiator as the polymerization initiator (d). By using the alkyl benzophenone-based polymerization initiator, a cured product (hard coat layer) having further improved scratch resistance can be obtained.

Examples of the above-mentioned alkylphenone-based polymerization initiator include α -hydroxyalkylbenzones such as 1-hydroxycyclohexyl ═ phenyl ═ ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, and 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; α -aminoalkylbenzones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl benzoylformate and the like.

In the present invention, it is desirable that the polymerization initiator (d) is used in an amount of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the active energy ray-curable polyfunctional monomer (a).

[ (e) solvent ]

The curable composition used in the present invention may further contain (e) a solvent, that is, be in the form of a varnish (film-forming material).

The solvent may be appropriately selected in consideration of the workability in coating, the drying properties before and after curing, and the like in the formation of a cured product (hard coat layer) described later, and the like, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; n-hexane and n-heptaneAliphatic or alicyclic hydrocarbons such as mineral spirits and cyclohexane; halogenated substances such as chloromethane, bromomethane, iodomethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene and the like; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1, 4-bis

Ethers such as alkane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol and ethylene glycol; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; heterocyclic compounds such as N-methyl-2-pyrrolidone, and mixed solvents of 2 or more of them.

In addition, a solvent having a high boiling point may be used for the purpose of controlling the dispersibility of the fine particles during drying after coating.

Examples of such solvents include cyclohexyl acetate, propylene glycol diacetate, 1, 3-butanediol diacetate, 1, 4-butanediol diacetate, 1, 6-hexanediol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1, 3-butanediol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol ═ methyl ═ propyl ═ ether, and the like.

The amount of the solvent (e) used is not particularly limited, and for example, the solvent (e) is used at a concentration of 1 to 70% by mass, preferably 5 to 50% by mass, of the solid content in the curable composition used in the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of the solid content (component obtained by removing the solvent component from the entire components) of the curable composition used in the present invention with respect to the total mass (total mass) of the components (a) to (e) (and other additives as needed).

[ other additives ]

In the curable composition used in the present invention, additives such as a polymerization accelerator, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, and a dye, which are usually added, may be appropriately added as necessary, as long as the effects of the present invention are not impaired.

Further, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured product (hard coat layer).

Anti-dazzle hard coating laminated body

As described above, the antiglare hard-coat laminate of the present invention is a 3-layer laminate composed of a substrate, a primer layer over the substrate, and a hard-coat layer over the primer layer.

The antiglare hard-coated laminate of the present invention is produced by the following steps:

(i) a step of applying a primer layer-forming composition to a substrate to form a coating film,

(ii) a step of forming a primer layer by heating and curing the coating film of the primer layer-forming composition,

(iii) a step of applying a curable composition on the primer layer to form a coating film, and

(iv) and a step of irradiating the coating film of the curable composition with active energy rays to cure the coating film to form a hard coat layer.

The primer layer-forming composition and the curable composition may be the respective compositions described above.

The coating method of the primer layer forming composition and the curable composition in the steps (i) and (iii) may be appropriately selected from a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, a spray coating method, a curtain coating method, an ink jet method, a printing method (relief printing, gravure printing, offset printing, screen printing, and the like), and among them, a spin coating method is preferably used because it can be applied in a short time, and therefore, even a highly volatile solution can be used, and further, it is easy to apply the composition uniformly. Further, it is desirable to use a roll coating method, a die coating method, or a spray coating method because of the advantages of easy coating and forming a smooth coating film without large-area coating unevenness. The composition for forming a primer layer and the curable composition used herein may be suitably used in the form of a varnish as described above. The primer layer-forming composition and the curable composition are preferably filtered in advance using a filter having a pore size of about 2 μm or the like and then applied.

After the primer layer forming composition in the step (i) is applied, the coating film is cured by heat treatment using an electric heating plate, an oven, or the like to form a primer layer in the step (ii). The heat treatment conditions in this case are, for example, preferably about 40 to 150 ℃ for 30 seconds to 10 minutes.

When the primer layer-forming composition contains an active energy ray-curable polyfunctional monomer and a polymerization initiator that generates radicals by active energy rays, an active energy ray irradiation step to be applied to a coating film of the curable composition described later can be applied.

After the application of the curable composition in the step (iii), it is preferable to perform preliminary drying using an electric heating plate, an oven, or the like, and then, as the step (iv), to form a hard coat layer by irradiating it with active energy rays such as ultraviolet rays and the like. Examples of the active energy ray include ultraviolet rays, electron beams, and X-rays. Examples of the light source used for the ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs.

Then, by performing post-baking, specifically, by heating using a hot plate, an oven, or the like, polymerization and polycondensation can be terminated.

In the laminate of the present invention obtained in this way, the thickness of the primer layer is not particularly limited, and may be, for example, in the range of 0.01 to 1 μm.

The hard coat layer is preferably set to have a thickness of 1 to 10/3 times the average particle diameter of the organic fine particles (c). For example, the thickness of the hard coat layer is in the range of 1 to 30 μm, preferably 1 to 20 μm, and more preferably 3 to 10 μm.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

In the examples, the apparatus and conditions used for the preparation of the sample and the analysis of the physical properties were as follows.

(1) Spin coating

The device comprises the following steps: ズースマイクロテック Labspin6TT, a spin coater

(2) Electric heating plate

The device comprises the following steps: アズワン strain MH-180CS and MH-3CS

(3) UV irradiation

The device comprises the following steps: アイ ultraviolet curing device US 5-04014 kW X1 lamp manufactured by アイグラフィックス Kabushiki Kaisha

(4) Scratch test

The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): 30S

Loading: 250g/cm²

Scanning speed: 3 m/min

(5) Gel Permeation Chromatography (GPC)

The device comprises the following steps: HLC-8220GPC manufactured by DONG ソー strain

Column: shodex (registered trademark) GPC KF-804L, product of Shorey electric corporation, GPC KF-805L

Column temperature: 40 deg.C

Eluent: tetrahydrofuran (THF)

A detector: RI (Ri)

(6) Film thickness

The device comprises the following steps: (Zu) ニコン digital length measuring machine デジマイクロ MH-15M + counter TC-101A

(7) Degree of gloss

The device comprises the following steps: GM-268Plus of gloss meter manufactured by コニカミノルタ K

Measuring an angle: 60 degree

(8) Total light transmittance and haze

The device comprises the following steps: NDH5000 haze Meter manufactured by Nippon Denshoku industries Ltd

(9) Contact angle

The device comprises the following steps: DropMaster DM-501 made by cooperative interfacial science (strain)

Measuring temperature: 20 deg.C

In addition, the abbreviation indicates the following meaning.

PFPE 1: perfluoropolyether having hydroxyl groups at both ends via poly (oxyalkylene) groups (repeating unit number 8-9) [ ソルベイスペシャルティポリマーズ Fluorolink5147X ]

BEI: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ カレンズ (registered trademark) BEI manufactured by SHOWA DENKO K.K. ]

DBTDL: dibutyl tin dilaurate (manufactured by Tokyo chemical industry Co., Ltd.)

HTES: triethoxy (hexyl) silane [ shin-Etsu シリコーン (registered trademark) KBE-3063, manufactured by shin-Etsu chemical Co., Ltd ]

MPTES: triethoxy (3-methacryloxypropyl) silane [ shin-Etsu シリコーン (registered trademark) KBE-503, manufactured by shin-Etsu chemical Co., Ltd ]

TEOS: tetraethoxysilane [ モメンティブ & パフォーマンス & マテリアルズ & ジャパン (same as TSL 8124)

DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture KAYALAD DPHA manufactured by Nippon Kagaku K.K.)

PETA: pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [ NK ester A-TMM-3LM-N, manufactured by Ningmura chemical industry Co., Ltd ]

UA: 6-functional aliphatic urethane acrylate oligomer [ EBECRYL (registered trademark) 5129 manufactured by ダイセル & オルネクス (Ltd.) ]

SM 2: UV-reactive fluorine-based surface modifier having perfluoropolyether structure [ メガファック (registered trademark) RS-75, available from DIC Co., Ltd., MEK/MIBK solution 40 mass% as an active ingredient ]

FP 1: cross-linked polymethyl methacrylate spherical particles [ テクポリマー (registered trademark) SSX-105 manufactured by Hydrogenfication industries, Ltd., average particle diameter 5 μm ]

FP 2: cross-linked polymethyl methacrylate spherical particles [ テクポリマー (registered trademark) SSX-103, manufactured by hydroprocessmg industries, Ltd., average particle diameter 3 μm ]

FP 3: cross-linked polymethyl methacrylate spherical particles [ テクポリマー (registered trademark) SSX-102, manufactured by hydroprocessmg industries, Ltd., average particle diameter 2 μm ]

I2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ IRGACURE 2959, manufactured by BASF ジャパン ]

EPA: ethyl p-dimethylaminobenzoate [ KAYACURE EPA manufactured by JAPONICA CHEMICAL (KOKAYACURE Co., Ltd.) ]

EtOH: ethanol

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

PGME: propylene glycol monomethyl ether

Production example 1 production of perfluoropolyether SM1 having acryloyl groups at both terminals via a poly (oxyalkylene) group and 1 urethane bond

1.05g (0.5mmol) of PFPE1, 0.26g (1.0mmol) of BEI, 10mg (0.016mmol) of DBTDL, and 1.30g of MEK were introduced into the threaded tube. The mixture was stirred at room temperature (about 23 ℃) for 24 hours using a stirrer. The reaction mixture was diluted with 3.93g of MEK to obtain a 20 mass% MEK solution of SM1 as a target compound.

The weight average molecular weight Mw of the obtained SM1 in terms of polystyrene obtained by GPC was 3,400, and the degree of dispersion: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

Production examples 2-1 to 2-3 preparation of primer compositions (compositions for Forming primer layer)

Alkoxysilane and ethanol were added to a reaction flask as described in table 1, and the mixture was stirred for 5 minutes under a nitrogen stream to prepare an alkoxysilane/ethanol solution. To this solution, an oxalic acid-water/ethanol solution prepared separately as described in table 1 was added dropwise over 10 minutes. After stirring the solution for 30 minutes, it was heated and stirred for 1 hour until the internal solution was refluxed (about 80 ℃). The reaction mixture was cooled to room temperature (about 23 ℃ C.), and a primer composition (PR 1-PR 3) having a siloxane oligomer concentration of 40 mass% was obtained.

Weight average molecular weight Mw and dispersity of the obtained siloxane oligomer in terms of polystyrene obtained by GPC: Mw/Mn is 1,400, 1.1(PR1), 1,500, 1.1(PR2), 1,500, 1.1(PR3), respectively.

TABLE 1

Production examples 3-1 to 3-4 preparation of hard coating compositions (curable compositions)

Hard coat compositions (HC1 to HC4) having a solid content of 40 mass% were prepared by mixing the following components as shown in table 2. The solid content here means a component other than the solvent. In the table, "part" means "part by mass".

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

(2) Surface modifier: 1 part by mass (in terms of solid content or active ingredient) of the surface modifier shown in Table 2

(3) Organic microparticles: the organic fine particles shown in Table 2 were added in the amounts shown in Table 2

(4) Polymerization initiator: i29595 parts by mass

(5) Polymerization accelerator: EPA 0.1 part by mass

(6) Solvent: amounts of PGME listed in Table 2

TABLE 2

Examples 1 to 8 and comparative examples 1 to 3

The primer composition diluted with PGME so as to have the solid content concentration (siloxane oligomer concentration) described in table 3 was spin-coated (1,000rpm × 30 seconds) on a glass substrate (10cm × 10cm, thickness 0.7mm) to obtain a coating film. The coating film was heated on a hot plate at 120 ℃ for 1 hour to form a primer layer (cured film) having a thickness shown in table 3.

On this primer layer, the hard coat composition described in table 3 was spin-coated (rotation speed × 30 seconds described in table 3) to obtain a coating film. The coating film was dried for 3 minutes on a hot plate at 120 ℃ to remove the solvent. The obtained film was irradiated with an exposure of 500mJ/cm in a nitrogen atmosphere²Was exposed to UV light to produce a hard coat laminate having a hard coat layer (cured film) having a thickness shown in table 3.

The obtained hard coat laminate was evaluated for anti-glare property, adhesion, scratch resistance, total light transmittance, haze, and contact angle between water and oleic acid. The following evaluation procedures for antiglare properties, adhesion, scratch resistance, and contact angle are shown. The results are shown in table 4.

[ anti-dazzle Property ]

The obtained hard coat laminate was placed on a black stage having a gloss Gs (60 °) of 11.8, and the gloss Gs (60 °) of the hard coat layer surface was measured and evaluated according to the following criteria. When the hard coat laminate is assumed to be practically used, at least B, preferably a is required.

A：Gs(60°)≤120

B：120＜Gs(60°)≤125

C：Gs(60°)＞125

[ Adhesivity ]

The hard coat layer was subjected to 25 cuts in a rectangular grid pattern (5X 5, 2mm intervals) using a grid plate [ CCI-2, manufactured by コーテック Corp.), and evaluated by the following criteria using a cross-hatch method (in accordance with JIS5600-5-6) using a transparent tape [ セロテープ (registered trademark) CT-18, manufactured by ニチバン Corp.) having a width of 18 mm.

A: 25 pieces of the composition were not peeled off

B: 1 to 11 pieces of peeling

C: peeling off more than 12 pieces

[ scratch resistance ]

Steel wool (ボンスター (registered trademark) #0000 (ultra fine) manufactured by ボンスター casing strain) mounted on a reciprocating abrasion tester was used for the hard coating surface]Application of 250g/cm²The load of (2) was wiped off 1,000 times, and マッキー fine (blue) color made by oil-based marker [ ゼブラ K ] was used]Drawing a line on the wiped portion. Then, the drawn nonwoven fabric rag for string [ BEMCOT (registered trademark) M-1 made by Asahi Kasei corporation ]]The degree of scratch was visually confirmed by rubbing and evaluated according to the following criteria. In addition, when the hard coat laminate is assumed to be practically used, at least B, preferably a is required.

A: the thread drawn by the oil-based marking pen is cleanly wiped off without being damaged

B: slightly injured, but the line drawn with the oil marker was cleanly wiped off

C: the ink of the oil-based marker enters the wound and cannot be wiped off

[ contact Angle ]

Water or oleic acid was allowed to adhere to the surface of the hard coat layer in an amount of 1 μ L, and the contact angle θ after 5 seconds was measured at 5 points, and the average value was defined as the contact angle value.

TABLE 3

TABLE 4

As shown in tables 1 to 4, when forming a hard coat layer using perfluoropolyether SM1 having acryloyl groups bonded to both ends via poly (oxyalkylene) groups and 1 urethane bond as a surface modifier, laminates 1 to 6, 10, and 11 of examples 1 to 8 provided with a primer layer were produced which had excellent antiglare properties, satisfactory adhesion and scratch resistance even in actual use, and excellent transparency.

On the other hand, when a siloxane oligomer having no radical polymerizable double bond (a siloxane oligomer exceeding the definition of the present invention) was used as the primer layer (comparative example 1) and when no primer layer was provided (comparative example 2), the adhesion of the hard coat layer to the glass substrate was low and the abrasion resistance was poor.

In addition, when the UV-reactive fluorine-based surface modifier SM2 having a perfluoropolyether structure was used as the surface modifier for the hard coat layer (comparative example 3), the desired scratch resistance could not be obtained although the results of the antiglare property and the adhesion property were satisfied.

As described above, as shown in the results of examples, in a laminate having a hard coat layer using a specific perfluoropolyether as a surface modifier, by providing a primer layer formed of a cured product of a material containing a specific siloxane oligomer having a radical polymerizable double bond, a laminate satisfying all of the performances of antiglare property, scratch resistance, and adhesion to a substrate can be obtained.

Claims

1. An anti-glare hard-coated laminate composed of a substrate, a primer layer over the substrate, and a hard-coated layer over the primer layer,

the primer layer is formed from a cured product of a primer layer forming composition containing:

a siloxane oligomer having a radical polymerizable double bond as component A, which is obtained by hydrolytic condensation of an alkoxysilane containing at least an alkoxysilane A represented by the formula [1] and an alkoxysilane B represented by the formula [2],

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

in the formula, R¹Represents a 1-valent organic group having a radically polymerizable double bond, R³Represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an amino group substituted with at least an alkyl group having 1 to 6 carbon atoms, an amino group substituted with at least a phenyl group, or a ureido group, R²And R⁴Each independently represents a methyl group or an ethyl group, a represents 1 or 2, and b represents an integer of 0 to 2;

100 parts by mass of an active energy ray-curable polyfunctional monomer as the component a,

and (b) 0.1 to 10 parts by mass of a perfluoropolyether having an active energy ray-polymerizable group bonded to both ends of a molecular chain containing a polyoxyperfluoroalkylene group via a polyoxyalkylene group or an active energy ray-polymerizable group bonded to both ends of a molecular chain via a polyoxyalkylene group and 1 urethane bond group in this order,

8 to 30 parts by mass of organic fine particles having an average particle diameter of 1 to 10 μm as component c, and

and (d) 1 to 20 parts by mass of a polymerization initiator which generates a radical by an active energy ray.

2. The antiglare hard-coated laminate according to claim 1, the siloxane oligomer of component A being a siloxane oligomer having a radical polymerizable double bond obtained by hydrolytic condensation of an alkoxysilane A represented by formula [1] and an alkoxysilane B represented by formula [2],

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

in the formula, R¹Represents a 1-valent organic group having a radically polymerizable double bond, R³Represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a fluorine atom, or a phenyl group, R²And R⁴Each independently represents a methyl group or an ethyl group, a represents 1 or 2, and b represents an integer of 0 to 2.

3. The antiglare hardcoat laminate of claim 1 or 2 of formula [1]R in (1)¹Is a 1-valent organic group having a vinyl group or a (meth) acryloyl group.

4. The anti-glare hard-coated laminate according to claim 3, wherein the alkoxysilane A is a compound represented by the following formula [3],

in the formula, R²Is represented by the formula [1]Wherein R is as defined in⁵Represents a hydrogen atom or a methyl group, L¹Represents an alkylene group having 1 to 10 carbon atoms.

5. The antiglare hardcoat laminate of claim 1 or 2, the siloxane oligomer having a radical polymerizable double bond of component a being a siloxane oligomer containing 10 to 99 mol% of a unit derived from the alkoxysilane a.

6. The anti-glare hard-coated laminate according to claim 1 or 2, wherein the polyoxyperfluoroalkylene group of the perfluoropolyether of the component b has- [ OCF [ ]₂]-and- [ OCF₂CF₂]-a group as a repeating unit.

7. The anti-glare hard-coated laminate according to claim 1 or 2, wherein the polyoxyalkylene group of the perfluoropolyether of the component b is a polyoxyethylene group.

8. The anti-glare hard-coated laminate according to claim 1 or 2, the polyfunctional monomer of the component a being at least 1 selected from a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.

9. The antiglare hard-coated laminate according to claim 1 or 2, the organic fine particles of the component c being regular spherical particles.

10. The antiglare hard-coated laminate according to claim 1 or 2, the organic fine particles of the component c being polymethyl methacrylate particles.

11. The antiglare hard-coated laminate according to claim 1 or 2, the polymerization initiator of the component d being an alkylphenone-based polymerization initiator.

12. The antiglare hard-coated laminate according to claim 1 or 2, wherein the thickness of the hard-coated layer is 1 to 10/3 times the average particle diameter of the organic fine particles of the component c.

13. The antiglare hard-coated laminate according to claim 1 or 2, the hard-coated layer having a film thickness of 1 to 20 μm.

14. The antiglare hard-coated laminate according to claim 13, the hard-coated layer having a film thickness of 3 to 10 μm.

15. The anti-glare hardcoat laminate of claim 1 or 2 wherein the substrate is glass.

16. A method for producing an antiglare hard-coated laminate comprising a primer layer on at least one surface of a substrate and a hard-coating layer provided over the primer layer, the method comprising:

the primer layer forming composition includes:

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

the curable composition comprises: