JP2002160330A - Cured product and structure containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured product having good abrasion properties and a structure using the same. SOLUTION: The cured product consists of a curable resin composition containing a multifunctional (meth)acrylate compound, an inorganic oxide particle having a number average particle diameter of 5 to 500 nm, and a curing agent. When the cured product has a minimum thickness of t1 and a maximum thickness of t2 in its cross-section, a following equation is satisfied: 1.3<=t2/t1<=3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cured product in which a structure excellent in scratch resistance can be easily formed, and a structure containing the same.

[0002]

2. Description of the Related Art As a material for forming an antireflection film, for example,
Thermosetting polysiloxane compositions are known, and are disclosed in JP-A-61-247743, JP-A-6-25599, JP-A-7-331115 and JP-A-10-115.
No. 2,232,301. However, the antireflection film obtained by using such a thermosetting polysiloxane composition has a problem of poor scratch resistance and, as a result, poor durability. In addition, in manufacturing such an antireflection film, it is necessary to perform heat treatment at a high temperature for a long time, and thus there has been a problem that productivity is low, or types of applicable base materials are limited.

Therefore, as disclosed in JP-A-8-94806, a high-refractive-index film in which fine particles are localized in a high-refractive-index binder resin on a substrate, and a fluorine-based copolymer An optical functional film has been proposed in which low refractive index films made of are sequentially laminated. More specifically, in order to form a high-refractive-index film, a fine particle layer of metal oxide particles of 200 nm or less is previously formed on a process paper, and is applied to a high-refractive-index binder resin on a base material. Then, the fine particle layer is buried in the high refractive index binder resin to be localized. As for the low refractive index film,
A monomer composition containing 30 to 90% by weight of vinylidene fluoride and 5 to 50% by weight of hexafluoropropylene is copolymerized to have a fluorine content of 60 to 70% by weight.
100 parts by weight of a fluorine-containing copolymer, and 30 to 150 parts by weight of a polymerizable compound having an ethylenically unsaturated group,
When the total amount of these is 100 parts by weight, 0.5 to
A resin composition comprising 10 parts by weight of a polymerization initiator is cured to form a thin film having a thickness of 200 nm or less.

[0004]

However, the optical functional film disclosed in Japanese Patent Application Laid-Open No. 8-94806 has a complicated manufacturing process for a high refractive index film, and as a result, the optical functional film having uniform characteristics. It was difficult to make a film. In addition, such an optical functional film does not consider any surface irregularities in the high refractive index film,
Therefore, there was a problem that the scratch resistance of the low refractive index film was poor. Therefore, the inventors of the present invention have conducted intensive studies and, as a result, used a specific curable resin composition,
It has been found that the above problem can be solved by considering the height of the surface irregularities. That is, an object of the present invention is to provide a cured product having a simple structure and excellent scratch resistance and a structure using the same.

[0005]

According to the present invention, a polyfunctional (meth) acrylate compound having a number average particle diameter of 5 to 5 is prepared.
A cured product made of a curable resin composition containing 00 nm inorganic oxide particles and a curing agent, wherein the minimum thickness in the cross section of the cured product is t ₁ and the maximum thickness is t ₂ A cured product characterized by satisfying the following relational expressions is provided, and the above-mentioned problem can be solved. 1.3 ≦ t ₂ / t ₁ ≦ 3 By satisfying these relationships, excellent scratch resistance can be obtained not only in the cured product but also in the surface layer provided thereon. Here, the film thickness in the cross section of the cured product refers to an average line of a lower layer roughness curve (based on JISB0601) as a reference line in a vertical cross section in the thickness direction of the cured product observed by an electron micrograph. sometimes,
It is defined as the measured value of the distance from the reference line to the cross section of the cured product. Therefore, according to the above definition, the minimum film thickness (t ₁ ) and the maximum film thickness (t ₂ ) correspond to the roughness curve of the hard coat layer 18 as a base in the vertical section 20 in the thickness direction of the cured product in FIG. Average line (JIS B060
1) as the reference line 14, and the reference line 1
4 as the actual measured value of the distance from the cured product section 20 to the lowest valley and the actual measured value of the distance to the highest peak.

In constituting the cured product of the present invention, the curable resin composition to be used preferably contains a reactive silane compound as a polyfunctional (meth) acrylate compound. That is, by containing such a reactive silane compound as a part of the polyfunctional (meth) acrylate compound or as the polyfunctional (meth) acrylate compound itself, the inorganic oxide particles can be strongly bonded. . Therefore, in the cured product,
Further excellent scratch resistance can be obtained.

[0007] In constituting the cured product of the present invention, the polyfunctional (meth) acrylate compound contained in the curable resin composition used is trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl. It is preferably at least one polyfunctional (meth) acrylate compound selected from the group consisting of (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol penta (meth) acrylate. By including these polyfunctional (meth) acrylate compounds, more excellent scratch resistance can be obtained, and the transparency of the cured product is less likely to be impaired.

In constituting the cured product of the present invention, the curable resin composition used comprises inorganic oxide particles comprising silicon oxide (SiO ₂ ), antimony-doped tin oxide (ATO), and zinc oxide (ZnO). ), Tin-doped indium oxide (ITO), and antimony zinc oxide (A
ZO) and at least one inorganic oxide particle selected from the group consisting of aluminum oxide (Al ₂ O ₃ ). By including these inorganic oxide particles, more excellent scratch resistance can be obtained, and the transparency of the cured product is less likely to be impaired.

Further, the cured product of the present invention may be used as an antireflection film laminate, antifouling film, water repellent film, antistatic film, alignment film, primer layer, color filter, fluorescent film, polarizing film, or light guide film. It is preferable to include it as a part. In such applications, if the cured product of the present invention is provided, excellent scratch resistance and transparency can be exhibited.

Another aspect of the present invention is a structure characterized by containing the above-described cured product, for example, an antireflection film laminate, an antifouling film, a water repellent film, an antistatic film, an alignment film, It is a surface layer with a primer layer, a color filter, a fluorescent film, a polarizing film, or a light guide film.

[0011]

[First Embodiment] The first embodiment is an example in which the cured product of the present invention is used for a high refractive index film of an antireflection film laminate. As shown in FIG. 2, the antireflection film laminate using the cured product of the present invention has a high refractive index film (second layer) 10 and a low refractive index film (first layer) on a substrate 12.
14 in that order. As a modified example of the antireflection film laminate, as shown in FIG. 3, an antireflection film laminate 24 having a hard coat layer 18 interposed between the base material 12 and the high refractive index film 20 is used. Is also preferred.

1. High-refractive-index film (1) Curable composition for high-refractive-index film A curable composition for a high-refractive-index film for forming a high-refractive-index film comprises the following components (A) to (C). There is a feature. (A) polyfunctional (meth) acrylate compound (B) inorganic oxide particles (C) curing agent

The polyfunctional (meth) acrylate compound (A)
Component) The polyfunctional (meth) acrylate compound of the component (A) is a compound containing at least two (meth) acryloyl groups in a molecule. By using such a polyfunctional (meth) acrylate compound, the curability of the curable composition for a high refractive index film can be improved.

More specifically, the polyfunctional (meth) acrylate compounds include trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, dipentaerythritol penta (meth) acrylate And at least one polyfunctional (meth) acrylate compound selected from the group consisting of pentaerythritol penta (meth) acrylate. However, it is also preferable to add a monofunctional (meth) acrylate compound, a chain transfer agent, or the like for the purpose of adjusting reactivity, hardness, and the like.

As the polyfunctional (meth) acrylate compound, a reaction compound obtained by reacting the above-mentioned polyfunctional (meth) acrylate compound with alkoxysilane via a polyisocyanate compound (hereinafter referred to as a reactive silane compound) May be used.). Examples of such an alkoxysilane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyldimethoxyethoxysilane, γ-mercaptopropyldiethoxymethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ -Mercaptopropyldiethoxymethylsilane and the like are preferred. Further, as the polyisocyanate compound, 2,4-tolylene diisocyanate
2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalenedi isocyanate, m-phenylene diisocyanate P-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate,
1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1 , 3-phenyldiisocyanate, 4-diphenylpropanediisocyanate
, Lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 (or 6) -bis (isocyanatomethyl ) -Bicyclo [2.2.1] heptane and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane and the like are preferable. The alkoxysilane and the polyisocyanate compound can be used alone or in combination of two or more. Therefore, as a polyfunctional (meth) acrylate compound as a reactive silane compound, a urethane bond [—O—C (＝ O) NH—] or a thiourethane bond [—S—C (＝ O) NH— And an alkoxysilane compound having an unsaturated double bond.

Inorganic Oxide Particles (Component B) The number average particle diameter of the inorganic oxide particles as the component (B) is preferably in the range of 5 to 500 nm. The reason is that the number average particle diameter of the inorganic oxide particles is 5n.
If it is less than m, it may be difficult to uniformly disperse the inorganic oxide particles, or it may be difficult to adjust the maximum film thickness, and the scratch resistance may decrease.
On the other hand, the number average particle diameter of the inorganic oxide particles is 500 n.
If it exceeds m, sedimentation is likely to occur during production, or it becomes difficult to adjust the minimum film thickness, and the abrasion resistance may decrease. Therefore, the number average particle diameter of the inorganic oxide particles is preferably set to a value in the range of 7 to 400 nm, and more preferably to a value in the range of 10 to 350 nm. In addition, the number average particle diameter of the inorganic oxide particles is an average value of the particle diameter measured by an electron microscope.

The type of the inorganic oxide particles is preferably determined in consideration of abrasion resistance, ease of adjusting the refractive index, and the like. More specifically, silicon oxide (SiO ₂ ,
Refractive index 1.47), zirconium oxide (ZrO ₂ , refractive index 2.05), tin oxide (SnO ₂ , refractive index 2.0)
0), antimony-doped tin oxide (ATO, refractive index 1.
95), titanium oxide (TiO _2, refractive index from 2.3 to 2.
7), zinc oxide (ZnO, refractive index 1.90), tin-doped indium oxide (ITO, refractive index 1.95), cerium oxide (CeO ₂ , refractive index 2.2), selenium oxide (Se)
O ₂ , refractive index 1.95), antimony oxide (Sb ₂ O ₅ ,
Refractive index 1.71), aluminum oxide (Al ₂ O ₃ , refractive index 1.63), yttrium oxide (Y ₂ O ₃ , refractive index 1.
87), and zinc antimonate (AZO, refractive index 1.
90) or a combination of two or more.

The addition of a relatively small amount of the inorganic oxide particles makes it possible to easily adjust the refractive index after curing to a value of 1.5 or more and to provide an antistatic function. Therefore, it is preferable to use conductive metal oxide particles having a refractive index of 1.9 or more. Specifically, zirconium oxide, tin oxide, antimony-doped tin oxide,
It is preferable to use titanium oxide, zinc oxide, tin-doped indium oxide, selenium oxide, or the like.

It is preferable that the inorganic oxide particles are treated with a coupling agent. The reason for this is that the inorganic oxide particles have been subjected to the coupling agent treatment, so that the bonding force between the resin and the surrounding resin can be increased, and as a result, the scratch resistance of the low refractive index film is significantly improved. This is because In addition, by performing the coupling agent treatment in this manner, the dispersibility of the inorganic oxide particles can be improved, and the storage stability of the curable composition for a high refractive index film at the time of production can be improved.

Here, in performing the coupling agent treatment, preferable coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane. Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
One kind of aminopropyltriethoxytitanium, γ-aminopropyltriethoxyaluminum and the like, or a combination of two or more kinds thereof may be mentioned. Incidentally, the treatment amount of the coupling agent, 0.1 parts by weight of the inorganic oxide particles, 0.1
To 20 parts by weight, preferably 0.5 to 1 part by weight.
The ratio is more preferably 5 parts by weight, and further preferably 1 to 10 parts by weight.

Further, the content of the inorganic oxide particles is preferably set to a value within the range of 3 to 90 vol% with respect to the total amount. The reason is that when the content of the inorganic oxide particles becomes less than 3 vol%, the minimum thickness (t ₁ )
This is because it may be difficult to adjust the maximum film thickness (t ₂ ), and as a result, the scratch resistance of the first layer may be reduced. On the other hand, when the content of the inorganic oxide particles exceeds 90 vol%, the mechanical strength of the second layer decreases, and as a result, the scratch resistance of the low refractive index film may decrease. is there. Therefore, the content of the inorganic oxide particles is more preferably set to a value in the range of 5 to 80 vol%, and the content of the inorganic oxide particles is further preferably set to a value in the range of 10 to 75 vol%. .

Curing Agent (Component C) Examples of the curing agent (C) include a photoradical generator and a photoacid generator. Such a curing agent can be used alone, but a photo radical generator,
It is also preferable to use a photoacid generator in combination. The amount of the curing agent is not particularly limited, but is preferably, for example, 0.1 to 30 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound. . The reason for this is that if the amount of the curing agent used is less than 0.1 part by weight, the curing of the polyfunctional (meth) acrylate compound may be insufficient. On the other hand, if the amount of the curing agent exceeds 30 parts by weight, the storage stability of the curable composition for a high refractive index film may decrease. Accordingly, the amount of the curing agent used is more preferably set to a value within the range of 0.5 to 20 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound.

Additive 1 The curable resin composition preferably also contains a hydroxyl group-containing polymer. By including such a hydroxyl group-containing polymer, not only is it easy to handle the curable composition for a high refractive index film, but also when a hard coat layer is provided below or when a surface layer is provided above. Excellent adhesion can be obtained between these layers. Examples of such a hydroxyl group-containing polymer include a polyvinyl acetal resin (polyvinyl butyral resin, polyvinyl formal resin), a polyvinyl alcohol resin, a polyacrylic resin, a polyphenolic resin, a phenoxy resin, and the like, alone or in combination of two or more. Can be

It is preferable that the amount of the hydroxyl group-containing polymer to be added falls within a range of 1 to 100 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound. The reason for this is that if the amount of the hydroxyl group-containing polymer added is less than 1 part by weight, the resulting high refractive index film may have insufficient adhesion to the substrate in some cases.
If the amount of the hydroxyl group-containing polymer exceeds 100 parts by weight, the amount of the inorganic oxide particles relatively decreases, and it may be difficult to adjust the refractive index after curing. Therefore, polyfunctional (meth) acrylate compound 1
The amount of the hydroxyl group-containing polymer to be added is 3 to 7 parts with respect to 00 parts by weight.
More preferably, the value is in the range of 0 parts by weight,
More preferably, the value is in the range of 0 parts by weight.

Additive 2 A compound having both a functional group capable of reacting with a hydroxyl group and a functional group capable of photopolymerization in the curable resin composition (hereinafter, referred to as “the compound”).
It may be referred to as a joint compound. ) Is also preferable. Examples of such a co-present compound include a functional group capable of reacting with a hydroxyl group (hereinafter, may be referred to as a hydroxyl-reactive functional group) and a photo-polymerizable functional group (hereinafter, referred to as a photo-polymerizable functional group). Are preferable. The reason for this is that the polyfunctional (meth) acrylate compound can be photocured by using the photopolymerizable functional group of the coexisting compound, or by heating using the hydroxyl-reactive functional group. This also makes it possible to cure the polyfunctional (meth) acrylate compound.

Here, the hydroxyl-reactive functional group includes, for example, an amino group, an isocyanate group, a carboxyl group,
Examples thereof include an acid anhydride group, an aldehyde group, and a halogen.
Similarly, examples of the photopolymerizable functional group include an epoxy group, an oxetane group, and a vinyl group. Therefore, the combined compounds include t-butylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate,
-Methacryloxy-N, N-dicarboxymethyl-p-
Phenylenediamine, melamine / formaldehyde / alkyl monoalcohol, 2- [o- (1′-methylpropylideneamino) carboxyamino] ethyl acrylate, 2,3-dibromopropyl acrylate, 2,3-
Dibromopropyl methacrylate, methacryloxyethyl phthalate, N-methacryloxy-N-carboxymethylpiperidine, 4-methacryloxyethyl trimellitic acid, acryloxyethyl terephthalate, ethylene oxide-modified phthalic acrylate, ethylene oxide-modified succinic acrylate, 4-methacryloxy Either one kind of ethyl trimellitic anhydride or a combination of two or more kinds can be mentioned. In addition, the addition amount of the co-present compound is based on 100 parts by weight of the polyfunctional (meth) acrylate compound.
It is preferable that the value be in the range of 10 to 300 parts by weight.

Additive 3 In the curable resin composition, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, n-butanol, ethyl cellosolve,
Ethyl lactate (EL), diacetone alcohol (DA
A), propylene glycol monomethyl ether (PG
It is preferable to use at least one organic solvent selected from the group consisting of ME), acetylacetone (AcAc), and ethyl acetoacetate (EAcAc). The reason is that by using such an organic solvent,
This is because when the high refractive index film is formed from the curable composition for a high refractive index film, it is easy to control the surface roughness (Rz) of the high refractive index film. The amount of the organic solvent to be added is not particularly limited, but the amount of the organic solvent is set to a value within the range of 50 to 20,000 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate compound. It is preferred that

Additive 4 The curable composition for a high refractive index film contains a photosensitizer, a polymerization inhibitor, a polymerization initiation auxiliary agent, a leveling agent, a wettability improving agent as long as the object and effects of the present invention are not impaired. Agents, surfactants,
It is also preferable to further include additives such as a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic filler, a pigment, and a dye.

In particular limitation is imposed on the [0029] values themselves (2) Minimum thickness (t ₁₎ and the maximum thickness (t ₂₎ From the film thickness (t ₁₎ From the film thickness of the high refractive index film section (t ₁₎ Although not something, 50-250n
It is preferable that the value be within the range of m. The reason is that when the minimum film thickness is less than 50 nm, the mechanical strength of the high refractive index film is reduced, and the scratch resistance of the cured product itself is reduced, or the resistance of the surface layer formed thereon is reduced. This is because the abrasion may decrease. On the other hand, if the minimum film thickness exceeds 250 nm, manufacturing becomes difficult, or the value of the maximum film thickness becomes excessively large in order to adjust the ratio of the maximum film thickness / minimum film thickness to a predetermined range. That's why. Therefore, the minimum film thickness (t ₁ ) in the high refractive index film cross section is more preferably set to a value in the range of 70 to 230 nm, and even more preferably to a value in the range of 100 to 200 nm.

[0030] For the values themselves up thickness (t ₂₎ the maximum thickness of the high refractive index film section (t _2), is not particularly limited, from 65 to 750
Preferably, the value is in the range of nm. The reason for this is
If the maximum film thickness is less than 65 nm, the value of the minimum film thickness may be excessively small in order to adjust the ratio of the maximum film thickness / minimum film thickness to a predetermined range. On the other hand, when the maximum thickness exceeds 750 nm, the production becomes difficult, the mechanical strength of the high refractive index film is reduced, and the scratch resistance of the cured product itself is reduced, or the cured product is formed thereon. This is because the scratch resistance of the surface layer may be reduced. Therefore, the maximum thickness (t) in the cross section of the high refractive index film
₂ ) is more preferably set to a value in the range of 98 to 575 nm, and even more preferably to a value in the range of 150 to 400 nm. In addition, the average line of the roughness curve of the high refractive index film in the cross section of the electron micrograph shown in FIGS.
The average value of the film thickness in the cross section of the high refractive index film calculated from the distance from the average line of the roughness curve of the hard coat layer as the base is not particularly limited, but is 50 nm to 700 nm.
It is preferably a value in the range of nm. The reason for this is
When the thickness of the high refractive index film is less than 50 nm, the antireflection effect and the adhesion to the substrate may be reduced when combined with the low refractive index film. If the thickness exceeds 700 nm, the production may be difficult, and the transparency and the scratch resistance may decrease. Therefore, the thickness of the high refractive index film is set to 10
The value is more preferably in the range of 0 nm to 300 nm, and even more preferably in the range of 120 nm to 200 nm.

Ratio of maximum film thickness / minimum film thickness When the minimum film thickness in the cross section of the high refractive index film is t ₁ and the maximum film thickness is t ₂ , the ratio of the maximum film thickness / minimum film thickness (t ₂ / t ₁ ) must satisfy the following relational expression. 1.3 ≦ t ₂ / t ₁ ≦ 3 The reason for this is that when t ₂ / t ₁ is less than 1.3, the scratch resistance of the cured product itself is reduced or formed on it. This is because the scratch resistance of the surface layer is reduced. On the other hand, if t ₂ / t ₁ exceeds 3, it becomes difficult to produce or the strength of the cured product is reduced, and conversely, the scratch resistance of the cured product and the surface layer formed thereon is reduced. This is because the property is reduced. Therefore, t ₂ / t ₁ is more preferably set to a value in the range of 1.4 to 2.5, and further preferably set to a value in the range of 1.5 to 2.

(3) Surface Roughness The surface roughness (Rz according to JIS B0601) of the high refractive index film is set to a value within the range of 0.01 to 2 μm. The reason is that the surface roughness of such a high refractive index film is 0.01 μm.
When the value is less than m, the ratio of the high refractive index film penetrating into the low refractive index film is reduced, and the scratch resistance is significantly reduced. FIGS. 4 and 5 show cross-sectional photographs of the antireflection film laminate, and it is understood that a part of the high refractive index film penetrates into the low refractive index film. On the other hand, when the surface roughness of the high refractive index film exceeds 2 μm, the surface roughness of the low refractive index film becomes relatively large, and light scattering is likely to occur,
As a result, the reflectance and the transparency are reduced.
Therefore, the surface roughness of the high refractive index film is set to 0.02 to 1 μm.
Is preferably in the range of 0.05 to 0.5
More preferably, the value is in the range of μm.

(4) Refractive Index It is more preferable that the refractive index of the high refractive index film (refractive index of Na-D line, measuring temperature 25 ° C.) be a value within the range of 1.45 to 2.1. . The reason for this is that if the refractive index is less than 1.45, the anti-reflection effect may be significantly reduced when combined with a low refractive index film. This is because usable materials may be excessively limited. Therefore, the refractive index of the high refractive index film is more preferably 1.55 to 2.0.
, And more preferably a value within the range of 1.6 to 1.9.

(5) Forming Method Forming Method 1 In forming a high refractive index film, after forming a coating film for the high refractive index film, the curable composition for the high refractive index film is cured by ultraviolet rays or electron beams. Is preferred. In this case, for example, it is preferable to use an ultraviolet irradiation device (a metal halide lamp, a high-pressure mercury lamp, or the like) under a light irradiation condition of 0.001 to 10 J / cm ² . The reason for this is that under such irradiation conditions, a sufficiently cured high refractive index film can be obtained, but the production time does not become excessively long. Therefore, the irradiation condition is set to 0.01 to 5 J / c.
m ² , more preferably 0.1 to 3 J / cm ² . The type of particles in the curable composition for high refractive index film, the number average particle diameter, the amount of particles added,
By appropriately changing the conditions such as the type of the solvent or the thickness of the high refractive index film, it is possible to form irregularities on the surface of the high refractive index film only by irradiating light.

Forming Method 2 In the step of forming a high-refractive-index film, it is preferable to carry out multiple coatings. The reason for this is that, assuming that a high refractive index film having the same thickness is formed, if the coating is performed at once, the inorganic oxide particles settle in the film, making it difficult to form surface irregularities. Because there is. That is, by performing the coating many times, it becomes easy to project or expose the inorganic oxide particles to the surface, so that the unevenness can be formed on the surface of the high refractive index film with high accuracy.

2. Low refractive index film (1) Curable composition for low refractive index film The curable composition for low refractive index film for forming the low refractive index film is not particularly limited. It is preferable that it is composed of components (a) to (d). (A) Fluorine-containing copolymer having a hydroxyl group: 100 parts by weight (b) Thermosetting agent having a functional group capable of reacting with a hydroxyl group: 1
To 70 parts by weight (c) Curing catalyst: 0.1 to 30 parts by weight (d) Organic solvent: 500 to 10,000 parts by weight

(2) Refractive Index The refractive index (refractive index of Na-D line, measuring temperature 25 ° C.) of the low refractive index film is more preferably set to a value within a range of 1.35 to 1.50. The reason is that such refractive index is 1.3.
When the value is less than 5, the types of usable materials may be excessively limited. On the other hand, when the value exceeds 1.5, the antireflection effect may be significantly reduced when combined with a high refractive index film. Because there is. Therefore, the refractive index of the low refractive index film is more preferably set to a value in the range of 1.3 to 1.45, and further preferably to a value in the range of 1.3 to 1.42. .

(3) Film Thickness The thickness of the low refractive index film is not particularly limited, but is preferably, for example, in the range of 0.05 to 1 μm. This is because if the thickness of the low-refractive-index film is less than 0.05 μm, the adhesion and abrasion to the high-refractive-index film as a base may be reduced, while the thickness is small. If the thickness exceeds 1 μm, light interference may occur and the light transmittance and the antireflection effect may decrease. Therefore, the thickness of the low refractive index film is set to 0.05 to
More preferably, the value is in the range of 0.5 μm,
More preferably, the value is in the range of 0.05 to 0.3 μm. The average value of the film thickness of the low-refractive-index film also corresponds to the average line of the roughness curve of the low-refractive-index film in the cross section of the electron micrograph shown in FIGS. It is defined as a value calculated from the distance from the average line of the curve.

3. Hard coat layer In forming the antireflection film laminate, it is preferable to provide a hard coat layer below the high refractive index film. By thus providing the hard coat layer, the high refractive index film can be firmly fixed. Therefore, even in the low refractive index film into which the high refractive index film has penetrated, the scratch resistance can be further improved by the function of the hard coat layer.

The hard coat layer has a thickness of 0.1 to 5
It is preferable to set the value within a range of 0 μm. The reason is that when the thickness of the hard coat layer is less than 0.1 μm,
This is because it may be difficult to firmly fix the low-refractive-index film. On the other hand, if the film thickness exceeds 50 μm, the production becomes difficult, or the base film is hardened due to curing shrinkage during the formation of the hard coat layer. This is because the material may be warped.
Therefore, the thickness of the high refractive index film is more preferably set to a value in the range of 0.5 to 40 μm, and even more preferably to a value in the range of 1 to 30 μm.

[Second Embodiment] In a second embodiment, a color filter (RGB pixel and black matrix) provided with a cured product (1.3 ≦ t ₂ / t ₁ ≦ 3) of the present invention as an underlayer is used. Including). With such a color filter, the cured product as the base layer has excellent scratch resistance, and as a result, the durability can be improved. Further, since the cured product of the present invention has a light transmittance of visible light of 90% or more, it can sufficiently transmit light incident on the color filter. Further, such a color filter can be firmly laminated on the surface of a light emitting element such as a liquid crystal element or organic electroluminescence by utilizing the properties of a cured product. In forming the base layer of the color filter, the curable composition for a high refractive index film described in the first embodiment can be used, and the thickness thereof is set to a value within a range of 100 to 500 nm. It is preferable that On the other hand, the color filter may have a known configuration. For example, the RGB pixels and the black matrix may include a photocurable resin containing a blue pigment, a photocurable resin containing a red pigment, and a photocurable resin containing a green pigment. Resin and a photocurable resin containing a black pigment can be easily formed by a resist method.

Third Embodiment In a third embodiment, the cured product of the present invention is used as a primer layer (1.3 ≦ t ₂ / t ₁ ≦ 3) between a surface layer and a substrate. It is an example of the laminated body used. It is preferable to provide the cured product of the present invention as a primer layer before forming a surface layer for reducing releasability or refractive index on a substrate such as a glass substrate or plastic. When such a primer layer is provided, the adhesion between the surface layer and the base material can be improved, and a resin having poor scratch resistance such as a fluorine compound or a silicon compound is used on the surface side. In this case, excellent scratch resistance can be exhibited. In addition, the primer layer made of the cured product of the present invention can transmit light sufficiently because the light transmittance of visible light is 90% or more. Furthermore, since the primer layer composed of the cured product of the present invention uses a specific polyfunctional (meth) acrylate compound or the like, a fluorine compound or a surface layer composed of a silicon compound or the like is used.
Strong adhesion can be obtained. In forming the primer layer, the curable composition for a high refractive index film described in the first embodiment can be used. Further, the thickness of the primer layer is preferably set to a value within the range of 100 to 500 nm.

[Fourth Embodiment] In a fourth embodiment, the cured product of the present invention is used as an underlayer (1.3 ≦
This is an example in which t ₂ / t ₁ ≦ 3) was used. Before forming an alignment film of liquid crystal molecules on a glass substrate or plastic,
It is preferable to provide the cured product of the present invention as an underlayer.
By providing such a base layer of the alignment film, excellent scratch resistance can be exhibited even when an alignment film made of a polyester resin, a TAC resin, or the like is provided on the surface side and the surface is rubbed. That is, the conventional alignment film is sometimes damaged when rubbing the surface because such an underlayer is not provided. The underlayer of the alignment film made of the cured product of the present invention has a visible light transmittance of 90%.
%, The light transmitted through the liquid crystal can be sufficiently extracted to the outside. Furthermore, since the underlayer of the alignment film made of the cured product of the present invention uses a specific polyfunctional (meth) acrylate compound or the like, a strong adhesion between the base material and the alignment film of the liquid crystal molecules. Can be obtained. In forming the base layer of the alignment film, the high refractive index film curing composition described in the first embodiment can be used. Further, the thickness of the base layer of the alignment film is set to 100 to 500.
Preferably, the value is in the range of nm.

[0044]

Hereinafter, embodiments of the present invention will be described in detail.
The scope of the present invention is not limited to the description of these examples. In the examples, the amounts of the respective components mean parts by weight unless otherwise specified.

[Synthesis Example 1] A reactive alkoxysilane was synthesized. That is, 20.6 g of isophorone diisocyanate was added dropwise to a solution composed of 7.8 g of mercaptopropyltrimethoxysilane and 0.2 g of dibutyltin dilaurate in dry air at 50 ° C. for 1 hour in a dry air. The mixture was further stirred at 60 ° C. for 3 hours. Next, 71.4 g of pentaerythritol triacrylate was dropped into the container at 30 ° C. for 1 hour, and further stirred at 60 ° C. for 3 hours to form a reaction solution containing a reactive alkoxysilane. did. When the amount of isophorone diisocyanate remaining in the reaction solution was measured by a titration method, it was 0.1% by weight or less, and the reaction between mercaptopropyltrimethoxysilane, isophorone diisocyanate, and pentaerythritol triacrylate was almost quantitative. Confirmed that it was done. Also,
It was confirmed that the reactive alkoxysilane had a thiourethane bond, a urethane bond, an alkoxysilyl group, and a reactive unsaturated bond in the molecule.

[Preparation 1 of coating solution] Synthesis Example 1 under dry air
8.7 g of the reactive alkoxysilane obtained in the above, and silica sol dispersed in methyl ethyl ketone (manufactured by Nissan Chemical Industries, Ltd.
(Trade name: MEK-ST, number average particle size: 22 nm, silica concentration: 30% by weight) A mixed solution containing 91.3 g, 0.2 g of isopropyl alcohol, and 0.1 g of ion-exchanged water was heated at 80 ° C. for 3 hours. After stirring under the conditions, 1.4 g of orthoformic acid methyl ester was added, and the mixture was further stirred at the same temperature for 1 hour. Next, after cooling to room temperature, trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-TMPT, and the same applies hereinafter) 2
1.9 g of trimethylolpropanetrioxyethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK Ester A-TMPT-3EO; the same applies hereinafter)
0.95 g and 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd .; hereinafter the same) 3.27
g was mixed to prepare a curable resin composition (hereinafter sometimes referred to as coating liquid A).

[Preparation 2 of coating solution] To a mixture of 50 g of trimethylolpropane triacrylate, 47 g of trimethylolpropanetrioxyethyl acrylate and 3 g of 1-hydroxycyclohexyl phenyl ketone was added isopropyl alcohol. 1,000g,
900 g of MEK was added to obtain a uniform mixed solution. While stirring the mixed solution, 10 g of a water-dispersed silica sol (trade name: MP-1040, manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 100 nm, silica concentration 40.7% by weight) was added, and the curable resin was added. A composition (hereinafter, sometimes referred to as a coating liquid B1) was prepared.

[Preparation 3 of coating solution] A mixture of 50 g of trimethylolpropane triacrylate, 47 g of trimethylolpropane trioxyethyl acrylate and 3 g of 1-hydroxycyclohexyl phenyl ketone was mixed with 500 g of isopropyl alcohol and ME
K400g to obtain a uniform mixed solution. While stirring this mixed solution, a water-dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MP-3040, number average particle diameter 31)
A curable resin composition (hereinafter sometimes referred to as a coating liquid B2) was prepared by adding 10 g of 0 nm and a silica concentration of 40.5% by weight.

[Preparation 4 of coating liquid] Synthesis Example 1 under dry air
25 g of the reactive alkoxysilane obtained in the above, and 260 g of an antimony-doped tin oxide dispersion (trade name: SNS-10M, manufactured by Ishihara Techno Co., Ltd., number average particle diameter 22 nm, antimony-doped tin oxide concentration 27.4% by weight) And p-
A mixture of 0.03 g of hydroquinone monomethyl ether and 0.3 g of ion-exchanged water was stirred at 65 ° C. for 5 hours. Then, orthoformic acid methyl ester 8
g was added and stirred at the same temperature for an additional hour. Next, after cooling to room temperature, 6.1 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and MIBK
And 1,708 g of a curable resin composition (hereinafter, referred to as “curable resin composition”).
It may be described as a coating liquid B3. ) Was prepared.

[Preparation 5 of coating liquid] 100 g of coating liquid B1
100 g of isopropyl alcohol and ME
K100g was added to prepare a curable resin composition (hereinafter sometimes referred to as a coating liquid B4).

[Preparation 6 of coating solution] To a mixture of 50 g of trimethylolpropane triacrylate, 47 g of trimethylolpropanetrioxyethyl acrylate and 3 g of 1-hydroxycyclohexyl phenyl ketone was added isopropyl alcohol. 1,000g,
With 900 g of MEK, a curable resin composition (hereinafter referred to as “curable resin composition”) is added.
It may be described as a coating solution B5. ) Was prepared.

Example 1 (1) Preparation of Scratch-Resistant Laminate The coating solution A obtained in Preparation Example 1 was applied to a polyester film A4300 using a wire bar coater (# 30).
(Manufactured by Toyobo Co., Ltd., film thickness 188 μm)
The coating was dried in a hot-air drying furnace at 80 ° C. for 1 minute to form a coating film. This coating film was cured with ultraviolet light in the atmosphere using a high-pressure mercury lamp under a light irradiation condition of 0.3 J / cm ² to form a cured film (cured film 1) having a thickness of 22 μm. Next, the coating liquid B1 obtained in Preparation Example 1 was coated on the cured film 1 using a wire bar coater (# 3), and dried in a hot-air drying furnace at 80 ° C. for 1 minute. A coating was formed. Using a high-pressure mercury lamp in the air,
UV curing was performed under a light irradiation condition of 0.3 J / cm ² to form a cured film (cured film 2) having a minimum thickness of 110 nm and a maximum thickness of 180 nm. Further, Opstar JN7215 (manufactured by JSR Corporation) as a coating material was applied on the cured film 2 using a wire bar coater (# 3), and air-dried at room temperature for 5 minutes to form a coating film. . This coating film was heated in a hot-air drying furnace at 120 ° C. for 1 minute to form a film having a thickness of 0.1 μm.
And a scratch-resistant laminate.

(2) Evaluation of Scratch-Resistant Scratch Resistance The surface of the obtained abrasion-resistant laminate was rubbed 30 times with # 0000 steel wool under a load of 200 g / cm ² to obtain a scratch-resistant laminate. Was visually evaluated based on the following criteria. Table 1 shows the obtained results. Evaluation 5: No scratch was observed. Evaluation 4: Generation of 1 to 5 scratches was observed. Evaluation 3: Generation of 6 to 50 scratches was observed. Evaluation 2: 51 to 100 scratches were observed. Evaluation 1: Peeling of the coating film was observed. A scratch resistance of evaluation 3 or more is within a practically acceptable range, and a scratch resistance of evaluation 4 or more is preferable because of excellent practical durability. If it is present, it can be said that it is more preferable because practical durability is remarkably improved.

Measurement of minimum film thickness and maximum film thickness The minimum film thickness and the maximum film thickness were measured from an electron micrograph of the obtained scratch-resistant laminate (cross section).

Examples 2 to 5 In Examples 2 to 6, Table 1
As shown in (1), the type of the coating liquid used for forming the cured film 2 was changed, and a scratch-resistant laminate was produced and evaluated in the same manner as in Example 1. Table 1 shows the obtained results.

Comparative Examples 1 to 3 In Comparative Examples 1 to 3, Table 1
As shown in Table ₂ , a scratch-resistant laminate having a ratio of t ₂ / t ₁ outside the range of the present invention was prepared and evaluated. Table 1 shows the obtained results.

[0057]

[Table 1]

[0058]

According to the cured product of the present invention, a polyfunctional (meth) acrylate compound and a number average particle diameter of 5 to 500
When a minimum film thickness in the cross-section of the cured product is t ₁ and a maximum film thickness is t ₂ , a predetermined relational expression is made of a curable resin composition containing an inorganic oxide particle of nm and a curing agent. By satisfying the above, a structure having excellent scratch resistance can be provided. Therefore, for example, when applied to an anti-reflection film laminate, even if a resin having poor scratch resistance such as a fluorine compound or a silicon compound is used on the surface side to reduce the refractive index, the simple structure of the present invention is obtained. By adopting it, it has become possible to provide an antireflection film laminate exhibiting excellent scratch resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing a minimum film thickness (t ₁ ) and a maximum film thickness (t ₂ ) in a cross section of a cured product of the present invention.

FIG. 2 is a cross-sectional view of an antireflection film laminate in which a cured product of the present invention has a high refractive index film.

FIG. 3 is a cross-sectional view of an antireflection film laminate including a hard coat layer in which a cured product of the present invention has a high refractive index film.

FIG. 4 is a cross-sectional photograph of the antireflection film laminate of the present invention (part 1).

FIG. 5 is a cross-sectional photograph of the antireflection film laminate of the present invention (part 2).

[Explanation of symbols]

 REFERENCE SIGNS LIST 12 base material 14 reference line 13 invading portion of second layer 18 hard coat layer 20 high refractive index film 22 low refractive index film 24 antireflection film laminate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 67:00 C08L 67:00 F term (Reference) 4F006 AA35 AB39 AB42 AB43 AB74 BA02 CA05 DA04 4F071 AA33 AB18 AB26 AD06 AG05 AG12 AG15 AG34 AH02 AH12 BB02 BC02 BC12 4F100 AA17A AA19A AA20A AA25A AA33A AH06A AK25A AK42 AL05A AT00B BA02 BA07 CA02A DE01A EH46 EJ08 EJ54 GB41 JK12 YY00FA4J03 HA03 FA034

Claims (6)

[Claims] 1. A polyfunctional (meth) acrylate compound,
The number average particle diameter of the inorganic oxide particles of 5 to 500 nm, a cured product obtained from the curable resin composition containing a curing agent, and the minimum thickness of the cured product section as t _1, the maximum thickness Satisfies the following relational expression when is defined as t ₂ . 1.3 ≦ t ₂ / t ₁ ≦ 3 2. The cured product according to claim 1, wherein the curable resin composition contains a reactive silane compound as a polyfunctional (meth) acrylate compound. 3. The polyfunctional (meth) acrylate compound is trimethylolpropane tri (meth) acrylate or trimethylolpropane trioxyethyl (meth).
Acrylate, dipentaerythritol penta (meth)
3. The cured product according to claim 1, wherein the cured product is at least one polyfunctional (meth) acrylate compound selected from the group consisting of acrylate and pentaerythritol penta (meth) acrylate. 4. 4. The method according to claim 1, wherein the inorganic oxide particles comprise silicon oxide (S
iO ₂ ), antimony-doped tin oxide (ATO), zinc oxide (ZnO), tin-doped indium oxide (IT
O), and at least one inorganic oxide particle selected from the group consisting of zinc antimonate (AZO) and aluminum oxide (Al ₂ O ₃ ). The cured product according to the item. 5. An antireflection film laminate, an antifouling film, a water repellent film, an antistatic film, an alignment film, a primer layer, a color filter,
The cured product according to claim 1, wherein the cured product is a part of a fluorescent film, a polarizing film, or a light guide film. 6. A structure comprising the cured product according to claim 1. Description: