JP2001316604A - Resin composition for forming low-reflection hard coat film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can form a hard coat film having low-reflection function suited for optical parts and having scratch resistance, mar resistance, chemical resistance or the like sufficient to protect a base material in a simple and convenient process with enhanced productivity, enhanced yield of product or the like. SOLUTION: The resin composition for forming a low-reflection hard coat film is produced by blending (A) a mixture of a hydrolyzate of a perfluoroalkyl group-containing silane and an acryl or methacryl functional silane with metal oxide fine particles and (B) a multifunctional acrylate or methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-reflection hard coat resin composition for forming a hard coat film formed on a surface thereof for protecting optical components such as various displays, lenses, mirrors, goggles and window glasses. About things
In particular, the present invention relates to a low-reflection hard coat resin composition capable of forming a hard coat film having a low reflection function suitable for an optical component and excellent properties as a hard coat film such as scratch resistance, scratch resistance, and chemical resistance. Specifically, a liquid crystal display device,
The present invention relates to a low reflection hard coat resin composition capable of forming a hard coat film suitable for protecting a screen of various display devices such as a CRT display device, a plasma display device, an electrochromic display device, a light emitting diode display device, and an EL display device.

[0002]

2. Description of the Related Art Conventionally, the surface of a base material such as glass or plastic used for optical parts is irradiated (UV / E
B) After providing a hard coat layer made of a curable acrylic / methacrylic resin, a thermosetting silicone resin, or the like,
A method of forming an optical thin film layer by dry coating such as evaporation or sputtering using an inorganic oxide such as titanium oxide or silicon oxide to obtain an optical multilayer film by light interference such as an anti-reflection film is known. ing.

Further, after a hard coat layer made of an irradiation (UV / EB) curable acrylic / methacrylic resin, a thermosetting silicone resin or the like is provided on a substrate, wet coating is performed using a metal alkoxide or the like as a starting composition. There is known a method of forming an optical thin film layer to obtain an antireflection film. In this method, S is used as the low refractive material.
i, a method using an alkoxide such as Ti or Zr as a high refractive material has been proposed.

[0004]

However, the above-mentioned method using dry coating has problems such as expensive equipment, low film forming speed, and low productivity. Further, in the above-mentioned method by wet coating, there is a problem in productivity because the dry polymerization of the metal alkoxide is carried out at a high temperature for a long time. Further, when an antireflection film is formed by this method on a substrate having antiglare properties formed by forming irregularities on the surface, the thickness of the hard coat film is large in the concave portions of the substrate and in the convex portions. There is a problem that the reflectance becomes higher than the design value because the thickness becomes thinner. In addition, in any of these methods, since a process of laminating an optical thin film layer after providing a hard coat layer on a base material is performed, a reduction in yield due to a large number of processes and an increase in the price of a product are achieved. There was a problem of inviting.

The present invention has been made in view of the above circumstances, and has a low reflection function suitable for an optical component and a scratch resistance, abrasion resistance, chemical resistance and the like capable of sufficiently protecting a substrate. It is an object of the present invention to provide a technique capable of improving productivity, product yield, and the like in a simple process when forming a coat film. Still another object is to provide a technique capable of forming a film having a uniform thickness regardless of the shape of the surface of the base material.

[0006]

In order to solve the above-mentioned problems, the low-reflection hard coat resin composition of the present invention comprises (A)
It is characterized by comprising a mixture of a hydrolyzate of a perfluoroalkyl group-containing silane and an acrylic or methacryl-functional silane, metal oxide fine particles, and (B) a polyfunctional acrylate or methacrylate. The low-reflection hard coat resin composition may contain (C) a photopolymerization initiator. Further, the perfluoroalkyl group-containing silane is represented by the following general formula (1)

[0007]

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(Wherein R ¹ represents an alkyl group having ¹ to 5 carbon atoms, and n is an integer of 1 to 12). Further, the acrylic or methacryl functional silane is represented by the following general formula (2)

[0009]

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Wherein R ¹ is a hydrogen atom or a methyl group, R ²
Is a divalent organic group having 3 to 6 carbon atoms, R ³ and R ⁴ are each a substituted or unsubstituted monovalent hydrocarbon group, and a is an integer of 0 to 2. The compound represented by the formula (1) is preferable. The average particle diameter of the metal oxide fine particles is preferably 5 to 100 nm. Furthermore, in the low-reflection hard coat resin composition of the present invention, it is preferable from the viewpoint of antiglare properties to mix inorganic or organic fine particles having an average particle diameter of 0.1 to 100 μm. Then, a hard coat film is formed using these low reflection hard coat resin compositions. The low reflection hard coat resin composition of the present invention can form a hard coat film by being applied and cured. Then, the hard coat film has the following relational expression nd = λ / 4 (where n is the refractive index of the component (A), d is the film thickness of the layer composed of the component (A), and λ is the reflected light of the hard coat film. Is preferable from the viewpoint of a low reflection function. The hard coat film of the present invention is preferably provided on the surface of a plastic molded product, particularly an optical component. A plastic molded article having a hard coat film can be produced by applying a low-reflection hard coat resin composition to a plastic molded article body and curing the resin composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the components (A) to (C) to be blended in the low reflection hard coat resin composition of the present invention will be described in detail.

(A) Mixture of Perfluoroalkyl Group-Containing Silane and Hydrolyzate of Acrylic or Methacryl Functional Silane and Fine Particles of Metal Oxide Among components (A), silane containing perfluoroalkyl group is a hard coat film. It contributes to antifouling performance of the surface and lowering of the refractive index. As the perfluoroalkyl group-containing silane, those represented by the general formula (1) are preferable. In the formula (1), R ¹ is 1 to 5, preferably 1
Represents an alkyl group having from 1 to 3 carbon atoms, wherein n is from 1 to 1
2, preferably an integer of 5 to 12. Specific examples include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluorodecyltriethoxysilane. And so on. These can be used alone or 2
It can be used in combination of more than one species.

The acrylic or methacryl functional silane is
It is a component that contributes to crosslinking and curing as a hard coat film, and is preferably a compound represented by the general formula (2).
In the formula (2), R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic group having 3 to 6, preferably 3 to 5 carbon atoms,
R ³ and R ⁴ are each a substituted or unsubstituted monovalent hydrocarbon group,
a is an integer of 0 to 2. Specific examples include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane and the like.

The perfluoroalkyl group-containing silane and the acryl or methacryl functional silane are, for example, from 1:99 to 8
0:20, preferably 10:90 to 70:30. When these mixing ratios are not satisfied, both effects cannot be sufficiently exerted.

The hydrolyzate of a perfluoroalkyl group-containing silane and an acrylic or methacryl-functional silane can be obtained as follows. That is,
Pure water is added to these compounds and mixed. Alternatively, acidic water to which an acid such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, citric acid or tartaric acid is added as a catalyst, or a base such as ammonia, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine or triethanolamine Is added as a catalyst and stirred. At this time, by controlling the amount of water added,
The degree of progress of the hydrolysis can be adjusted. In general, the amount of water to be added is at least equimolar to the hydrolyzable group of the compound to be hydrolyzed, specifically, for example, 1.0 mol.
Desirably, it is about 2.0 times mol. For the purpose of homogenizing the hydrolysis reaction system, a solvent such as alcohols such as methanol, ethanol, propanol and isopropyl alcohol can be added in an amount of about 10 to 80% by weight based on water.

The metal oxide fine particles have a hydroxyl group on the particle surface and can undergo a dehydration condensation reaction with the above-mentioned hydrolyzate. By blending the metal oxide fine particles, the refractive index of the hard coat film can be lowered to give a low reflection function, and further, the hard coat film can be given surface hardness and wear resistance. As the metal oxide fine particles, generally, a colloidal metal oxide in which a metal oxide is dispersed in water or an organic solvent is used. The average particle diameter of the metal oxide fine particles is 1 to 100 nm, preferably 5 to 100 nm, and more preferably 5 to 70 nm. If it is less than 1 nm, the surface hardness of the hard coat film may not be improved in some cases. On the other hand, if the thickness exceeds 100 nm, the transparency is disadvantageously reduced.

Specific examples of the metal oxide fine particles include those composed of silica, alumina, titania, antimony, tin oxide, tungsten oxide and the like.
These can be used alone or in combination of two or more. In particular, in the present invention, the refractive index is relatively low,
Colloidal silica having good transparency is preferred.

The above-mentioned mixture of the hydrolyzate and the metal oxide fine particles may be produced by mixing the metal oxide fine particles after producing the hydrolyzate, or may be prepared in advance by using a perfluoroalkyl group-containing silane and acrylic or It can also be obtained by hydrolyzing a mixture of methacryl-functional silane and fine metal oxide particles.

In the component (A), the amount of the hydrolysis is such that the perfluoroalkyl group-containing silane and the acrylic or methacryl-functional silane can form a monomolecular layer on the surface of the metal oxide fine particles. Preferably, it is an amount. Specifically, the perfluoroalkyl group-containing silane and the acryl or methacryl functional silane are used in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of the solid content of the metal oxide fine particles.
0 parts by weight, preferably 1.0 to 20 parts by weight.

(B) Polyfunctional acrylate or methacrylate The polyfunctional acrylate or methacrylate has at least three, substantially three to six, (meth) acryloyl groups from the viewpoint of satisfying surface hardness and scratch resistance as a hard coat. Is preferred.

Specifically, a (meth) acryloyl group is
Examples of the compound having trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris [(meth) acryloxyethyl] isocyanate Nurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate, pentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, and the like. Examples of the compound having four (meth) acryloyl groups include trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkyl-modified dipentaerythritol tetra (meth) acrylate.

Examples of the compound having five (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate and alkyl-modified dipentaerythritol penta (meth) acrylate. Examples of the compound having six (meth) acryloyl groups include dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

These compounds can be used alone or in combination of two or more. Further, among these exemplified compounds, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or a mixture containing these is particularly preferable from the viewpoint of scratch resistance.

Further, a reactive diluent for adjusting viscosity can be blended with the component (B). For example, relatively low-viscosity 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, pentaerythritol tri (meth) acrylate, Bifunctional or higher functional monomers and oligomers such as trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and neopentyl glycol di (meth) acrylate, and monofunctional monomers.

Specifically, acrylates such as N-vinylpyrrolidone, ethyl acrylate, propyl acrylate, etc., ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, isooctyl methacrylate, 2-hydroxyethyl methacrylate Methacrylates such as cyclohexyl methacrylate and nonylphenyl methacrylate; derivatives such as tetrahydrofurfuryl methacrylate and its modified caprolactone; styrene, α-methylstyrene, acrylic acid and the like.
They can be used alone or in combination of two or more. The amount of the reactive diluent is 5 to 50% by weight, preferably 10 to 30% by weight, based on the polyfunctional acrylate or methacrylate.

The components (A) and (B) are
The hard coat film made of the low reflection hard coat resin composition acts as follows. First, in the component (A), a hydroxyl group on the surface of the metal oxide fine particles and a silanol group of the hydrolyzate undergo a dehydration condensation reaction, and as a result, a perfluoroalkyl group contributing to antifouling property and a low refractive index, An acryloyl or methacryloyl group contributing to crosslinking and curing of the film is chemically fixed on the surface of the metal oxide fine particles.

For example, as described later, the component (A) and the component (B) dispersed and dissolved in an appropriate solvent are mixed to form a low-reflection hard coat resin composition, which is applied to a substrate, When this coating film is cured to form a hard coat film, the component (A) having a relatively low surface energy moves to the interface with air, that is, to the outermost surface of the coating film during the formation process. As a result, a phase separation film structure including an upper layer composed of the component (A) on the surface side and a lower layer composed of the component (B) below the upper layer is formed. At this time, a clear interface is formed between the upper layer and the lower layer by the metal oxide fine particles blended in the component (A), and the metal oxide fine particles at this interface function as an optical interference film.

Preferably, the optical thickness of the upper layer is set so as to be １ ／ of the detection center sensitivity wavelength (center wavelength of the peak of the detected wavelength spectrum) λ of the reflected light of the hard coat film. , A low reflection function can be realized. The optical thickness refers to the product of the refractive index n of the component (A) and the thickness d of the upper layer composed of the component (A). That is, this relation can be expressed by the following relational expression nd = λ / 4. Further, the film thickness d can be adjusted by the mixing ratio of the component (A) and the component (B). Note that λ is usually in the visible light range (360 to 830 nm).

(C) Photopolymerization initiator (C) Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzyl methyl ketal, and alkyl ethers thereof. Acetophenones, such as acetophenone, 2,2, -dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone; anthraquinones, such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthon, 2,
Thioxanthones such as 4-diethylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone; and azo compounds. Can be. These can be used alone or as a mixture of two or more.

(C) Photopolymerization initiators include tertiary amines such as triethanolamine and methyldiethanolamine; and photobenzoic acid derivatives such as benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate. It can be used in combination with a starting aid or the like.

The amount of the photopolymerization initiator (C) used is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polymerizable resin component. If it is less than 0.5% by weight, it is difficult to initiate polymerization, and if it exceeds 20% by weight, the effect is saturated. In addition, the polymerizable resin component is a polyfunctional acrylate or methacrylate of the component (B). The photopolymerization initiator (C) is not necessarily essential, and need not be blended when the low-reflection hard coat resin composition is cured using an electron beam as described later.

Further, the low-reflection hard coat resin composition of the present invention may optionally contain organic or inorganic fine particles. By blending these organic or non-fine particles, antiglare properties can be imparted. The average particle size of the organic or inorganic fine particles is 0.1 to 100 μm.
m, preferably 0.5 to 5.0 μm. 0.1μ
If it is less than m, the effect of addition cannot be obtained, and if it exceeds 100 μm, the resolution of the transmitted image of the hard coat film may be reduced.

As the organic fine particles, for example, they have an appropriate cross-linking structure inside the particles, and may be made of an ultraviolet curable resin, a monomer,
Hard fine particles which hardly swell due to a solvent or the like are suitable. For example, styrene resin of particle internal cross-linking type, styrene-acrylic copolymer resin, acrylic resin, divinylbenzene resin, silicone resin, urethane resin, melamine resin, styrene-isoprene resin,
Benzoguanamine resins or microgels containing these resins as main components can be used. As the inorganic fine particles, silica and the like are preferable from the viewpoint of the transparency of the hard coat film.

The compounding amount of the organic or inorganic fine particles is 1 to 30% by weight, preferably 3 to 15% by weight, based on the low reflection hard coat resin composition. If it is less than 1% by weight, the effect of addition cannot be obtained, and if it exceeds 30% by weight, the effect is saturated.

The low-reflection hard coat resin composition of the present invention may contain a small amount of a known general paint additive within a range that does not affect the intended function.
For example, a silicone-based or fluorine-based additive that imparts leveling and surface slip properties is effective in preventing the surface of the hard coat film from being damaged. Furthermore, when ultraviolet rays are used as active energy rays when curing the resin composition as described below, these additives bleed to the air interface, thereby curing the resin with oxygen. Inhibition can be reduced. Therefore, the coating can be formed by curing the low-reflection hard coat resin composition even under the condition that the irradiation intensity is relatively low. The addition amount of silicone-based and fluorine-based additives
0.01 to 0.5 part by weight is appropriate for 100 parts by weight of the low reflection hard coat resin composition.

In the present invention, for example, a mixture of the component (A) and the component (B) dispersed or dissolved in an appropriate solvent and the component (C) mixed with another component such as a photopolymerization initiator is used. The reflective hard coat resin composition is applied to the surface of a substrate made of plastic or the like, and is irradiated with ultraviolet light or the like as an active energy ray of the photopolymerization initiator (C), thereby having a low reflection function, scratch resistance, and resistance to scratches. An excellent hard coat film having abrasion resistance, chemical resistance and the like can be formed. The solvent for dispersing or dissolving the component (B) is not particularly limited, and examples thereof include 2-butanone, isopropyl alcohol, and toluene. Although the amount of the solvent used is not particularly limited, it is used in an amount of about 10 to 90% by weight based on the component (B).

As the substrate, the above-mentioned optical components are preferable in order to make use of the low reflection function of the hard coat film. The material is not particularly limited, but a plastic molded product is suitable because the hard coat film has a sufficient hardness suitable for protecting plastic. Various plastics are selected as the plastic constituting the base material (plastic molded product main body) depending on the application. Examples thereof include polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polycarbonate (PC), and cyanuric acid triacrylate. Examples include allyl ester (TAC) and polyether sulfone (PES).

When the low-reflection hard coat resin composition of the present invention is used, an upper layer composed of the low-reflection functional layer (component (A)) having a uniform thickness along (following) the surface shape of the substrate. ) Is formed. Therefore, the performance as designed can be exhibited even in an optical component or the like in which irregularities are formed for imparting antiglare properties as described above. In addition, a smooth low-reflection functional layer having the same shape as the surface of the substrate can be formed on a smooth surface without performing any special treatment. The thickness of the hard coat film is appropriately set depending on the application, and is not particularly limited, but is, for example, about 2 to 20 μm.

In the case where (C) a photopolymerization initiator is blended and ultraviolet rays are used as the active energy rays, a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, etc. Can be used. Generally, a high-pressure mercury lamp is used for a transparent hard coat film containing no filler. A metal halide lamp is generally used when a filler is contained or a thick hard coat film is cured.

When curing using an electron beam,
(C) Using a photocurable low-reflection hard coat resin composition having a composition not containing a photopolymerization initiator, the following electron beam is applied. For example, 50 to 1000 KeV, preferably 100 to 300 KeV emitted from various electron beam accelerators such as Cockloft-Wald type, Bande-Crafts type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type and High frequency type
It is preferable to use an electron beam having an energy of

[0041]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Note that “parts” and “%” are based on weight unless otherwise specified. <Example 1> First, the component (A) was produced as follows. That is, isopropyl alcohol was added to 37 g of tridecafluorooctyltrimethoxysilane and 30 g of 3-acryloxypropyltrimethoxysilane for 37 g.
g and stirred, then add 29 g of 0.05N diluted hydrochloric acid to about 10
The mixture was added dropwise at 30 ° C. over 30 minutes and then aged at room temperature for 6 hours to produce a hydrolyzate of tridecafluorooctyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane. Then, 50 g of a hydrolysis solution of tridecafluorooctyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane and 200 g of an IPA dispersion of colloidal silica (IPA-ST: silica solid content 30 wt%, manufactured by Nissan Chemical Industries, Ltd.) were mixed. And aged at room temperature for 4 hours.

On the other hand, the component (B) (20 g of dipentaerythritol hexaacrylate, 60 g of pentaerythritol triacrylate, 20 g of trimethylolpropane triacrylate, 40 g of isopropyl alcohol)
And (C) component (photopolymerization initiator) (Darocure)
1173, manufactured by Nippon Ciba Geigy Co., Ltd.) 4 g).

Then, a low-reflection hard coat resin composition was prepared by mixing 1.6 g of the component (A) with the components (B) and (C).

Then, the low-reflection hard coat resin composition was formed on one side of a 150 μm-thick double-sided easily-adhesive treated polyester film by wire bar coating so as to have a dry film thickness of about 5 μm. Irradiate ultraviolet rays from a high-pressure mercury UV lamp (120 W / cm) under the conditions of an integrated light quantity of 400 mJ / m ² , and cured to form a hard coat film. The obtained hard coat film was evaluated by the following method. The hard coat film was designed to satisfy the relational expression of nd = λ / 4, where n was 1.47, d was 93.5 nm, and λ was 550 nm.

(1) Optical Characteristics The reflectance at 550 nm at an incident angle of 5 ° was measured by a spectrophotometer. (2) Pencil hardness JIS K using pencils of different hardness under 1 kg load
The presence or absence of scratches was determined by the test method indicated by 5400. (3) Scratch resistance The surface of the hard coat film was rubbed 10 times with a # 0000 steel wool while applying a load of 400 g, and the presence or absence of scratches and the degree of scratches were visually observed. Therefore, it was evaluated. A: No scratch is observed. B: Several fine scratches are observed. C: Countless scratches are observed.

The reflectivity of the hard coat film was 1.9%, and a good low reflection function was obtained. The pencil hardness is 3
H, Abrasion resistance was A, and mechanical strength as a hard coat film was also good. In addition, without blending the component (A),
When a hard coat film was formed from a composition comprising only the components (B) and (C), the reflectance was 4.6%.
Met.

Example 2 Crosslinked acrylic fine particles (MR-2G, average particle size: 0.9 μm, manufactured by Soken Chemical Co., Ltd.) were added to the low reflection hard coat resin composition of Example 1, and the coating dry film thickness was 5 μm. At this time, a low-reflection hard coat resin composition having antiglare properties was prepared by adjusting the blending amount so that the Haze value became 10%, and a hard coat film was formed. In addition,
The Haze value is a value for evaluating the antiglare property, and is an ASTM value.
D 1003-61. Further, in this hard coat film, nd = λ /
4 is satisfied, n is 1.47, d
Was 93.5 nm and λ was 550 nm.

The reflectance of the obtained hard coat film was 1.2.
%, And a good low reflection function was obtained. The pencil hardness was 2H to 3H, the scratch resistance was A, and the mechanical strength as a hard coat film was good.

<Comparative Example> A resin composition without the component (A) was prepared from the low reflection hard coat resin composition of Example 2 and cured under the same conditions as in Example 1 to obtain a dry film thickness of about 5 μm. Was formed. Next, a photopolymerization initiator (Darocure 117) was added to the component (A) in Example 1.
3, a composition containing 5 wt% of Nippon Ciba Geigy Co., Ltd.) was coated on the lower film with an optical film thickness of nd = 550 of the upper film.
Coating was performed with the concentration adjusted to / 4 nm, and the coating was cured under the same conditions to form an upper film on the lower film to form a hard coat film. Note that n was 1.47 and d was 93.5 nm.

The reflectivity of this hard coat film was 2.1%, and the result of Example 2 in which a layer composed of the component (A) and a layer composed of the component (B) were simultaneously formed to obtain a hard coat film ( 1.2%).

This is because, in the comparative example, the lower layer film composed of the component (B) and the upper layer film composed of the component (A) were formed in separate steps, so that the lower layer film did not follow the irregularities on the substrate surface. It is conceivable that the reflectance was increased as compared with the hard coat film of Example 2 as a result of being formed thicker in the concave portions and thinner in the convex portions. Then, since the shape of the substrate surface as designed was not obtained in this way, the formation of the hard coat film lowered the anti-glare property at the time of the initial design, and the Haze value was 1
It is considered that it decreased from 0% to 7.4%. Also,
The pencil hardness was 2H, the scratch resistance was B, and the mechanical strength as a hard coat was also reduced. This is considered to be due to weak adhesion between the lower film and the upper film.

As described above, in the embodiment according to the present invention, since the hard coat film is formed from the mixture of the component (A) and the component (B), it mainly has the mechanical properties as the hard coat film ( The lower layer composed of the component (B) and the upper layer composed of the component (A) having a low reflection function suitable for an optical component can be obtained in one step, and the properties of each layer can be sufficiently exhibited, and the adhesion of each layer can be improved. It became clear that a good hard coat film was obtained.

[0053]

As described above, the present invention is characterized by the formation of an optical interference film based on phase separation, so that fine particles are blended in a hard coat composition for the purpose of imparting antiglare properties. Even when forming irregularities on the film surface, an optical interference film having a low refractive index that follows the irregularities on the surface can be formed by wet coating. Also,
Since a hard coat film having a low reflection function can be manufactured in one step, the cost of the product can be reduced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08F 290/06 C08F 290/06 G02B 1/10 G02B 1/10 Z 1/11 A (72) Inventor Ohata Koichi 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 2K009 AA12 AA15 BB11 CC03 CC09 CC24 CC42 4J011 PA07 PA13 PA99 PB22 QA03 QA09 QA12 QA13 QA22 QA23 QA24 QA27 QA39 QA38 SA SA22 SA24 SA32. HA446 JA18 JA21 JB09 KA03 KA06 KA08 KA12 KA20 MA07 MA10 NA04 NA11 NA19 PA17 PA19 PB08 PC03 PC08

Claims (12)

[Claims] 1. A composition comprising (A) a mixture of a perfluoroalkyl group-containing silane and a hydrolyzate of an acrylic or methacryl-functional silane and metal oxide fine particles, and (B) a polyfunctional acrylate or methacrylate. Low-reflection hard coat resin composition. 2. The low reflection hard coat resin composition according to claim 1, further comprising (C) a photopolymerization initiator. 3. The perfluoroalkyl group-containing silane is represented by the following general formula (1): (Wherein R ¹ represents an alkyl group having ¹ to 5 carbon atoms, and n is an integer of 1 to 12). The low reflection hard coat resin composition according to the above. 4. The acrylic or methacryl-functional silane is represented by the following general formula (2): (Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is
6, a divalent organic group, R ³ and R ⁴ are each a substituted or unsubstituted monovalent hydrocarbon group, and a is an integer of 0 to 2. The low-reflection hard coat resin composition according to any one of claims 1 to 3, which is a compound represented by the formula: 5. The low-reflection hard coat according to claim 1, wherein the metal oxide fine particles have an average particle diameter of 5 to 100 nm. Resin composition. 6. The low-reflection hard coat resin composition according to any one of claims 1 to 5, wherein the resin composition has an average particle size of 0.1.
A low-reflection hard coat resin composition comprising inorganic or organic fine particles of 1 to 100 μm. 7. A hard coat film comprising the low reflection hard coat resin composition according to any one of claims 1 to 6. 8. The hard coat film according to claim 7, wherein the following relational expression nd = λ / 4 (where n is a refractive index of the component (A) and d is a film of a layer composed of the component (A)) The thickness and λ indicate the detection center sensitivity wavelength of the reflected light of the hard coat film.). 9. A method for forming a hard coat film, comprising applying and curing the low-reflection hard coat resin composition according to claim 1. Description: 10. A plastic molded article provided with the hard coat film according to claim 7. Description: 11. The plastic molded product according to claim 10, wherein the plastic molded product is an optical component. 12. The plastic molded article body according to claim 1,
7. A method for producing a plastic molded product, comprising applying and curing the low-reflection hard coat resin composition according to any one of 6.