JP2003034761A - Hard coating composition and hard coating product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coating composition capable of providing a hard coating having antiglare properties, abrasion resistance, water repellency, and effects for reducing and easily removing stains, while maintaining visible light transmission properties by one step (of application work) in a process for applying and curing the hard coating composition on both surfaces or one side of transparent resins. SOLUTION: An active energy ray-curable hard coating composition comprises multifunctional acrylates, reaction products of multifunctional acrylates with amino-organic functional silanes, fluorine-containing silicon compounds, colloidal silica, and fine particles having average particle diameter of 50 nm-10 μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hard coat composition and a hard coat resin product. More specifically, it relates to a hard coat composition that gives a hard coat excellent in antiglare property and water repellency, and a hard coat product provided with the hard coat obtained therefrom.

[0002]

2. Description of the Related Art Conventionally, a technique for obtaining an antiglare hard coat product by forming a liquid, which is a combination of a hard coat and an antiglare effect, on a transparent resin substrate or film has existed for a long time.
In fact, it has been commercialized as a film used for a display of a notebook computer.

In many cases, the antiglare effect utilizes the light scattering effect of fine particles on the film surface (Japanese Patent Laid-Open No. 2771/1993).
No. 03, No. 8-309910, No. 9
-230103, JP-A-10-20103, and JP-A-11-326608).

However, since these techniques utilize surface irregularities made of fine particles in order to obtain an antiglare effect, stains are accumulated on the irregularities, which makes it difficult to remove once stains are attached. There is.

On the other hand, in order to improve this, a technique combined with a water repellent treatment, that is, a technique of performing a water repellent treatment on an uneven surface is also known (Japanese Unexamined Patent Publication Nos. 2000-16838 and 2000-258606). reference).

However, in these techniques, the number of steps is increased because the treatment is performed on the antiglare layer, and the cost and defects are likely to occur. Further, Japanese Patent Laid-Open No. 2000-16838 cannot be applied to something like plastic because the base material is glass.

A technique has also been proposed in which a hard coat is cured by utilizing active energy, and the same fine particles scatter to impart an antiglare function (Japanese Patent Laid-Open No. 2000-258).
606, JP-A-11-352899, JP-A-10-20103 and JP-A-8-30991.
No. 0 publication).

[0008]

The object of the present invention is to coat and cure both sides or one side of a transparent resin so that visible light transmittance can be maintained in one step (coating operation).
It is an object of the present invention to provide a hard coat composition capable of imparting a hard coat having antiglare properties, scratch resistance, water repellency, stain reduction, and stain removal easiness.

Another object of the present invention is to provide a hard coat resin product having a hard coat having the above-mentioned excellent performance by the hard coat composition of the present invention.

Further objects and advantages of the present invention will be apparent from the following description.

[0011]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a polyfunctional acrylate; (B) an aminoorganofunctional silane; and (C) a fluoroalkylsilane. , (D) colloidal silica and (E) fine particles having an average particle size of 50 nm to 10 μm.

Secondly, the above objects and advantages of the present invention are characterized in that a hard coat layer comprising the above hard coat composition of the present invention is provided on a resin substrate through a primer layer. This is achieved by a coated resin product (hereinafter sometimes referred to as a first resin product).

Further, the above objects and advantages of the present invention are as follows.
Thirdly, it is achieved by a hard coat resin product (hereinafter sometimes referred to as a second resin product), which comprises a hard coat layer of the hard coat composition of the present invention on a resin substrate.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. First, the hard coat composition of the present invention will be described.

The hard coat composition of the present invention contains the components (A) to (E) as described above. Examples of the polyfunctional acrylate of the component (A) include 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate. , Neopentyl glycol diacrylate,
1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate,
Diacrylates such as triisopropylene glycol diacrylate, polyethylene glycol diacrylate and bisphenol A dimethacrylate; such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxytriacrylate and trimethylolpropane triethoxytriacrylate. Mention may be made of triacrylates; tetraacrylates such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate; and pentaacrylates such as dipentaerythritol (monohydroxy) pentaacrylate. The polyfunctional acrylate is used alone or in combination of two or more.

As the aminoorganofunctional silane of the component (B), an aminoorganofunctional silane represented by the following formula (1) is preferably used. X _a Si (R ¹ (NHR ² ) _b NR ³ H) _4-a (1) Here, X is an alkoxyl group having 1 to 6 carbon atoms, and R ¹ and R ² are the same or different divalent. It is a hydrocarbon group, R ³ is a hydrogen atom or a monovalent hydrocarbon group, a is an integer of 1 to 3, and b is an integer of 0 to 6.

Silanes in which b in formula (1) is 0 or 1 are preferred. Examples of the silane represented by the formula (1) include n- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and anilinopropyltrimethoxysilane. Mention may be made of methoxysilane.

The fluoroalkylsilane as the component (C) is represented by the following formula (2) R ¹ _a R ² _b Si (OR ³ ) _4-ad (2) where R ¹ is fluorine having 1 to 12 carbon atoms. R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Group, an acyl group, and a is 1,2
Or 3 and b is 0, 1 or 2, provided that a is
+ B is 1, 2 or 3, and a fluorine-containing silicon compound represented by is preferably used.

Examples of the compound represented by the above formula (2) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane and heptadecafluorodecyltrisilane. Mention may be made of fluoroalkyltrialkoxysilanes such as methoxysilane, heptadecafluorodecyltriethoxysilane; fluoroalkylalkyldialkoxysilanes such as heptadecafluorodecylmethyldimethoxysilane and heptadecafluorodecylmethyldiethoxysilane.

These may be used alone or in combination of two or more.

Colloidal silica (D) is, for example, 10-5.
Colloidal silica (sol) containing 0% by weight of SiO ₂ (particle size 1 to 200 nm, preferably 1 to 100 nm) as an active ingredient or SiO ₂ having a particle size of 1 to 200 nm, more preferably 1 to 100 nm. It can be derived from composite oxide fine particles.

The composite oxide is SiO₂With metal oxides
The metal oxide is, for example, A
l, Sn, Sb, Ta, Ce, La, Fe, Zn, W,
1 selected from the group consisting of Zr, Pd, In and Ti
Can include oxides of one or more metals
Wear. Specific examples of the metal oxide include Al₂O₃, SnO
₂, Sb₂O_Five, Ta₂O_Five, CeO₂, La₂O₃, Fe
₂O₃, ZnO, WO₃, ZrO₂, PdO₂, In₂O₃Oh
And TiO₂Can be mentioned.

The composite oxide may be surface-modified with an organic silane compound in order to enhance dispersibility in a solvent. The amount of the organic silane compound used is based on the weight of the composite oxide particles.
It is preferably 20% by weight or less.

The surface treatment may be carried out with the organic silane compound used for the treatment having a hydrolyzable group or after the hydrolysis.

Examples of such an organic silane compound include those represented by the following formula R ₃ SiX, where R is an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group or an epoxy group, and X is a hydrolyzed group. A possible functional group, a monofunctional silane represented by the following formula R ₂ SiX ₂ wherein R and X are the same as defined above, a bifunctional silane represented by the following formula RSiX ₃ Wherein the definitions of R and X are the same as above, and a trifunctional silane represented by and the following formula SiX ₄ wherein the definition of X is the same as above, You can

As the monofunctional silane of the above formula, for example, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, Vinyldimethylmethoxysilane, vinyldimethylethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldimethylethoxysilane, N-β (aminoethyl ) Γ-Aminopropyldimethylmethoxysilane, γ-
Aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethoxyethoxysilane and β- (3.4-epoxycyclohexyl) ethyldimethylmethoxysilane. be able to.

Further, as the bifunctional silane, for example,
Dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-acryloxypropylmethyl Dimethoxysilane, γ-methacryloxypropyldimethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Mention may be made of glycidoxypropylmethoxydiethoxysilane and β- (3.4-epoxycyclohexyl) ethylmethyldimethoxysilane.

Further, as the trifunctional silane, for example,
Methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane, γ -Acryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl)
γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, β
-Glycidoxypropyltriethoxysilane and β-
Mention may be made of (3.4-epoxycyclohexyl) ethyltrimethoxysilane.

Furthermore, examples of the tetrafunctional silane include tetraethyl orthosilicate and tetramethyl orthosilicate.

The treatment of the composite oxide with such a silane compound is preferably carried out in, for example, water, alcohol or another organic medium.

Examples of the alcohol include saturated aliphatic alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol and 2-butanol;
Cellosolves such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve; propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl acetate; esters such as methyl acetate, ethyl acetate, butyl acetate;
Ethers such as diethyl ether and methyl isobutyl ether; ketones such as acetone and methyl isobutyl ketone; aromatic hydrocarbons such as xylene and toluene;
Examples thereof include ethylene glycol, tetrahydrofuran, N, N, -dimethylformamide, dichloroethane and the like.

The fine particles (E) having an average particle diameter of 0.05 to 10 μm, preferably 2 to 10 μm are, for example, S
i, Al, Sn, Sb, Ta, Ce, La, Fe, Z
Examples thereof include n, W, In, Ti, Mg, oxides thereof, complex oxides, CaCO ₃ and BaSO ₄ .
These can be used alone or in combination of two or more. Of these, SiO ₂ is the most preferable.

These fine particles can be used after being surface-modified with an organic silane compound or an organic compound in order to enhance dispersibility in a solvent. As the organic silane compound, the organic silane compounds exemplified for the surface modification of colloidal silica, especially the monofunctional silane represented by the formula R ₃ SiX, are preferably used.

Average particle size 0.05 μm (50 nm) to 10
A product obtained by dispersing 15 to 60% by weight in a dispersion medium as the microparticles (E) having a diameter of μm is commercially available as follows.

Silica fine particles ... "Cyroid C803"
(Average particle size 3.6 μm, manufactured by WR Grace Japan), “Sylysia 350” (average particle size: 3.9 μm,
(Manufactured by Fuji Silysia Chemical Ltd.), "Cylosphere C-1
504 "(average particle size 4 μm, manufactured by the same company),“ CYLOSPHERE C-1510 ”(average particle size 10 μm, manufactured by the same company),“ R ”
X200 "(average particle size 12 nm, manufactured by Japan Aerogel Co., Ltd.)," JA-450 "(average particle size 4-8 μm,
Jujo Chemical Co., Ltd.), “MP-3040” (Average particle size: 0.30 μm, Nissan Chemical Co., Ltd.), “MP-
4540 "(average particle size: 0.45 µm, manufactured by Nissan Chemical Industries, Ltd.)," KE-W50 "(average particle size: 0.50-
0.56 μm, manufactured by Nippon Shokubai Co., Ltd., “KE-E15
0 "(average particle size: 1.40 to 1.60 μm, manufactured by Nippon Shokubai Co., Ltd.). Other than silica fine particles, titanium oxide fine particles “Palladium characteristic matting agent N” (average particle size 2 to 5 μm)
m, manufactured by Ohara Palladium Co., Ltd., calcium stearate fine particles “palladium # 1000” (average particle diameter 2-5)
μm, manufactured by Ohara Palladium Co., Ltd., and the like.

These fine particles are preferably spherical or nearly spherical, and may be solid particles or porous particles. Further, the refractive index thereof is preferably the same as or smaller than the refractive index of the photocured product of the remaining composition excluding the fine particles.
By doing so, interference unevenness due to film thickness unevenness is easily reduced.

The preferred particle size of the fine particles (E) is 2 to 10 μm.
m, and a more preferable particle size is 4 to 8 μm.

Colloidal silica (D) is a component that enhances the hardness of the hard coat layer. The fine particles (E) are components that form predetermined irregularities on the surface of the hard coat layer to impart antiglare properties. Colloidal silica with a large average particle size,
For example, colloidal silica having an average particle diameter of 50 nm to 200 nm also acts as fine particles (E). Therefore, if the hard coat composition of the present invention contains the colloidal silica (D) having an average particle diameter of 50 nm to 200 nm, the fine particles (E) may not be contained.

The hard coat composition of the present invention preferably contains a photopolymerization initiator for photopolymerization of the polyfunctional acrylate. As the photopolymerization initiator, a radical photopolymerization initiator, a cationic photopolymerization initiator or the like can be used. As the radical photopolymerization initiator, benzophenone,
[2-hydroxy-2-methyl-1-phenylpropan-1-one], [1- (4-isopropylphenyl)-
2-hydroxy-2-methylpropan-1-one],
[4- (2-hydroxyethoxy) phenyl-2-hydroxy-2-propylketone], [2,2-dimethoxy-1,2-diphenylethan-1-one], [1-hydroxy-cyclohexyl-phenyl-ketone] ], [2-
Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one], [bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide], [2 -Benzyl-2-dimethylamino-1--1- (4-morpholinophenyl)
-Butanone-1] can be exemplified. Further, as the cationic photopolymerization initiator, phenyl- [m- (2-hydroxytetradecyclo) phenyl] iodonium hexafluoroantimonate, dialkyliodonium,
Examples thereof include tetrakis (pentafluorophenyl) borate. The amount of the photopolymerization initiator is 0. 0, based on 100 parts by weight of the polyfunctional acrylate (A) of the hard coat composition.
The amount is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight.

The hard coat composition of the present invention is preferably 1.5 to 50 parts by weight, preferably 8 to 25 parts by weight, with respect to 100 parts by weight of the polyfunctional acrylate (A), the aminoorganofunctional silane (B). Fluoroalkylsilane (C)
1.0 to 20 parts by weight, preferably 3 to 15 parts by weight, colloidal silica (D) (solid content) 10 to 150 parts by weight, preferably 40 to 85 parts by weight and an average particle diameter of 0.05 μm.
(50 nm) to 10 μm fine particles (E) 1.0 to 150
Parts by weight, preferably 3 to 100 parts by weight. The more preferable content of the fine particles (E) depends on the average particle diameter of the fine particles (E). When the average particle size of the fine particles (E) is relatively large, for example, more than 2 μm and 10 μm or less, the content of the fine particles (E) is preferably 1.0 to 40 parts by weight, and 3 to 20 parts by weight. More preferable. Fine particles (E)
When the average particle size of is relatively small, for example, 0.05 μm
When it is (50 nm) to 2 μm, the content of the fine particles (E) is preferably 20 to 150 parts by weight, more preferably 50 to 100 parts by weight.

Colloidal silica (D) containing only colloidal silica (D) which also serves as fine particles (E)
The content of (solid content) is 40 to 185 parts by weight, preferably 60 to 130 parts by weight.

The hard coat composition of the present invention is preferably prepared as a dispersion in a liquid medium containing the above-mentioned active ingredient in a predetermined amount.

The polyfunctional acrylate (A) reacts with the aminoorganofunctional silane (B) during the preparation of the hard coat composition or during the aging after the preparation.

In the reaction of the polyfunctional acrylate with the aminoorganofunctional silane, the primary or secondary amine functionality of the aminoorganofunctional silane is one of the acrylate double bonds of the polyfunctional acrylate monomer. Add Michael to 2 or more. The reaction can be carried out at temperatures from room temperature to 100 ° C. In the reaction, the polyfunctional acrylate and the aminoorganofunctional silane can be used alone or in combination of two or more kinds.

Examples of the liquid medium of the hard coat composition include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol. Monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol di Glycols such as chill ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; cyclohexanone, o-methylcyclohexanone, m-methyl Cyclohexanone, p
-Aliphatic cyclic ketones such as methylcyclohexanone;
Acetic acid esters such as ethyl acetate n-propyl acetate and n-butyl acetate; alcohols such as methanol, ethanol, 1-propanol and 2-propanol can be mentioned.

Further, the above dispersion liquid may contain a leveling agent for the cured film and a lubricity imparting agent as optional components. As such an agent, for example, a copolymer of polyoxyalkylene and polydimethylsiloxane (Paint Additive 19 manufactured by Dow Corning) and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. Such an agent is preferably used in an amount of 0.001 to 10% by weight based on the total amount of liquid.

Other optional components may include antioxidants, weather resistance imparting agents, antistatic agents, bluing agents and the like.

The above dispersion has a solid content concentration of, for example, 2 to 5
It is preferably adjusted to 0% by weight and used.

Next, the first resin product of the present invention will be described.

The first resin product is a product in which the hard coat composition of the present invention is applied to a resin substrate via a primer.

The primer layer comprises an organic resin and preferably 5% by weight or more of an effective non-volatile content of an ultraviolet absorber.

As the organic resin, a resin which is in close contact with a resin substrate such as a polycarbonate plate and which can be adhered to the silicon hard coat is used. Such organic resins are known, and preferred examples thereof include an acrylic polymer, a copolymer of an acrylic monomer and methacryloxysilane, or a copolymer of a methacrylic monomer having a benzotriazole group or a benzophenone group and an acrylic monomer. it can. Among these, acrylic polymers and copolymers of acrylic monomers and methacryloxysilane are more preferable. The organic resins may be used alone or in combination of two or more.

As the ultraviolet absorber contained in the primer layer, for example, benzotriazole type and benzophenone type are preferable.
Of these, benzophenone type is more preferable. The ultraviolet absorber may be used alone or in combination of two or more.

Examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butyl. Phenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-
Butylphenyl) -5-chloro-benzotriazole,
Alternatively, Tinuvin 328, Tinuvin 384, Tinuvin 900, Tinuvin 928, and Tinuvin 1130 from Ciba Specialty Chemicals Co., Ltd. can be mentioned.

As the benzophenone type ultraviolet absorber,
For example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2,2 ', 4,
Mention may be made of 4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

In addition, as the ultraviolet absorber, a silane compound having a benzotriazole or benzophenone group can also be used.

The ultraviolet absorber is contained in an amount of 5% by weight or more, preferably 10 to 60% by weight, and more preferably 20 to 50% by weight of the effective non-volatile component in the primer layer.

For the primer layer, a solvent solution containing a predetermined amount of an ultraviolet absorber and an organic resin is applied onto a resin base material,
It is formed by removing the solvent and heat-curing.

Examples of the solvent include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl acetate. Propyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
Ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Glycols such as diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether; cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone, Aliphatic cyclic ketones such as p-methylcyclohexanone; ethyl acetate n-propyl acetate, acetic acid n-
Acetic acid esters such as butyl; alcohols such as methanol, ethanol, 1-propanol and 2-propanol, solvent naphtha, methyl ethyl ketone and the like can be mentioned.

The above-mentioned solvent solution is used as an optional component.
A leveling agent for the cured film and a lubricity imparting agent may be contained. As such an agent, for example, a copolymer of polyoxyalkylene and polydimethylsiloxane (Paint Additive 31 manufactured by Dow Corning) and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. Such an agent is 0.001 to 10 with respect to the total amount of liquid.
It is preferably used in weight%.

As other optional components, an antioxidant, a weather resistance-imparting agent, an antistatic agent, a bluing agent and the like may be contained.

The solvent solution has a solid content concentration of, for example, 2 to
It is preferably adjusted to 50% by weight and used.

The coating can be carried out, for example, by a dip method, a flow method, a spinner method, a spray method, a roll coating method, a gravure coating method, a flexographic printing method, a screen printing method, or a brush coating method.

The coating is preferably carried out so that the film thickness after curing is 1 to 10 μm. If it is less than 1 μm, the yellowing resistance and weather resistance are not sufficient, while if it is more than 10 μm, the hardness tends to be lowered after the hard coating.

After coating, the solution coating film is, for example, for 1 minute to several hours.
The primer layer is provided by being heat-treated at a temperature of 15 to 120 ° C.

The first hard coat composition can be applied onto the primer layer by, for example, dipping method, flow method, spinner method, spray method, roll coating method, gravure coating method,
It can be performed by a flexographic printing method, a screen printing method, or a brush coating method. After application, the liquid medium is vaporized and removed by drying or during the irradiation described below.

The coating is preferably carried out so that the cured film has a thickness of 1.0 to 9 μm. If it is less than 1.0 μm, the hardness is insufficient, while if it is more than 9 μm, the antiglare effect is reduced.

However, when the underlying hard coat layer is provided below the hard coat layer as described below, the thickness of the hard coat layer after curing can be set to 0.05 to 1.5 μm. Since the surface of the hard coat layer has minute irregularities, the thickness of the hard coat layer is defined as an average thickness including surface irregularities.

After coating, the dispersion coating film is irradiated with ultraviolet rays or electron beams to form a cured coating film.

By this irradiation, the (meth) acrylic groups of the polyfunctional acrylate (A) are photopolymerized. The hydrolyzable groups such as alkoxyl groups in the aminoorganofunctional silane (B) and the fluoroalkylsilane (C) may be added during the preparation of the hard coat composition, the aging, the post-application irradiation or the post-application irradiation. Hydrolyzes and polycondensates.

The second resin product of the present invention is obtained by applying the hard coat composition of the present invention on a resin substrate. The hard coat composition can be applied to the resin substrate in the same manner as described for the first resin product.

The first resin product of the present invention may have a hard coat layer on one surface or both surfaces of the resin base material, for example, the transparent plate, through a primer.

Similarly, for the second resin product, for example, only on one surface of the transparent plate, or on both surfaces,
The hard coat layer can be directly provided.

Further, according to the present invention, there is also provided a product having a hard coat layer on one surface of a transparent plate through a primer and a hard coat layer directly on the other surface.

An undercoating hard coat layer is further provided between the primer layer and the hard coat layer of the first resin product of the present invention or between the resin base material and the hard coat layer of the second resin product of the present invention. Can be provided.

The base hard coat layer comprises (F) a polyfunctional acrylate, (G) the following formula (3) R ⁷ _n Si (R ⁸ ) _4-n (3) where R ⁷ is a methacryloxy group or an acryloxy group, An organic functional group having a functional group selected from a vinyl group, an allyl group and an amino group, R ⁸ is one or more kinds of hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine, and n is 1 The active energy ray-curable underlayer hard coat liquid containing the silane compound represented by the formula 2 or 3 and (H) colloidal silica is applied and then cured to form.

Examples of the silane compound represented by the above formula (3) include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl). ) 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N- [2- (vinylbenzylamino ) Ethyl] -3
-Aminopropyltrimethoxysilane and the like can be enumerated. Of these, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are particularly preferably used.

As the polyfunctional acrylate (F) and the colloidal silica (H), those described for the polyfunctional acrylate (A) and the colloidal silica (D) can be similarly used.

The base hard coat liquid was prepared by adding 1.100 parts by weight of the polyfunctional acrylate (F) to 1 part of the silane compound (G).
5 to 50 parts by weight, preferably 8 to 25 parts by weight, and 40 to 85 parts by weight of colloidal silica (H) (solid content).
This base hard coat liquid is prepared as a dispersion liquid in a liquid medium containing the above-mentioned active ingredient in a predetermined amount. As the liquid medium, those described for the liquid medium used in the above hard coat composition can be similarly used.

The base hard coat liquid may further contain at least one of a photopolymerization initiator, a hydrolysis catalyst and a physical property modifier. As for these, those described in the above hard coat composition can be similarly used. Further, the base hard coat liquid is an optional component,
A leveling agent, a lubricity imparting agent, an antioxidant, a weather resistance imparting agent, an antistatic agent, and a bluing agent may be contained.

The base hard coat layer is formed by coating the base hard coat liquid on the surface of the base material or on the primer layer and curing it by irradiation with ultraviolet rays or electron beams, similarly to the above hard coat layer. This underlying hard coat layer has a hardness almost equal to that of the hard coat layer. The above-mentioned hard coat layer is provided on this underlying hard coat layer. The thickness of the hard coat layer is preferably 0.05 to 1.5 μm, and the thickness of the underlying hard coat layer is such that the total thickness of this layer and the hard coat layer is preferably 1.0 to 9 μm. Adjusted.

The hard coat composition for the hard coat layer used together with the underlying hard coat layer contains fine particles (E) having a relatively small average particle size, for example, 0.05 μm (50 n).
m) to 2 μm average particle diameter is preferably contained. As a result, the fine particles (E) having a small average particle diameter are embedded in the hard coat layer, and a part of the fine particles (E) is projected on the surface of the hard coat layer, so that uniform antiglare property is easily imparted. can do.

In the resin product of the present invention, another coating may be optionally provided on the hard coat layer.
Also in this case, the antiglare effect of the hard coat layer is sufficiently exhibited.

As the resin substrate in the present invention, a transparent plate material such as polycarbonate resin, polyethylene terephthalate resin, acrylic resin or the like is preferably used.

In the resin product of the present invention, preferably, the fine particles (E) have a height (diameter in the case of a true sphere) in the hard coat layer.
It is preferable to be buried at a depth of at least half of the above, and it is preferable that the outermost surface of the fine particles (E) is covered with a thin layer of a hard coat. By embedding the fine particles (E) at a height of at least half, it is possible to advantageously prevent the fine particles from falling out of the hard coat layer. Furthermore, fine particles (E)
Are preferably distributed as single particles on the outer surface of the hard coat layer adjacent to each other without overlapping. The surface roughness of the outer surface of the hard coat layer is 10 μm in average roughness (Rz) of 6 μm.
It is preferably m or less.

However, if the entire fine particles (E) are buried in the hard coat layer, the antiglare property cannot be exhibited. Therefore, the surface roughness is 0.05 μm or more in terms of 10-point average roughness (Rz). Preferably there is.

The preferable distribution or surface roughness is
This can be achieved by appropriately adjusting the proportion of the fine particles (E) in the hard coat layer, the thickness of the hard coat layer, and the like.

[0088]

[Effects of the Invention] When the ambient light is reflected and reflected on the surface of a display or a television of a personal computer, the original image may be difficult to see. In addition, recently, there are many opportunities to use a handy video equipped with a mobile computer and a monitor outdoors, and it is difficult to see the original image because the surrounding light is reflected more than when used indoors. According to the present invention, in order to improve such a situation, the outermost surface of the display is subjected to an antiglare treatment to reduce reflection due to glare and make the image easier to see. The treated surface has scratch resistance, water repellency, stain reduction, and stain removal easiness.

According to the present invention, there are provided other products such as a rearview mirror, a fluorescent lamp cover, and ground glass-like parts which are required to have antiglare properties, such as building materials.

The hard coat composition of the present invention can also be used as a release treatment for transparent / opaque resins or release films which require matting.

[0091]

EXAMPLES The present invention will be described in more detail below with reference to examples. The various substances used in the examples are as follows. Polycarbonate plate: Panlite PC1111 (manufactured by Teijin Chemicals Ltd.) plate (thickness: 4 mm).

Primer 1: A copolymer of methylmethacrylate and methacryloxypropyltrimethoxysilane in a molar ratio of 4: 1 (Mn = 10,000, Mw = 40,
000) 100 g, 2,2 ', 4,4'-tetrahydroxy-4-methoxybenzophenone 5 g, propylene glycol monomethyl ether 895 g and surfactant D
ow Corning Paint Additive 19
A solution consisting of 1 g. Primer 2: Paraloid A-11 (water-soluble acrylic resin manufactured by Rohm & Haas) 60 g, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole 3
g, propylene glycol monomethyl ether 905
g, 5 g of toluene, and 0.1 g of Dow Corning Paint Additive 19.

Hard Coat 1 (Antiglare / Water Repellent Hard Coat) As a polyfunctional acrylate, 12.4 g of trimethylolpropane triacrylate, 2.6 g of γ-aminopropyltrimethoxysilane and 6.3 of 2-methoxypropanol.
g, acetic acid 0.4 g, colloidal silica (average particle size 90
˜120 nm, 26.0 g of “IPA-ST-ZL” (manufactured by Nissan Chemical Industries, Ltd., silica component: 30 wt%), 1.3 of perfluorooctylethyltriethoxysilane.
After adding g and reacting, 14.5 g of epoxy ester “3002M” (Kyoeisha Chemical Co., Ltd.) and 14.5 g of butyl acetate are added as epoxy acrylate. Next, benzophenone was added as a photopolymerization initiator to 0.8
g, 0.1 g of a flow control agent is added.

Thereafter, 10 parts of 2-methoxypropanol was added.
Add 0 g. Then, 0.8 g (2% by weight of the hard coat active ingredient) of crystalline silica fine particles having an average particle size of 6 μm was added to the above solution, stirred and uniformly dispersed to obtain a hard coat solution 1.

Hard coat 2 (active energy ray-curable hard coat) 12.4 g of trimethylolpropane triacrylate as a polyfunctional acrylate, 2.6 g of γ-aminopropyltrimethoxysilane, 6.3 of 2-methoxypropanol 6.3.
g, acetic acid 0.4 g, colloidal silica (average particle size 90
˜120 nm, 26.0 g of “IPA-ST-ZL” (manufactured by Nissan Chemical Industries, Ltd., silica component: 30 wt%) was added and reacted, and then epoxy ester 3002M (Kyoeisha Chemical Co., Ltd. )) To 14.
5 g and 14.5 g butyl acetate are added. Next, 0.8 g of benzophenone and 0.1 g of a flow control agent are added as photopolymerization initiators.

Thereafter, 2-methoxypropanol was added to 10
Add 0 g. Then, 0.8 g (2% by weight of the hard coat active ingredient) of crystalline silica fine particles having an average particle diameter of 6 μm was added to the above solution, stirred and uniformly dispersed to obtain a hard coat liquid 2.

Hard coat 3 (hard coat for imparting antiglare and water repellency) 100 g of 1,6-hexanediol diacrylate as a polyfunctional acrylate (A) and 1 gamma-aminopropyltrimethoxysilane as an aminosilane (B).
0 g, 2-methoxypropanol 50 g, acetic acid 5 g, colloidal silica (D) having an average particle diameter of 10 to 20 nm
Of "IPA-ST" (active ingredient: 30 wt% Nissan Chemical Industries, Ltd.), dispersion of amorphous silica fine particles as fine particles (E) "KE-W50" (particle size: 0.50-0.50)
0.56 μm, active ingredient: 15 wt% 500 g of Nippon Shokubai Co., Ltd., 10 perfluorooctylethyltriethoxysilane as fluoroalkylsilane (C)
g, and stirred, and then 5 g of benzophenone as a photoinitiator and 0.1 g of a flow control agent were added to obtain a hard coat liquid 3.

Hard Coat 4 (Active Energy Ray-Curing Undercoat Hard Coat) As a polyfunctional acrylate, 12.4 g of 1,6-hexanediol diacrylate, 2.6 g of γ-aminopropyltrimethoxysilane and 6.3 of 2-methoxypropanol.
g, 0.4 g of acetic acid, “MA-ST-M” as a colloidal silica (average particle size 20 to 30 nm) (active ingredient:
20.0 g of 40 wt% NISSAN CHEMICAL INDUSTRIAL CO., LTD., "Epoxy ester 3002" as epoxy acrylate
M "(manufactured by Kyoeisha Chemical Co., Ltd.) 5.0 g, butyl acetate 14.
Add 5 g. Next, 0.8 g of benzophenone and 0.1 g of a flow control agent are added as photopolymerization initiators. Thereafter, 100 g of 2-methoxypropanol was added, and the mixture was stirred and uniformly dispersed to obtain a hard coat liquid 4.

The conditions such as the coating method and various test methods used in the examples are as follows. Application method: Flow coating. However, only the hard coat 3 of Example 5 is spinner method. Primer curing conditions: 110 ° C. for 30 minutes (primer 1) and 30 ° C. for 15 minutes (primer 2), hard coat curing conditions: total UV irradiation energy: 10
00 (mJ / cm ² ), integrated photometer (model: UIT-1
02 Measured by USHIO INC. Adhesion test: Gome board test conforms to JIS K5400. Stainability test: After applying the wax, wipe off with a cotton-free dust cloth, and visually check the remaining condition of the wax (whether or not the trace of the wax wipe remains as stain). Film strength test: Based on the pencil hardness test described in JIS K5400. Contact angle measurement: The contact angle with a water drop of 0.1 cc was measured. It indicates that the larger the contact angle, the less likely it is to get dirty. Optical property measurement: Visible light transmittance (%) and haze value (haze value,%) were measured according to JISR3212.
The higher the haze value, the higher the antiglare property. Surface roughness measurement: 10-point average roughness Rz (μm) is measured.

Example 1 Hard coat 1 was applied to a polycarbonate plate and cured. Example 2 A primer 1 was applied to a polycarbonate plate and cured, and then a hard coat 1 was applied and cured. Example 3 Example 2 was repeated except that primer 2 was used instead of primer 1.

Comparative Example 1 Hard coat 2 was applied to a polycarbonate plate and cured. Comparative Example 2 After applying and curing the primer 1 on the polycarbonate plate, the hard coat 2 was applied and cured. Comparative Example 3 A primer 2 was applied and cured on a polycarbonate plate, and then a hard coat 2 was applied and cured.

The performance of the products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 is shown in Table 1. The film thickness of each product was about 4.0 μm.

[0103]

[Table 1]

Example 4 Inorganic fine particles were added to the hard coat 1 (before adding 2 wt% of fine particles) to the weight of the active ingredient of the hard coat at 0.9 wt
%, 1.8 wt%, 3.2 wt%, 4.4 wt%, 6.0 w
A liquid added with t% and 7.7 wt% was prepared. This hard coat liquid was applied to a polycarbonate plate and cured. The results are shown in Table 2.

[0105]

[Table 2]

Further, the sample prepared in Example 4 was magnified 300 times with an optical microscope (BH2-UMA / manufactured by Olympus) and the surface was observed. The fine particles were arranged in a single layer, and more than half of the fine particles were embedded in the hard coat (binder). Table 3 shows the number of fine particles protruding in the unit area.

[0107]

[Table 3]

It has also been clarified that there is a correlation between the number of protruding fine particles and the haze value, and the antiglare effect can be controlled by controlling this number.

Example 5 A hard coat 4 was applied as a base hard coat layer to a polycarbonate plate and cured, and then the hard coat 3 was applied and cured by a spinner method. The film thickness of the underlying hard coat layer (hard coat 4) after curing was 4 μm.
The film thickness after curing of the layer was 0.15 μm. Example 5
Table 4 shows the performance of the product obtained in Step 1.

[0110]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/00 C09D 5/00 Z 163/10 163/10 167/07 167/07 175/16 175/16 183/04 183/04 183/08 183/08 G02B 1/10 G02B 1/10 Z F-term (reference) 2K009 AA15 CC03 CC09 CC12 CC24 CC26 CC42 4F100 AA20C AA20D AH03C AH05C AH05D AH06C AH06D AH10C AK01A AK01B AK41C AK51C AK53C AL05C BA03 BA04 BA07 BA10A BA10C BA10D BA25D CA07B CA30C DE01C DE01D DE06C DE06D EJ08C EJ08D EJ52C EJ52D EJ64C EJ64D EJ65B JB06 JK09 JL06 JN30 NA07 GA07 GA07 GA07 NA07 GA07 GA07 GA02 GA02 GA02 FA02 DIA2 FA2 DIA2 FA2 BB02 PA02 PA02 PA13 PA02 PA13 PA47 PA13 PA47 PA13 PA02 PA13 PA02 PA13 PA02 NA19 PA07 PA17

Claims (11)

[Claims] 1. A polyfunctional acrylate (A), an aminoorganofunctional silane (B), a fluoroalkylsilane (C),
(D) Colloidal silica and (E) Average particle size 50n
An active energy ray-curable hard coat composition comprising fine particles of m to 10 μm. 2. The aminoorganofunctional silane is represented by the following formula (1) XaSi (R ¹ (NHR ² ) _b NR ³ H) _4-a (1) wherein X is an alkoxyl group having 1 to 6 carbon atoms. And R ¹ and R ² are the same or different divalent hydrocarbon groups, R ³ is a hydrogen atom or a monovalent hydrocarbon group,
The active energy ray-curable hard coat composition according to claim 1, wherein a is an integer of 1 to 3 and b is an integer of 0 to 6. 3. The fluoroalkylsilane represented by the following formula (2) R ¹ _a R ² _b Si (OR ³ ) _4-ad (2) wherein R ¹ is a fluoroalkyl group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, and R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an acyl group. Yes, a is 1, 2
Or 3 and b is 0, 1 or 2, provided that a is
The active energy ray-curable hard coat composition according to claim 1 or 2, wherein + b is 1, 2 or 3. 4. A photopolymerization initiator, a hydrolysis catalyst, and at least one kind of physical property modifier are further contained.
The active energy ray-curable hard coat composition according to any one of 1. 5. The active energy ray-curable hard coat composition according to claim 4, wherein the physical property modifier comprises one or more of epoxy acrylate, urethane acrylate and polyester acrylate. 6. The resin substrate according to any one of claims 1 to 5.
Item 10. A hard coat resin product having a hard coat layer formed from the hard coat composition according to item. 7. A hard coat resin product having a hard coat layer of the hard coat composition according to any one of claims 1 to 5 on a resin substrate via a primer layer. 8. The hard coat resin product according to claim 7, wherein the primer layer is composed of an organic resin having adhesiveness to a resin base material and capable of adhering to a silicon hard coat, and an ultraviolet absorber. 9. The base hard coat layer according to claim 6, further comprising a base hard coat layer between the resin substrate and the hard coat layer or between the primer layer and the hard coat layer. Hard coat resin product. 10. The base hard coat layer comprises (F) a polyfunctional acrylate, (G) a compound represented by the following formula (3), R ⁷ _n Si (OR ⁸ ) _4-n (3), wherein R ⁷ is a methacryloxy group or acryloxy group. An organic functional group having a functional group selected from a group, a vinyl group, an allyl group and an amino group, R ⁸ is one or more kinds of hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine, and n Is 1, 2, or 3, and is formed by applying an active energy ray-curable liquid containing a silane compound represented by and a (H) colloidal silica, and then curing the liquid. Hard coat resin product. 11. The hard coat layer comprises fine particles (E).
The hard coat composition containing fine particles having an average particle diameter of 0.2 to 2 μm is applied and cured so that the hard coat layer thickness after curing is 0.05 to 1.5 μm. Hard coat resin products.