KR20020083473A - Material with High Refractive Index and Anti-Reflective Laminate Using the Same - Google Patents

Abstract

PURPOSE: To provide a high refractive index material which has excellent stability in preservation and antistatic performance, and a laminate for preventing reflection which has excellent antireflection performance and antistatic performance. CONSTITUTION: The high refractive index material 10 consists of (1) 100 pts.wt. electroconductive metal oxide particles the average particle size of which ranges 0.01-2 μm, (2) 1-70 pts.wt. polymer containing hydroxyl group, (3) 1-70 pts.wt. hardener containing a functional group reacting with hydroxyl group, and its refractive index after setting is 0.60 or more. The laminate for preventing reflection 16 is obtained by using the same.

Description

High refractive index material and anti-reflective laminate using the same {Material with High Refractive Index and Anti-Reflective Laminate Using the Same}

The present invention relates to a high refractive index material and an antireflection laminate using the same. More specifically, it is related with the high refractive index material excellent in storage stability and antistatic property, and the antireflective laminated body excellent in antireflection and antistatic property using the same.

As a material for forming an antireflection film, for example, a thermosetting polysiloxane composition is known, and Japanese Patent Laid-Open No. 61-247743, Japanese Patent Laid-Open No. 6-25599, Japanese Patent Laid-Open No. 7-331115 and Japanese Patent It is disclosed in Unexamined-Japanese-Patent No. 10-232301.

However, the antireflective film obtained from such a thermosetting polysiloxane composition needs to heat-process at high temperature for a long time, and there existed a problem that productivity was low or the kind of application base material was limited. In addition, these thermosetting polysiloxane compositions have a problem in that handling is complicated by a two-component type in which a main body and a curing agent are separated because of poor storage stability.

Therefore, as disclosed in Japanese Patent Application Laid-Open No. 8-94806, a high refractive index film (refractive index = 1.6 or more) and a fluorine-based copolymer obtained by polarizing fine particles in a high refractive index binder resin on a substrate are used. The optical functional film which laminated | stacked the low refractive index film (refractive index = less than 1.6) containing sequentially is proposed.

More specifically, although a high refractive index film is formed, microparticles | fine-particles in high refractive index binder resin are formed by previously forming fine particle layers, such as 200 nm or less metal oxide particles, on a process paper, and pressure-bonding it with respect to the high refractive index binder resin on a base material. The floor is buried and dramatized.

Moreover, about the low refractive index film, the fluorine-containing copolymer 100 whose fluorine content ratio obtained by copolymerizing the monomer composition containing 30-90 weight% of vinylidene fluoride and 5-50 weight% of hexafluoropropylene is 60-70 weight%. A thin film having a thickness of 200 nm or less by curing a resin composition comprising a weight part, a polymerizable compound having an ethylenically unsaturated group, 30 to 150 parts by weight, and a total amount of 100 parts by weight, and a polymerization initiator of 0.5 to 10 parts by weight. To prepare.

However, since the optical functional film disclosed in Japanese Patent Laid-Open No. 8-94806 uses a polymerization initiator in a low refractive index material, the curing reaction is susceptible to the influence of oxygen (air) present in the surroundings. It was easy to see the problem.

Moreover, the manufacturing process at the time of manufacture is also complicated about a high refractive index film, and as a result, it was difficult to manufacture stable optical functional film. Moreover, since the kind of polymer body used for a high refractive index material and the kind of hardening | curing agent are not suitable, the problem that the storage stability of a high refractive index material is lacking was seen.

Moreover, the optical functional film disclosed in Unexamined-Japanese-Patent No. 8-94806 has the problem that compatibility with a low refractive index film and a high refractive index film is not good, and an antireflection is inadequate or it peels easily at an interface. .

Then, in order to solve the said problem, Unexamined-Japanese-Patent No. 2000-186216 has proposed the high refractive material containing the metal oxide particle whose average particle diameter is 0.1 micrometer or less, and the antireflection laminated body using this high refractive index material.

However, in the above publication, since nonconductive zirconium oxide or the like is suitably used as the metal oxide particles contained in the high refractive index material, the antireflective laminate obtained from such a high refractive material is excellent in antireflection property and transparency, but antistatic There was a problem of lack of sex.

As a result of earnestly examining, the inventors of the present invention have found that the above-described problems can be solved by mixing conductive metal oxide fine particles having a specific average particle diameter in an additive amount within a predetermined range. That is, this invention does not produce a problem with applicability | paintability and transparency, and provides the high refractive index material which has the outstanding storage stability and antistatic property, and the antireflective laminated body which has the outstanding antireflective property and antistatic property using the same The purpose.

1 shows a cross section of a laminate of the present invention.

2 shows a cross section of the laminate of the present invention.

<Explanation of symbols for the main parts of the drawings>

10, 20 high refractive index layer

12 description

14, 22 Low Refractive Index Layer

16, 24 anti-reflective laminate

18 hard coating layers

The present invention relates to a high refractive index material,

(1) 100 parts by weight of conductive metal oxide fine particles having an average particle diameter of 0.01 to 2 µm,

(2) 1 to 70 parts by weight of a hydroxyl group-containing polymer,

(3) 1 to 70 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group

The refractive index after hardening is 1.60 or more, It is characterized by the above-mentioned.

By using electroconductive metal oxide fine particles, the high refractive index material excellent in antistatic property can be obtained.

In this way, even when stored for 30 days or more at an excellent storage stability, for example, at room temperature (25 ° C.), there is no sedimentation of the conductive metal oxide fine particles, and the reaction between the hydroxyl group-containing polymer and the curing agent during storage is achieved. It can prevent effectively. In addition, the high refractive index film formed from such a high refractive index material has good compatibility with the low refractive index film, and can obtain excellent antireflection property or adhesion.

Moreover, in forming the high refractive index material of this invention, it is preferable that the said electroconductive metal oxide fine particle is antimony containing tin oxide or indium containing tin oxide.

By using antimony-containing tin oxide or indium-containing tin oxide, it is easy to obtain a high refractive index material which, when cured, yields a high refractive index film excellent in antireflection and antistatic properties.

Another aspect of the present invention is a reflection preventing laminate comprising a substrate and a high refractive index film and a low refractive index film obtained by curing the high refractive index material on the substrate.

In this case, another layer may be included between the substrate and the high refractive index film, and another layer may be included between the high refractive index film and the low refractive index film.

By providing a high refractive index film containing conductive metal oxide fine particles, an antireflection laminate excellent in antistatic properties can be obtained.

In addition, by including the high refractive index film constituted as described above, when combined with the low refractive index film, an excellent antireflection property, for example, a value of 1% or less as a reflectance can be obtained, and compatibility with the low refractive film is good. Excellent adhesion can be obtained.

Moreover, in forming the anti-reflective laminated body of this invention, it is preferable that the said low refractive index film is obtained by hardening the low refractive index material containing a curable fluorine-containing copolymer, and it is preferable that refractive index is a value of less than 1.60.

If comprised in this way, the adhesive force of a high refractive index film and a low refractive index film will become more favorable, and the outstanding antireflection property, for example, the reflectance of 1.0% or less can be obtained.

Moreover, as an example of a preferable curable fluorine-containing copolymer, the curable composition containing the fluorine-containing copolymer which has a hydroxyl group, and the hardening | curing agent which has a functional group which can react with a hydroxyl group is mentioned.

Embodiment (1st embodiment) regarding the high refractive index material of this invention, and embodiment (2nd and 3rd embodiment) regarding the antireflective laminated body are demonstrated concretely.

<1st embodiment>

A first embodiment of the present invention relates to a high refractive index material,

(1) 100 parts by weight of conductive metal oxide fine particles having an average particle diameter of 0.01 to 2 μm,

(2) 1 to 70 parts by weight of a hydroxyl group-containing polymer,

(3) 1 to 70 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group,

(4) 0.1 to 30 parts by weight of the curing catalyst,

(5) 100 to 20,000 parts by weight of an organic solvent,

The refractive index after hardening is made into the value of 1.60 or more.

(1) conductive metal oxide fine particles

When the electroconductive metal oxide microparticles | fine-particles used for a high refractive index material are spherical, it is preferable that the average particle diameter (number average particle diameter, the same below) is 0.01 micrometer-0.5 micrometer. In addition, when electroconductive metal oxide fine particle is needle shape, it is preferable that the average particle diameter is 0.01 micrometer-2 micrometers. Here, the average particle diameter when electroconductive metal oxide microparticles | fine-particles are needle shape means the major axis diameter of needle shape particle | grains.

This is because, when the number average particle diameter of the conductive metal oxide fine particles is less than 0.01 μm, it is difficult to form a conductive path in the cured coating film, and thus, the antistatic property may be remarkably impaired. This is because it is difficult to uniformly disperse the conductive metal oxide fine particles in the high refractive index material, the conductive metal oxide fine particles are easily precipitated, and the storage stability is insufficient. Moreover, when the number average particle diameter of electroconductive metal oxide fine particle exceeds 2 micrometers, transparency of the antireflective film obtained may fall, or haze (Haze value) may increase.

Therefore, it is more preferable to make the number average particle diameter of electroconductive metal oxide fine particle into the value within the range of 0.01-2 micrometers, and it is more preferable to set it as the value within the range which is 0.01-1 micrometer.

The type of the conductive metal oxide fine particles is preferably determined in consideration of the volume resistivity of the particles and the ease of adjusting the refractive index, but more specifically, the antimony-containing tin oxide (ATO, refractive index 1.95) and the indium-containing tin oxide (ITO). , Refractive index 1.95, tin oxide (SnO ₂ , refractive index 2.00), titanium oxide (TiO ₂ , refractive index 2.3 to 2.7), zinc oxide (ZnO, refractive index 1.90), indium oxide (I ₂ O ₅ ), antimony oxide (Sb ₂ O ₅ , refractive index 2.1), zinc sulfide (ZnS, refractive index 2.4) selenium oxide (SeO ₅ , refractive index 1.75), tungsten oxide (W ₂ O ₅ ), antimony acid (AZO, refractive index 1.90), glass ceramics, vanadium oxide ( V ₂ O _5, refractive index 1.76) may be mentioned singly or in combination of two or more of such.

However, among these conductive metal oxide fine particles, conductive metal oxide fine particles having a refractive index of 1.9 or more are used in that the refractive index value after curing can be easily adjusted to a value of 1.6 or more by a relatively small amount of addition, and an antistatic function can be provided. It is desirable to. As such conductive metal oxide fine particles, antimony-containing tin oxide and indium-containing tin oxide are particularly preferable.

Moreover, it is preferable to process a coupling agent on the surface of electroconductive metal oxide fine particle. By treating the coupling agent in this manner, the dispersibility of the conductive metal oxide fine particles can be improved, and the storage stability of the high refractive index material can be further improved.

Here, as a preferable coupling agent in a coupling agent process, isopropyl triisostearoyl titanate, titanium n-butoxide, titanium ethoxide, titanium 2-ethylhexoxide, titanium isobutoxide, titanium isopropoxide Seed, titanium methoxide, titanium methoxy propoxide, titanium n-nonyloxide, titanium n-propoxide, titanium stearyl oxide, triisopropoxyheptadecsinate titanium, γ-aminopropyltriethoxysilane γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxytitanium, γ-aminopropyltriethoxyaluminum and the like Can be mentioned.

(2) hydroxyl group-containing polymer

As a hydroxyl-containing polymer, if it is a polymer which has a hydroxyl group in a molecule | numerator, it can be used conveniently. More specifically, one kind or a combination of two or more kinds of polyvinyl acetal resin (polyvinyl butyral resin, polyvinyl formal resin), polyvinyl alcohol resin, polyacrylic resin, polyphenol resin, phenoxy resin and the like Can be mentioned.

However, among these hydroxyl-containing polymers, polyvinyl butyral resins (including modified polyvinyl butyral resins) include excellent adhesion to a substrate and mechanical properties and relatively easy uniform dispersion of conductive metal oxide fine particles. Most preferred. Moreover, it is more preferable that the average degree of polymerization among polyvinyl butyral resin is 1,000 or less, the polyvinyl alcohol unit in one molecule is 18 weight% or more, and has a physical property whose glass transition point is 70 degreeC or more.

Moreover, it is preferable to make the addition amount of a hydroxyl-containing polymer into the value within the range of 1-70 weight part with respect to 100 weight part of electroconductive metal oxide fine particles. This is because when the amount of the hydroxyl group-containing polymer is less than 1 part by weight, the adhesion to the substrate of the antireflective film obtained may decrease. On the other hand, when the amount of the hydroxyl group-containing polymer is more than 70 parts by weight, the conductive metal oxide fine particles are relatively This is because the amount decreases, the adjustment of the refractive index of the antireflection film after curing is difficult, and the antistatic property may be impaired.

Therefore, it is more preferable to make the addition amount of a hydroxyl-containing polymer into the value within the range of 3-50 weight part with respect to 100 weight part of electroconductive metal oxide fine particles, and it is more preferable to set it as the value within the range which is 5-30 weight part.

(3) curing agents that can react with hydroxyl groups

As a hardening | curing agent which can react with a hydroxyl group, if it has a functional group which can react with a hydroxyl group, it can be used suitably. More specifically, single 1 type, or 2 or more types of combinations, such as a melamine compound, a urea compound, a guanamine compound, a phenol compound, an epoxy compound, an isocyanate compound, a polybasic acid, are mentioned.

However, among these curing agents, the melamine compound having a methylol group and an alkoxylated methyl group or two or more in the molecule is most preferred in view of relatively excellent storage stability and relatively low temperature curing. Among these melamine compounds, hexamethyl ether methylol melamine compound, hexabutyl ether methylol melamine compound, methyl butyl mixed ether methylol melamine compound, methyl ether methylol melamine compound, butyl ether methylol melamine compound, etc. The methylated melamine compound of is more preferable.

Moreover, it is preferable to make the addition amount of the hardening | curing agent which has a functional group which can react with a hydroxyl group into the value within the range of 1-70 weight part with respect to 100 weight part of electroconductive metal oxide fine particles. This is because when the amount of the curing agent added is less than 1 part by weight, curing of the hydroxyl group-containing polymer may be insufficient. On the other hand, when the amount of the curing agent exceeds 70 parts by weight, the storage stability of the high refractive index material may decrease. Because.

Therefore, it is more preferable to make the addition amount of a hardening | curing agent into the value within the range of 5-60 weight part with respect to 100 weight part of electroconductive metal oxide fine particles, and it is more preferable to set it as the value within the range which is 10-40 weight part.

(4) curing catalyst

Moreover, it is preferable to add a hardening catalyst in a high refractive index material. As such a hardening catalyst, if it promotes reaction between a hydroxyl-containing polymer and a hardening | curing agent, it can be used conveniently. More specifically, 1 type or 2 types, such as aliphatic sulfonic acid, aliphatic sulfonate, aliphatic carboxylic acid, aliphatic carboxylate, aromatic sulfonic acid, aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, metal salt, and phosphate ester The above combination is mentioned.

However, among these curing catalysts, aromatic sulfonic acid is most preferable at the point which can improve the hardening rate of hardening | curing agents, such as a methylation melamine compound with respect to a hydroxyl-containing polymer.

The addition amount of the curing catalyst is not particularly limited, but the amount of the curing catalyst added is preferably within a range of 0.1 to 30 parts by weight based on 100 parts by weight of the conductive metal oxide fine particles. This is because when the addition amount of the curing catalyst is less than 0.1 part by weight, the effect of adding the curing catalyst may not be expressed. On the other hand, when the addition amount of the curing catalyst exceeds 30 parts by weight, the storage stability of the high refractive index material is lowered. Because there is.

Therefore, it is more preferable to make the addition amount of a hardening catalyst into the value within the range of 0.5-20 weight part with respect to 100 weight part of electroconductive metal oxide fine particles, and it is more preferable to set it as the value within the range which is 1-10 weight part.

(5) organic solvent

In addition, it is preferable to add an organic solvent in a high refractive index material. By adding an organic solvent in this manner, an antireflection film of a thin film can be uniformly formed. As such an organic solvent, one kind or two kinds of methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, t-butanol and isopropanol The above combination is mentioned.

The addition amount of the organic solvent is not particularly limited, but the amount of the organic solvent added is preferably within a range of 100 to 20,000 parts by weight based on 100 parts by weight of the conductive metal oxide fine particles. This is because when the amount of the organic solvent added is less than 100 parts by weight, it may be difficult to adjust the viscosity of the high refractive index material. On the other hand, when the amount of the organic solvent added exceeds 20,000 parts by weight, the viscosity is excessively lowered. This is because it may become difficult.

Therefore, it is more preferable to make the addition amount of an organic solvent into the value within the range of 300-10,000 weight part with respect to 100 weight part of electroconductive metal oxide fine particles, and it is more preferable to set it as the value within the range of 500-5,000 weight part.

(6) additive

In the high refractive index material, a radical photopolymerization initiator, a photosensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, and an antioxidant without departing from the object or effect of the present invention. It is also preferable to further contain additives such as an antistatic agent, a silane coupling agent, an inorganic filler, a pigment and a dye.

(7) refractive index

It is necessary to make refractive index (refractive index of Na-D line | wire, 25 degreeC of measurement temperature), ie, the refractive index of a high refractive index film after cured film formation of a high refractive index material into a value 1.6 or more. This is because when the refractive index of the high refractive index film is less than 1.6, when combined with the low refractive index film, the antireflection effect may be remarkably lowered.

Therefore, the refractive index of the high refractive index film is more preferably set to a value within the range of 1.6 to 2.0, and more preferably to a value within the range of 1.6 to 1.9. Moreover, when the refractive index after hardening of a high refractive index material exceeds 2.0, the kind of material which can be used may be restrict | limited excessively.

In the case where a plurality of high refractive index films are provided, at least one of them may have a value of the refractive index within the above range, and the other high refractive index film may have a value of the refractive index of less than 1.6.

(8) surface resistance

It is preferable to make the surface resistance value after the cured film formation of a high refractive index material into the value of 10 <^10> ohm / square or less, and it is more preferable to set it as 10 <^8> ohm / square or less. On the other hand, when the surface resistance of the high refractive index film is 10 ¹² Ω / square or more, antistatic property is not sufficiently developed in practical use, and adhesion of dust and the like becomes remarkable.

<2nd embodiment>

As shown in FIG. 1, the second embodiment of the present invention includes a high refractive index film 10 obtained from a high refractive index material and a low refractive index film 14 obtained from a low refractive index material, on a base 12. The antireflection laminate 16 is provided. In the antireflection laminate 16, the high refractive index film 10 plays the function of the hard coating layer without providing a hard coating layer. Therefore, the structure of the anti-reflective laminated body 16 becomes simple, and the anti-reflective laminated body 16 can be formed precisely. Hereinafter, 2nd Embodiment is described concretely.

(1) high refractive index material

The values of the refractive index in the high refractive index material and the high refractive index film obtained therefrom are the same as those in the first embodiment. Therefore, detailed description thereof will be omitted.

(2) low refractive index material

Further, the low refractive index material for forming the low refractive index film,

① 100 parts by weight of a fluorine-containing copolymer having a hydroxyl group,

② 1 to 70 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group,

③ 0.1 to 15 parts by weight of the curing catalyst,

④ 500 to 10,000 parts by weight of organic solvent,

The refractive index after hardening is made into the value less than 1.60.

① Fluorine-containing copolymer having hydroxyl group

As a fluorine-containing copolymer which has a hydroxyl group, if it is a fluorine-containing copolymer which has a hydroxyl group in a molecule | numerator, it can be used conveniently. More specifically, it can obtain by copolymerizing the monomer (component a) containing a fluorine atom, and the monomer (component b) containing a hydroxyl group or an epoxy group. Moreover, it is preferable to add ethylenically unsaturated monomers (component c) other than a component and b component as needed.

As a monomer containing the fluorine atom which is a component, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, trifluoroethylene, tetrafluoroethylene, (fluoroalkyl) vinyl ether, ( Fluoroalkoxyalkyl) vinyl ether, perfluoro (alkyl vinyl ether), perfluoro (alkoxy vinyl ether), fluorine-containing (meth) acrylic acid esters and the like.

Moreover, although the compounding quantity of the a component in the fluorine-containing copolymer which has a hydroxyl group is not specifically limited, For example, it is preferable that it is a value within the range of 10-99 mol%, More preferably, it is the range of 15-97 mol% Is a value within.

Moreover, as a monomer containing the hydroxyl group or epoxy group which is a b component, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyethyl allyl ether, Hydroxybutyl allyl ether, glycerol monoallyl ether, allyl alcohol, hydroxyethyl (meth) acrylic acid ester, vinyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid glycidyl ester, crotonic acid glycidyl ester And single 1 type, or 2 or more types of combinations, such as methyl maleic acid methylglycidyl ester, are mentioned.

In addition, the compounding quantity of the b component in the fluorine-containing copolymer which has a hydroxyl group is not specifically limited, For example, it is preferable that it is a value within the range of 1-40 mol%, More preferably, it is the range of 3-30 mol%. Is a value within.

Next, the polymerization degree of the fluorine-containing copolymer which has a hydroxyl group is demonstrated. The degree of polymerization is preferably determined in consideration of the mechanical strength and the applicability of the low refractive index film. For example, the intrinsic viscosity (using N, N-dimethylacetamide solvent, measurement temperature of 25 ° C.) is in the range of 0.05 to 2.0 dl / g. It is preferable to set it as the value within, and it is more preferable to set it as the value within the range of 0.1-1.5 dl / g. By setting it as the value within such a range, the outstanding mechanical strength and applicability | paintability in a low refractive index film can be obtained.

In addition, the polymerization method for obtaining such an intrinsic viscosity is not restrict | limited, The solution polymerization method, suspension polymerization method, emulsion polymerization method, block polymerization method etc. which used a radical polymerization initiator can be used.

② curing agent having a functional group capable of reacting with a hydroxyl group

As a hardening | curing agent which has a functional group which can react with a hydroxyl group, the hardening | curing agent similar to the hardening | curing agent in a high refractive index material can be used. For example, it is preferable to use the melamine compound which has a methylol group and an alkoxylated methyl group, or two or more in a molecule | numerator.

Moreover, it is preferable to make the hardening | curing agent in a low refractive index material the same as the hardening | curing agent in a high refractive index material. That is, it is preferable that a high refractive index film and a low refractive index film are respectively hardened and obtained by the same kind of hardening | curing agent. With this arrangement, the compatibility between the high refractive index film and the low refractive index film is better, and more excellent antireflection property and adhesion can be obtained.

Moreover, the melamine compound mentioned above is mentioned as a homogeneous hardening | curing agent, More specifically, a hydroxylalkylated amino group containing melamine compound, an alkoxyalkylated amino group containing melamine compound, etc. are mentioned.

③ curing catalyst and organic solvent

The kind and addition amount of a curing catalyst and an organic solvent are the same as the content in a high refractive index material. Therefore, description thereof is omitted.

(3) the refractive index of the low refractive index film

The value of the refractive index in the low refractive index film (the refractive index of the Na-D line and the measurement temperature of 25 ° C.) is a low degree, the degree to which an excellent antireflection effect is obtained when combined with the high refractive index film, specifically, a value of less than 1.6. desirable. This is because when the refractive index exceeds 1.6, in combination with the high refractive index film, the antireflection effect may be significantly reduced. Therefore, the refractive index of the low refractive index film is more preferably set to a value within the range of 1.3 to 1.6, and more preferably set to a value within the range of 1.3 to 1.5. Moreover, when the refractive index of a low refractive index film is less than 1.3, the kind of material which can be used may be excessively restrict | limited.

In the case where a plurality of low refractive index films are provided, at least one of them may have a value of the refractive index within the above-described range, and thus the other low refractive index films may exceed 1.6.

In addition, when providing a low refractive index film, since the outstanding reflection prevention effect can be acquired, it is preferable to make the difference of refractive index with a high refractive index film into 0.05 or more value. This is because when the difference in refractive index between the low refractive index film and the high refractive index film is less than 0.05, the synergistic effect in such an antireflection film layer is not obtained, but the antireflection effect may be lowered.

Therefore, the refractive index difference between the low refractive index film and the high refractive index film is more preferably set to a value within the range of 0.1 to 0.5, and more preferably to a value within the range of 0.15 to 0.5.

(4) thickness

Next, the thicknesses of the high refractive index film and the low refractive index film will be described. First, the thickness of the high refractive index film is not particularly limited, but is preferably a value within the range of 50 to 30,000 nm, for example. This is because when the thickness of the high refractive index film is less than 50 nm, in combination with the low refractive index film, the antireflection effect and the adhesion to the substrate may be lowered. On the other hand, when the thickness exceeds 30,000 nm, the optical interference is reduced. It is because it does not produce and the antireflection effect may fall.

Therefore, it is more preferable to make the thickness of a high refractive index film into the value within the range of 50-1,000 nm, and it is more preferable to set it as the value within the range of 60-500 nm.

In addition, in order to obtain higher antireflection property, when providing a multi-layered structure by providing two or more layers of high refractive index films, the sum total thickness can be made into the value within the range of 50-30,000 nm.

In addition, when providing a hard-coat layer between a high refractive index film and a base material, the thickness of a high refractive index film can be made into the value within the range of 50-300 nm.

The thickness of the low refractive index film is not particularly limited, but is preferably a value within the range of 50 to 300 nm, for example. This is because if the thickness of the low refractive index film is less than 50 nm, the adhesion to the high refractive index film as the underlying layer may be lowered. On the other hand, if the thickness exceeds 300 nm, no optical interference occurs and the antireflection effect is lowered. This is because there is a case.

Therefore, it is more preferable to make the thickness of the low refractive index film into the value within the range of 50 to 250 nm, and more preferably to the value within the range of 60 to 200 nm.

In order to obtain a higher antireflection property, when a plurality of low refractive index films are provided in a multi-layered structure, the total thickness may be a value within a range of 50 to 300 nm.

(5) mention

Next, the base material for providing a high refractive index film, a hard coating layer, etc. is demonstrated. Although the kind of base material which provides such a high refractive index film | membrane etc. is not restrict | limited, For example, the base material containing glass, a polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin (TAC), etc. are mentioned. have. By producing an antireflection laminate comprising such a substrate, an excellent antireflection effect is used in a wide range of antireflection films such as a lens part of a camera, a screen display part of a television (CRT), or a color filter in a liquid crystal display device. Can be obtained.

(6) forming method

When forming a high refractive index film or a low refractive index film from a high refractive index material or a low refractive index material, respectively, it is preferable to coat with respect to a base material (application member). As such a coating method, methods such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an ink jet method can be used.

The means for curing the high refractive index material and the low refractive index material is not particularly limited, but heating is preferable, for example. In that case, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. By heating in this manner, an antireflection laminate excellent in antireflection can be obtained more efficiently without damaging the substrate or the antireflection film formed. Therefore, it is more preferable to heat 2 to 120 minutes at the temperature within the range of 50-180 degreeC, and to heat for 5 to 60 minutes at the temperature within the range of 80-150 degreeC.

In addition, when the melamine compound is used as a curing agent, the degree of curing of the high refractive index material or the low refractive index material is determined by infrared spectroscopic analysis of the amount of the methylol group or the alkoxylated methyl group in the melamine compound or the gelation rate of the Soxhlet extractor. It can be confirmed quantitatively by measuring using.

<Third embodiment>

As shown in FIG. 2, 3rd Embodiment is the anti-reflective laminated body 24 through which the hard-coat layer 18 was interposed between the base material 12 and the high refractive index film 20. As shown in FIG. Thus, the adhesive force with respect to the base material 12 of the high refractive index film 20 can be improved further through the hard-coat layer 18. In addition, the durability of the antireflective laminate 24 can be further improved by the mechanical properties of the hard coat layer 18.

Hereinafter, although the hard-coat layer which is the characteristic of 3rd Embodiment is demonstrated centeringly, since a base material, a high refractive index film, a low refractive index film, or these formation methods are the same as the content demonstrated in 2nd Embodiment, it is here. Will be omitted.

The hard coat layer according to the third embodiment, for example, it is preferable that a material such as Si0 _2, an epoxy resin, an acrylic resin, a melamine-based resin.

In addition, the thickness is not particularly limited, but it is particularly preferable to set the value within the range of 1 to 50 µm, and more preferably the value within the range of 5 to 10 µm. This reason is because when the thickness of the hard coating layer is less than 1 m, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, when the thickness exceeds 50 m, it may be difficult to form uniformly.

Hereinafter, although the Example of this invention is described in detail, the scope of the present invention is not limited to description of these Examples. In addition, in the Example, the compounding quantity of each component means a weight part, unless there is particular notice.

<Example 1>

(Preparation of high refractive index material)

16 parts by weight of antimony-containing tin oxide (SN-100P manufactured by Ishihara Techno Co., Ltd.) having an average particle diameter of 0.01 µm, and Denkabutyral # 2000-L (manufactured by Denki Chemical Co., Ltd., polyvinyl butyral resin, average A solvent-dispersed antimony-containing tin oxide sol comprising a polymerization degree of about 300, 21 parts by weight or more of polyvinyl alcohol units in one molecule, 71 parts by weight of glass transition point), 48 parts by weight of methyl isobutyl ketone, and 32 parts by weight of t-butanol. (Solid content concentration 20% by weight) 4 parts by weight of Cymel 303 (Mitsui Cytec Co., Ltd. product, methylated methylolmelamine compound) was added to 100 parts by weight of a container with a stirrer, and a catalyst 4050 (Mitsui Scitech Co., Ltd.) was stirred. ), Aromatic sulfonic acid compound) 2.25 parts by weight (active ingredient 0.72 parts by weight) were added sequentially, followed by stirring for 10 minutes to give a high refractive index material having a viscosity of 8 cps (measurement temperature of 25 ° C) and a solid content concentration of 23.3% by weight (high concentration product: A Type).

Subsequently, 100 parts by weight of the obtained high refractive index material (type A) was placed in a container with a stirrer, and 219.2 parts by weight of methyl isobutyl ketone and 146.2 parts by weight of t-butanol were added while stirring, followed by stirring for 10 minutes, and a viscosity of 3 mpa. S (measurement temperature 25 degreeC) and the high refractive index material (low concentration product: B type) of 5.0 weight% of solid content concentration were obtained.

The storage stability and applicability | paintability of the obtained high refractive index material (A and B type), and the refractive index and antistatic property of the high refractive index film obtained by hardening such a high refractive index material were respectively evaluated on the following references | standards. The results are shown in Table 1.

(1) storage stability

(Circle): Even after leaving a high refractive index material at room temperature for 30 days, sedimentation of electroconductive metal oxide microparticles | fine-particles is not observed and can be heat-hardened on 120 degreeC and the conditions for 10 minutes.

(Triangle | delta): Although settling a high refractive index material at room temperature for 30 days, although some sedimentation of electroconductive metal oxide microparticles | fine-particles is observed, it can heat-harden on 120 degreeC and the conditions for 10 minutes.

X: After leaving a high refractive index material at room temperature for 30 days, remarkable sedimentation of electroconductive metal oxide microparticles | fine-particles is observed, or cannot heat-harden on 120 degreeC and the conditions for 10 minutes.

(2) applicability

(Circle): High refractive index material was able to apply | coat with uniform thickness using the wire bar coater (# 3).

(Triangle | delta): The high refractive index material was able to be apply | coated to substantially uniform thickness using the wire bar coater # 3.

X: The high refractive index material could not be apply | coated to a uniform thickness using the wire bar coater # 3.

(3) refractive index

The obtained high refractive index material was apply | coated on the silicon wafer (thickness 1mm) using the wire bar coater (# 3), and it air-dried at room temperature for 5 minutes, and formed the coating film. Then, it heated on 120 degreeC and the conditions of 10 minutes using oven, and the high refractive index film of 0.1 micrometer thickness was hardened and formed. The refractive index of Na-D line | wire in the obtained high refractive index film was measured on the conditions of 25 degreeC of measurement temperature using the ellipsometer.

(4) antistatic

The obtained high refractive index material was formed into a film on the PET untreated surface using a wire bar coater (# 3), and the surface resistance (Ω / □) of the obtained high refractive index film was obtained by using a high resistance meter (HP4339 manufactured by Hewlett-Packard Co., Ltd.). It measured on the conditions of 26 mm (phi) electrode diameters, and the applied voltage 100V using the following, and antistatic property was evaluated on the following references | standards.

(Double-circle): Surface resistance is a value of 10 <^8> ohm / square or less.

○: The surface resistance is a value of 10 ¹⁰ Ω / □ or less.

(Triangle | delta): Surface resistance is a value of 10 <^12> ohm / square or less.

X: Surface resistance is the value over 10 <^15> ohm / square.

(Preparation of low refractive index material)

After fully replacing the interior autoclave made of stainless steel with an internal volume of 1.5 L with nitrogen gas, 500 g of ethyl acetate, 57.2 g of ethyl vinyl ether (EVE), 10.2 g of hydroxybutyl vinyl ether (HBVE), and peroxide 3 g of lauroyl was added, cooled to -50 ° C with dry ice-methanol, and oxygen in the system was removed again with nitrogen gas. Then, 146 g of hexafluoropropylene (HFP) was put in, and temperature rising was started. The pressure at the point when the temperature in the autoclave reached 60 ° C. was 5.2 × 10 ⁵ Pa. Thereafter, the reaction was continued under stirring at 60 ° C. for 20 hours, and the autoclave was water-cooled and the reaction was stopped when the pressure was reduced to 1.5 × 10 ⁵ Pa. After reaching room temperature, the unreacted gas monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 28.1 wt%. The polymer solution was poured into methanol to precipitate the polymer, and the polymer was then washed with methanol and dried in vacuo at 50 ° C. to obtain a fluorine-containing copolymer having 193 g of hydroxyl groups.

The intrinsic viscosity (using N, N-dimethylacetamide solvent, measurement temperature of 25 ° C) was 0.26 dl / g with respect to the obtained fluorine-containing copolymer having a hydroxyl group, the glass transition temperature (DSC measurement, heating rate of 5 ° C / min, It was confirmed that the nitrogen stream was 20 ° C, the fluorine content (Alizarin complexson method) was 53.4% by weight, and the hydroxyl value (acetyl value method using acetic anhydride) was 27.1 mg KOH / g.

Subsequently, in a container with a stirrer, 100 parts by weight of a fluorine-containing copolymer having a hydroxyl group, 10 parts by weight of Cymel 303 (manufactured by Mitsui Cytec Co., Ltd., an alkoxylated methylmelamine compound), and 900 parts by weight of methyl isobutyl ketone, respectively While adding and stirring, the fluorine-containing copolymer having a hydroxyl group and cymel 303 were reacted under conditions of 100 ° C. and 5 hours. Subsequently, 2 parts by weight of Catalyst 4050 (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid compound) was further added, followed by stirring for 10 minutes to obtain a low refractive index material having a viscosity of 2 mpa · s (measurement temperature of 25 ° C.).

In addition, the refractive index of the low refractive index film obtained by hardening the obtained low refractive index material was measured similarly to the high refractive film. That is, the low refractive index material was apply | coated on the silicon wafer (thickness 1mm) using the wire bar coater # 3, and it air-dried for 5 minutes at room temperature, and formed the coating film. Subsequently, it heated on 120 degreeC and the conditions of 60 minutes using oven, and the low refractive index film of 0.1 micrometer thickness was hardened and formed. The refractive index of the Na-D ray in the obtained low refractive index film was measured using an ellipsometer on the conditions of 25 degreeC of measurement temperature. The obtained results are shown in Table 1.

(Formation and Evaluation of Antireflection Laminate)

The obtained high refractive index material (Type A) is applied onto a polycarbonate plate (thickness 1 mm, manufactured by Teijin Kasei Co., Ltd.) using a wire bar coater (# 20), and air-dried at room temperature for 5 minutes to apply A film was formed. Subsequently, it heated on 120 degreeC and the conditions of 10 minutes using oven, The high refractive index film (type A) of 4 micrometers in thickness was hardened and formed. It was 1.63 when the refractive index of the obtained high refractive index film was measured using the ellipsometer on the conditions of 25 degreeC of measurement temperature.

In addition, using the obtained antistatic high refractive index material (B type) using a wire bar coater (# 3), a polycarbonate plate with a hard coating (refractive index of 1.55 of the hard coating, a thickness of 1 mm of the polycarbonate plate, Teijin Kasei ( It was applied to the production), and air-dried at room temperature for 5 minutes to form a coating film. Then, it heated on 120 degreeC and the conditions of 10 minutes using oven, and the antistatic high refractive index film (type B) of 0.12 micrometer thickness was hardened and formed. It was 1.63 when the refractive index of the obtained high refractive index film was measured similarly.

Subsequently, a low refractive index material was applied onto each of the high refractive index films (types A and B) using a wire bar coater (# 3) and air dried at room temperature for 5 minutes to form a coating film. Subsequently, it heated on 120 degreeC and the conditions for 60 minutes using oven, the low refractive index film of thickness 0.10micrometer was hardened, and it combined with the high refractive index film on the base material, and produced the reflection prevention laminated bodies (I and II type). That is, the anti-reflective laminate which does not have a hard coating is type I, and the anti-reflective laminate which has a hard coating is type II.

The antireflection, transparency, haze (Haze value), antistatic property and hardness in the obtained antireflection laminates (types I and II) were measured by the measuring method shown below. In addition, the adhesiveness between an antireflection film and a base material was evaluated based on the following criteria.

(1) antireflection

Magnetic spectrophotometer U-3410, Hitachi Seisakusho Co., Ltd. combining spectroscopic reflectance measuring device (large sample chamber integrating sphere accessory 150-09090) in the obtained antireflective laminates (types I and II) Manufacture), and evaluated the reflectance in the range of wavelength 340-700 nm. That is, the reflectance in the aluminum vapor deposition film is made into the reference | standard (100%), and the reflectance of the antireflective laminated body (antireflection film) in each wavelength is measured, and the following reference | standard from the reflectance of the light in wavelength 550nm among these is measured. The antireflection was evaluated as follows. The results are shown in Table 1.

(Double-circle): A reflectance is a value of 1% or less.

○: The reflectance is a value of 2% or less.

(Triangle | delta): A reflectance is a value of 3% or less.

X: The reflectance is a value exceeding 3%.

(2) transparency

The light transmittance (T%) of wavelength 550nm in the obtained antireflective laminated body (types I and II) was measured using the spectrophotometer, and transparency was evaluated on the following references | standards from the obtained light transmittance. The obtained results are shown in Table 1.

○: The light transmittance is a value of 95% or more.

(Triangle | delta): The light transmittance is a value below 80 to 95%.

X: The light transmittance is a value of less than 80%.

(3) turbidity

Haze (Haze value) in the obtained antireflection laminates (I and II types) was measured using a Haze system. The obtained results are shown in Table 1.

(4) antistatic

The surface resistance (Ω / □) of the obtained antireflective laminates (types I and II) was subjected to a main electrode diameter of 26 mm Φ and an applied voltage of 100 V using a high resistance meter (HP4339 manufactured by Hewlett-Packard). It measured and evaluated antistatic property on the following references | standards. The results are shown in Table 1.

(Double-circle): Surface resistance is a value of 10 <^8> ohm / square or less.

○: The surface resistance is a value of 10 ¹⁰ Ω / □ or less.

(Triangle | delta): Surface resistance is a value of 10 <^12> ohm / square or less.

X: Surface resistance is the value over 10 <^15> ohm / square.

(5) hardness

Instead of the polycarbonate plate, a high-refractive index film and a low-refractive index film were sequentially laminated from the lower side in place of the polycarbonate plate so as not to affect the flexibility of the substrate, and the antireflection laminate for hardness measurement (no hard coating layer) ) Was prepared. The pencil hardness in the obtained antireflection laminated body was measured based on JISK5400. In addition, the determination of the pencil hardness was performed by visually observing the presence or absence of a flaw generation. The obtained results are shown in Table 1.

(6) adhesion

The obtained antireflection laminates (I and II types) were subjected to a checkerboard scale test in accordance with JIS K5400, and evaluated according to the following criteria. The obtained results are shown in Table 1.

(Circle): Peeling was not observed in 100 checkerboard scales.

(Triangle | delta): Peeling of 1 to 3 checker scales was observed in 100 checkerboard scales.

X: In 100 checkerboard scales, peeling of 4 or more checkerboard scales was observed.

<Examples 2 and 3>

The high refractive index material (types A and B) and the low refractive index material in the same manner as in Example 1 except that the ratio of the polyvinyl butyral resin and the curing agent to the antimony-containing tin oxide in the high refractive index material of Example 1 was changed. Were prepared, and the high refractive index material and the antireflection laminates (types I and II) were evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

Comparative Example 1

A high refractive index material (types C and D) was prepared in the same manner as in Example 1 except that zirconium oxide was used as the nonconductive metal oxide fine particles instead of the conductive metal oxide fine particles. That is, type C is a high concentration product and type D is a low concentration product.

Subsequently, each of the high refractive index materials (types C and D) was evaluated in the same manner as in Example 1. In addition, antireflection laminates (types III and IV) were formed from the respective high refractive index materials and evaluated in the same manner as in Example 1. The obtained results are shown in Table 2.

<Comparative Examples 2 to 3>

A high refractive index material (types C and D) was prepared in the same manner as in Example 1 except that the addition amount of the curing agent was outside the range of the present invention (less in Comparative Example 2, and larger in Comparative Example 3). Subsequently, each high refractive index material was evaluated similarly to Example 1. In addition, the antireflection laminates (types III and IV) were formed and evaluated in the same manner as in Example 1 except that the respective high refractive index materials were used. The obtained results are shown in Table 2.

According to the high refractive index material of the present invention, excellent storage stability and antistatic property can be obtained, and excellent antireflective property and antistatic property can be obtained by the antireflective laminate of the present invention.

In addition, according to the antireflection laminate of the present invention in which a specific high refractive index layer and a specific low refractive index layer are combined, more excellent antireflection property, for example, an antireflection rate of 1.0% or less can be obtained.

Claims (4)

(1) 100 parts by weight of conductive metal oxide fine particles having an average particle diameter of 0.01 to 2 µm, (2) 1 to 70 parts by weight of a hydroxyl group-containing polymer, (3) 1 to 70 parts by weight of a curing agent having a functional group capable of reacting with a hydroxyl group The refractive index after hardening is 1.60 or more, The high refractive index material characterized by the above-mentioned. The high refractive index material according to claim 1, wherein the conductive metal oxide fine particles are antimony-containing tin oxide or indium-containing tin oxide. Substrate, The high refractive index film and the low refractive film which were obtained by hardening the high refractive index material of Claim 1 or 2 on the said board | substrate. Antireflection laminate comprising a. The antireflection laminate according to claim 3, wherein the low refractive index film is obtained by curing a low refractive index material containing a curable fluorine-containing copolymer, and has a refractive index of less than 1.60.