KR20080012347A - Antireflective laminate - Google Patents

Abstract

This invention provides a laminate comprising a base material and at least an antistatic layer and a low refractive index layer stacked in that order on the base material. The antistatic layer is a cured film layer formed by curing a liquid curable composition comprising the following components (A) to (C): (A) phosphorus-containing tin oxide particles, (B) a compound containing two or more polymerizable unsaturated groups in its molecule, and (C) a photopolymerization initiator having a molar extinction coefficient of not more than 5,000 L/mol.cm at 313 nm. The low refractive index layer is a cured film layer formed by curing a liquid curable resin composition comprising (D) an ethylenically unsaturated group-containing fluoropolymer having a fluorine content of not less than 40% by mass, and (E) particles composed mainly of silica.

Description

Anti-reflective laminate {ANTIREFLECTIVE LAMINATE}

The present invention relates to an antistatic laminate. More specifically, while excellent in curability, various substrates such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS Resin, norbornene-based resin, etc.), a liquid curable composition capable of forming a coating film (film) having excellent antistatic property, hardness, scratch resistance and transparency on the surface of metal, wood, paper, glass, ceramic, slate and the like. It relates to an antistatic laminate comprising a cured film layer formed by curing.

Conventionally, in view of securing performance and safety measures of an information communication device, a coating film (hard coating) having scratch resistance and adhesion or an antistatic function (antistatic film) is formed on the surface of the device by using a radiation curable composition. That was done.

In addition, in order to provide an antireflection function to the optical article, a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer was formed on the surface of the optical article.

Recently, the development and generalization of information and communication devices have been remarkable, and further improvements in productivity and productivity have been demanded, such as hard coatings, antistatic films, and antireflection films.

In particular, in an optical article such as a plastic lens, prevention of dust adhesion by static electricity and improvement of a decrease in transmittance due to reflection are required, and also in a display panel, prevention of dust adhesion by static electricity and a screen Projection prevention of the is required.

In response to these demands, various radiation-curable materials have been proposed in view of high productivity and curing at room temperature.

As such a technique, for example, a composition containing sulfonic acid and a phosphoric acid monomer as an ion conductive component (following patent document 1), a composition containing a chain metal powder (following patent document 2), tin oxide particles, and a polyfunctional acrylate , And a composition containing a copolymer of methyl methacrylate and polyether acrylate as a main component (Patent Document 3), a conductive coating composition containing a pigment coated with a conductive polymer (Patent Document 4), trifunctional acrylic acid ester , An optical disk material (patent document 5) containing a monofunctional ethylenically unsaturated group-containing compound, a photopolymerization initiator, and a conductive powder, hydrolyzate of antimony-doped tin oxide particles and tetraalkoxysilane dispersed with a silane coupler, and light A conductive coating containing the sensitizer, and an organic solvent (Patent Document 6), containing a polymerizable unsaturated group in a molecule Is a liquid curable resin composition (Patent Document 7) containing a reaction product of an alkoxysilane and metal oxide particles, a trifunctional acrylic compound, and a radiation polymerization initiator, a conductive oxide fine powder having a primary particle size of 100 nm or less, and the conductive oxide fine powder And a transparent conductive film-forming paint containing the dispersible low-boiling solvent of the above, a low-dispersibility low-boiling solvent of the conductive oxide fine powder, and a binder resin (Patent Document 8).

In addition, in various display panels, such as a liquid crystal display panel, a cold cathode ray tube panel, and a plasma display, the hardened | cured material excellent in low refractive index, abrasion resistance, coating property, and stain resistance is prevented, in order to prevent the reflection of external light and to improve image quality. There is a need for an antireflection film including a low refractive index layer.

In these display panels, in order to remove the attached fingerprint, dust, etc., the surface is often wiped with the gauze impregnated with ethanol, and scratch resistance is calculated | required. In addition, there is also a demand for stain resistance that can easily wipe off fingerprints, dust, and the like.

In particular, in the liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to the polarizing plate. In addition, although triacetyl cellulose etc. are used as a base material, in order to increase the adhesiveness at the time of bonding with a polarizing plate in an anti-reflective film using such a base material, it is usually necessary to saponify in alkaline aqueous solution.

Therefore, in the use of a liquid crystal display panel, the antireflection film excellent in alkali resistance especially in durability is calculated | required.

As the material for the low refractive index layer of the antireflection film, for example, a fluororesin paint containing a hydroxyl group-containing fluorine-containing polymer is known (for example, Patent Documents 9 to 11 below).

However, in such a fluororesin-based paint, it is necessary to crosslink by heating a hydroxyl group-containing fluorine-containing polymer and a curing agent such as a melamine resin under an acid catalyst in order to cure the coating film. There was a problem that the kind of the base material was limited.

Moreover, although the obtained coating film was excellent in weatherability, there existed a problem of being scratch-resistant and lacking in durability.

Therefore, in order to solve the above problem, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group and a hydroxyl group-containing fluorine-containing polymer have a ratio of the number of the number of hydroxyl / hydroxyl groups of the isocyanate group of 0.01 to 1.0. The coating composition containing the unsaturated group containing fluorine-containing vinyl polymer obtained by making it react by the ratio is proposed (for example, following patent document 12).

However, the above publication does not use an isocyanate group-containing unsaturated compound in an amount sufficient to react all hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer when producing the unsaturated group-containing fluorine-containing vinyl polymer, and actively reacts the unreacted hydroxyl group in the polymer. It was to remain.

For this reason, although the coating composition containing this polymer enables low temperature and hardening in a short time, it was necessary to harden | cure further using hardening | curing agents, such as melamine resin, in order to react the remaining hydroxyl group. Moreover, the coating film obtained by the said publication had a problem that coating property and abrasion resistance are not enough.

Patent Document 1: Japanese Patent Laid-Open No. 47-34539

Patent Document 2: Japanese Patent Laid-Open No. 55-78070

Patent Document 3: Japanese Patent Laid-Open No. 60-60166

Patent Document 4: Japanese Patent Application Laid-Open No. 2-194071

Patent Document 5: Japanese Patent Application Laid-Open No. 4-172634

Patent Document 6: Japanese Patent Application Laid-Open No. 6-264009

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-143924

Patent Document 8: Japanese Patent Application Laid-Open No. 2001-131485

Patent Document 9: Japanese Patent Application Laid-Open No. 57-34107

Patent Document 10: Japanese Patent Application Laid-Open No. 59-189108

Patent Document 11: Japanese Unexamined Patent Publication No. 60-67518

Patent Document 12: Japanese Patent Application Laid-Open No. 61-296073

However, although these conventional techniques each exhibit a certain effect, they are not always sufficiently satisfactory as a cured film which is required to be fully equipped with all functions as a hard coating, an antistatic film and an antireflection film in recent years.

For example, the prior art as described in the above-mentioned prior art document has the following problems. Although the composition of patent document 1 uses the ion conductive material, antistatic performance is not enough and a performance fluctuates by drying. Since the composition of patent document 2 disperse | distributes the chain-shaped metal powder with a big particle diameter, transparency falls. Since the composition of patent document 3 contains a large amount of non-hardening dispersing agents, the intensity | strength of a cured film falls. Since the material of patent document 5 mix | blends a high concentration of charged inorganic particle, transparency falls. The paint described in Patent Document 6 does not have sufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic properties. When the coating material of patent document 8 was apply | coated and dried, and a transparent conductive film was formed, since the crosslinked structure was not provided in the organic matrix containing the compound of binder, it cannot be said that organic solvent tolerance is enough.

In order to increase the antistatic performance, it is easy to increase the blending amount of the conductive particles, but in that case, the transparency decreases due to the increase in the visible light absorption by the cured film, and the curability decreases due to the decrease in ultraviolet ray permeability. The problem that the adhesiveness with the base material and the leveling property of a coating liquid were impaired was inevitable. On the other hand, when the compounding quantity of electroconductive particle is reduced, sufficient antistatic performance will not express.

<Start of invention>

This invention is made | formed in view of the above-mentioned problem, It can express sufficient antistatic performance, is excellent in sclerosis | hardenability, and is excellent in antistatic property, hardness, and abrasion resistance on the surface of various base materials, transparency and surface resistance value It aims at providing the antistatic laminated body which has a cured film layer which hardens the liquid curable composition which can form the coating film (film) which made compatible, and the antireflective film laminated body which has an antistatic function especially.

Another object of the present invention is to provide an antireflective laminate having excellent scratch resistance and stain resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the above-mentioned subject, the present inventors hardened the composition containing the electroconductive particle which has a specific primary particle diameter, the compound which has a specific polymerizable unsaturated group, the photoinitiator which has a specific light absorption characteristic, and a solvent. The laminated body having a cured film layer can solve the problems related to the antistatic performance and at the same time improve scratch resistance and chemical resistance, and further comprise a specific ethylenically unsaturated group-containing fluorine-containing polymer and particles containing silica as a main component. By combining the low refractive index film | membrane obtained by hardening curable resin composition, it was discovered that the outstanding antireflection characteristic is acquired, and the scratch resistance and contamination resistance of an antireflective laminated body improve, and completed this invention.

That is, this invention provides the following laminated bodies and an anti-reflective film.

[1] A laminate having a base material, an antistatic layer and a low refractive index layer in this order,

The antistatic layer is

(A) phosphorus-containing tin oxide particles,

(B) a compound having two or more polymerizable unsaturated groups in a molecule, and

(C) The photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less.

It is a cured film layer which hardens the liquid curable composition containing,

The low refractive index layer

(D) an ethylenically unsaturated group-containing fluorine-containing polymer containing 40% by mass or more of fluorine, and

(E) Particles based on silica

The laminated body which is a cured film layer formed by hardening | curing the liquid curable resin composition containing.

[2] The laminate according to [1], wherein the antistatic layer has a thickness of 0.05 to 30 µm.

[3] The ethylenically unsaturated group-containing fluorine-containing polymer (D) containing 40% by mass or more of fluorine

Hydroxyl group-containing fluorine-containing polymer, and

Compound containing functional group and ethylenically unsaturated group which can react with hydroxyl group

It is obtained by making it react, The laminated body as described in said [1] or [2] characterized by the above-mentioned.

[4] When the hydroxyl group-containing fluorine-containing polymer sets the total of the following structural units (a), (b) and (c) to 100 mol%, (a) 20 to 70 mol% and (b) 1 to 70 mol % And (c) 5-70 mol%, and also

The laminated body as described in said [3] whose polystyrene reduced number average molecular weight measured by gel permeation chromatography is 5,000-500,000.

(a) The structural unit represented by following formula (1)

(b) a structural unit represented by the following formula (2)

(c) a structural unit represented by the following formula (3)

[In Formula 1, R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ² (R ² represents an alkyl group or a fluoroalkyl group.)

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ^5, or a group represented by -OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by-(CH ₂ ) _v -OR ²⁷ or -OCOR ²⁷ (R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group. And v represents a number from 0 to 2).

[5] The hydroxyl group-containing fluorine-containing polymer further contains 0.1 to 10 mol parts of the following structural unit (d) derived from an azo group-containing polysiloxane compound based on 100 mol parts in total of the above (a), (b) and (c). The laminated body as described in said [3] or [4].

(d) a structural unit represented by the following formula (4)

[In Formula 4, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

[6] The above-mentioned [3], wherein the hydroxyl group-containing fluorine-containing polymer contains 0.1 to 5 mol parts of the following structural unit (f) based on 100 mol parts in total of (a), (b) and (c). The laminated body in any one of [5].

(f) The structural unit represented by following formula (5)

In formula (5), R ¹⁰ represents a group having an emulsifying action.

[7] The laminate according to any one of [3] to [6], wherein the functional group capable of reacting with the hydroxyl group is a group selected from the group consisting of an isocyanate group, a carboxyl group, an acid halide, and an acid anhydride group.

[8] The laminate according to any one of [1] to [7], wherein a refractive index of the antistatic layer is higher than that of the low refractive index layer.

[9] The laminate according to any one of [1] to [8], wherein a hard coat layer is formed on the substrate.

[10] An antireflection film, comprising the laminate according to any one of [1] to [9].

According to the present invention, for antistatic having a cured film formed by curing a liquid curable composition capable of forming a coating film (coating) having excellent curability and excellent antistatic property, hardness, scratch resistance, and transparency on the surface of various substrates. The laminate can be provided.

Conventionally, although it was necessary to mix | blend electroconductive particle with high content in order to acquire sufficient electroconductivity, according to this invention, even if content of electroconductive particle is low, sufficient electroconductivity can be expressed and it has the antistatic property which has a cured film excellent in antistatic performance. A laminate can be obtained.

Moreover, according to this invention, even if content of electroconductive particle is suppressed low, transparency of cured film and sufficient surface resistance value can be made compatible, and it is useful as an optical component which has an antistatic function, especially an antireflection film which has an antistatic function.

Moreover, by having the low refractive index layer which has a specific structure, the antireflection laminated body excellent in scratch resistance and contamination resistance can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the most basic structure (1st aspect) of the laminated body of this invention.

It is a schematic diagram which shows the 1st form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the other form of the 1st form of the antireflection film which has an antistatic function of this invention.

It is a schematic diagram which shows the basic structure of the 2nd form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the other form of the 2nd form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the other form of the 2nd form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the basic structure of the 3rd form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the other form of 3rd form of the anti-reflective film which has an antistatic function of this invention.

It is a schematic diagram which shows the other form of 3rd form of the anti-reflective film which has an antistatic function of this invention.

<Embodiment of the invention>

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described concretely.

In the laminate of the present invention, at least the substrate, the antistatic layer, and the low refractive index layer are laminated in this order from the side close to the substrate.

An antistatic layer is characterized by including the cured film formed by hardening | curing the liquid curable composition containing the following components (A)-(C).

[Liquid curable composition (hereinafter, may be referred to as "composition for antistatic layer formation")]

(A) Phosphorus-containing tin oxide particles

(B) a compound having two or more polymerizable unsaturated groups in a molecule

(C) The photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less.

Furthermore, a low refractive index layer is characterized by including the hardened | cured material formed by hardening | curing curable resin composition containing the following components (D) and (E).

[Liquid curable resin composition (hereinafter, may be referred to as "composition for forming a low refractive index layer")]

(D) Ethylenic unsaturated group containing fluorine-containing polymer containing 40 mass% or more of fluorine

(E) Particles based on silica

I. Laminates

The most basic structure of the laminated body of this invention is shown in FIG. The laminated body 1 of this invention has the base material 10, the antistatic layer 12 which hardens the said antistatic layer formation composition, and the low refractive index layer 18 which hardens the said composition for low refractive index layer formation.

The laminate 1 of the present invention has an antistatic layer 12 having excellent scratch resistance and adhesion, and the antistatic layer 12 is used as a hard coating and the laminate 1 of the present invention is used as an antireflection film. It is also useful as a high refractive index layer expressing high refractive index.

Moreover, the laminated body 1 of this invention is useful as an antistatic laminated body by arrange | positioning the antistatic layer 12 which provides the outstanding electroconductivity on the base material of various shapes, such as a film form, a plate form, or a lens.

As an application example of the laminated body of this invention, the anti-reflective film provided with the antistatic function for various display panels, such as a CRT, a liquid crystal display panel, a plasma display panel, an electroluminescent display panel, for example, "reflection with an antistatic function" Use as an anti-reflection film having an antistatic function such as a plastic lens, a polarizing film, a solar cell panel, and the like.

Next, the structural example of each layer at the time of using the laminated body of this invention as an antireflection film which has an antistatic function is demonstrated, referring drawings.

When providing an anti-reflective function to an optical article, the method of forming a low refractive index layer or the multilayer structure of a low refractive index layer and a high refractive index layer is known to be effective for a base material or a hard-coated base material.

The most basic structure (1st form) at the time of using the laminated body of this invention as an anti-reflective film which has an antistatic function is as showing in FIG. The anti-reflective film 2 which has an antistatic function forms the antistatic layer 12 which is a cured film layer formed by hardening | curing the said antistatic layer formation composition on the base material 10, and also for the said low refractive index layer formation on it. It is made by forming the low refractive index layer 18 which is a cured film layer formed by hardening a composition. In the first aspect, the antistatic layer 12 also has an antistatic function, a function as a hard coating layer, and also a function as a high refractive index layer. In the most basic form, it is necessary that the refractive index of the antistatic layer 12 is higher than the refractive index of the low refractive index layer 18.

As another aspect, the antistatic layer 12 of the antireflection film 2 of the present invention may also function as a hard coating layer, but a hard coating layer may be provided separately. In this case, the hard coat layer 11 is provided between the base material 10 and the antistatic layer 12 or between the antistatic layer 12 and the low refractive index layer 18. When the hard coating layer 11 is provided between the antistatic layer 12 and the low refractive index layer 18, the refractive index of the hard coating layer 11 must be higher than the refractive index of the low refractive index layer 18. These embodiments are shown in Figures 2A and 2B.

The 2nd aspect at the time of using the laminated body of this invention as an antireflection film which has an antistatic function is shown in FIG. In the second aspect, the antireflection film 2 having an antistatic function forms an antistatic layer 12, which is a cured film layer formed by curing the liquid curable composition, on a substrate 10, and further having a high refractive index layer ( 16) and the low refractive index layer 18 are formed in this order. In the second aspect, the antistatic layer 12 may have a function as an antistatic function and a hard coating, and also as a medium refractive index layer. In the second aspect, in order for the antistatic layer 12 to have a function as a medium refractive index layer, the refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16 and higher than the refractive index of the low refractive index layer 18. It is necessary.

Similarly to the first aspect, the second aspect can also be provided with a hard coat layer. The hard coating layer 11 can be provided between any one of the base material 10 and the antistatic layer 12, or between the antistatic layer 12 and the high refractive index layer 16. FIG. These forms are shown in FIGS. 4A and 4B.

The third aspect at the time of using the laminated body of this invention as an antireflection film which has an antistatic function is shown in FIG. In the third aspect, the antireflection film 2 having an antistatic function forms an antistatic layer 12, which is a cured film layer formed by curing the liquid curable composition on the substrate 10, and further has a medium refractive index layer ( 14), the high refractive index layer 16 and the low refractive index layer 18 are formed in this order. In the third aspect, the antistatic layer 12 has a function as an antistatic function and a hard coating.

Also in a 3rd aspect, like a 1st aspect, it is also possible to provide a hard-coat layer separately. The hard coat layer 11 can be provided between any one of the base material 10 and the antistatic layer 12, or between the antistatic layer 12 and the medium refractive index layer 14. These forms are shown in FIGS. 6A and 6B.

In each layer and base material which are provided as needed other than the antistatic layer and the low refractive index layer which harden specific liquid curable composition, respectively essential for the laminated body of this invention provided in the 1st-3rd aspect of the said anti-reflective film, Explain.

On the other hand, the antistatic layer and the low refractive index layer of the following (1), (2) is a description as a layer arbitrarily provided in addition to the antistatic layer and the low refractive index layer essential in the laminate of the present invention, and the antistatic layer and The low refractive index layer will be described later.

(1) antistatic layer

An antistatic layer provides electroconductivity to a laminated body, and prevents static electricity generate | occur | produces and dust adheres.

In the laminated body of this invention, the antistatic layer formed using the curable composition containing components (A)-(C) mentioned later is essential, and the antistatic layer demonstrated here is arbitrary layers provided separately other than an essential antistatic layer.

Specific examples of the antistatic layer include metals having conductivity such as antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, and Al-doped ZnO particles, in addition to the phosphorus-containing tin oxide (PTO) particles used in the present invention. And a film containing an oxide particle or a curable film to which an organic or inorganic conductive compound is added, a metal oxide film obtained by depositing or sputtering the metal oxide, and a film containing a conductive organic polymer. Examples of the conductive organic polymer include polyacetylene-based conductive polymers, polyaniline-based conductive polymers, polythiophene-based conductive polymers, polypyrrole-based conductive polymers, and polyphenylenevinylene-based conductive polymers.

(2) low refractive index layer

The low refractive index layer is a layer whose thickness is in the range of 0.05 to 0.20 mu m and the refractive index is 1.30 to 1.45. In addition, the refractive index in this invention means the refractive index of 589 nm in 25 degreeC.

As a material used for a low refractive index layer, if the target characteristic is acquired, it will not specifically limit, For example, the curable composition containing a fluoropolymer, an acrylic monomer, a fluorine-containing acrylic monomer, an epoxy-group-containing compound, a fluorine-containing epoxy group Hardened | cured material, such as a containing compound, is mentioned. Moreover, in order to raise the intensity | strength of a low refractive index layer, you may mix | blend a silica fine particle etc ..

In the laminated body of this invention, the low refractive index layer formed using the curable resin composition containing component (D) and component (E) mentioned later is essential, and the low refractive index layer demonstrated here is arbitrary provided other than an essential low refractive index layer. Of layers.

(3) high refractive index layer

The high refractive index layer has a thickness in the range of 0.05 to 0.20 µm and a refractive index in the range of 1.55 to 2.20.

In order to form a high refractive index layer, high refractive index inorganic particles, for example, metal oxide particles, may be blended.

Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (ZnO) particles, antimony-containing ZnO, Al-containing ZnO particles, ZrO ₂ particles, TiO ₂ particles, And silica coated TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, CeO ₂ particles, and the like. Preferably, they are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles. These metal oxide particles can be used individually by 1 type or in combination of 2 or more types.

It is also possible to give the high refractive index layer the function of a hard coat layer.

(4) medium refractive index layer

When combining three or more types of layers having a refractive index, the refractive index is 1.50 to 1.90, and a layer having a refractive index higher than the low refractive index layer and lower than the high refractive index layer is referred to as a medium refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.80, more preferably 1.50 to 1.75. The medium refractive index layer is in the range of 0.05-0.20 micrometer in thickness.

In order to form the medium refractive index layer, high refractive index inorganic particles, such as metal oxide particles, may be blended.

Specific examples of the metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, Al-containing ZnO particles, ZrO ₂ particles, TiO ₂ particles, silica coated TiO ₂ particles. , Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles, CeO ₂ particles, and the like. Preferably, they are antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and ZrO ₂ particles. These metal oxide particles can be used individually by 1 type or in combination of 2 or more types.

By combining the low refractive index layer and the high refractive index layer, the reflectance can be lowered. Furthermore, by combining the low refractive index layer, the high refractive index layer, and the medium refractive index layer, the reflectance can be lowered and the color tone (splash) can be reduced.

(5) hard coating layer

Specific examples of the hard coat layer, SiO _2, is preferably made of a material such as epoxy resin, acrylic resin, melamine-based resin. Moreover, silica particle can be mix | blended with these resin.

The hard coating layer has the effect of increasing the mechanical strength of the laminate. The thickness of the hard coat layer is usually in the range of 0.5 to 50 mu m, preferably 1 to 30 mu m. In addition, the refractive index of the hard coat layer is usually in the range of 1.45 to 1.70, preferably 1.45 to 1.60.

(6) mention

Although the base material used for the laminated body of this invention does not have a restriction | limiting in particular, such as a metal, a ceramic, glass, a plastic, a wood, a slate, etc., As a material which can exhibit industrial productivity with high productivity, such as radiation hardening property, For example, a film It is preferably applied to a fibrous base material. Particularly preferred materials are plastic films and plastic plates. As such a plastic, for example, polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR -39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (e.g., norbornene-based resin), and the like. When using the laminated body of this invention as an anti-reflection film, polycarbonate, a polystyrene / polymethyl methacrylate copolymer, a triacetyl cellulose resin, a cyclized polyolefin resin is mentioned, and, for high transparency, such as norbornene-type resin, Preference is given to cyclic olefin resins.

Although the thickness of a base material is not specifically limited, Usually, it is 30-300 micrometers, Preferably it is the range of 50-200 micrometers.

(7) other layers

In the manufacture of the laminate of the present invention, in order to further impart other requirements, for example, non-glare effect, selective absorption effect of light, weather resistance, durability, transferability, and the like, For example, adding a layer containing light scattering particles of 1 μm or more, adding a layer containing a dye, adding a layer containing an ultraviolet absorber, adding an adhesive layer, adding an adhesive layer and a release layer It is also possible to add these functional provision components as one component of the composition for antistatic layer formation and / or the composition for low refractive index layer formation used in the present invention.

The laminate of the present invention is hard for preventing scratches or stains of plastic optical components, touch panels, film-like liquid crystal elements, plastic housings, plastic containers, floorings as building interior materials, wall materials, artificial marble and the like, for example. Coating material; Adhesives and sealants of various substrates; It can use suitably as a binder material of printing ink, etc.

These layers may form only one layer, and may also form two or more different layers.

The film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm, the film thickness of the hard coating layer is usually 1 to 20 µm, and the film thickness of the antistatic layer is usually 0.05 to 30 µm.

The manufacturing method of the layer in this invention can be manufactured by well-known application | coating, hardening, vapor deposition, sputtering, etc. methods.

II. Antistatic layer

The antistatic layer provided on the base material of the laminated body of this invention is obtained by hardening the said antistatic layer formation composition, and can give a laminated body a function as an electroconductivity, a function as a high refractive index film, and / or a hard coating.

Hereinafter, each component of a liquid curable composition is demonstrated concretely.

1. Ingredient (A)

The phosphorus containing tin oxide particle (component (A)) used for a liquid curable composition is an essential component for expressing the electroconductivity of the hardened film of the liquid curable composition obtained.

As a commercial item as powder of such phosphorus containing tin oxide particle, the Shokubai Kasei Kogyo Co., Ltd. brand name: ELCOM TL-30S (PTO) is mentioned, for example.

Although the phosphorus containing tin oxide particle used as a component (A) can be used in the state disperse | distributed to powder or a solvent, it is preferable to use in the state disperse | distributed in a solvent from the point which is easy to obtain uniform dispersibility.

As a commercial item which disperse | distributed the oxide particle used as a component (A) to a solvent, the brand name: ELCOM JX-1001PTV (PTO of propylene glycol monomethyl ether dispersion | distribution) by Shokubai Kasei Kogyo Co., Ltd. is mentioned, for example.

The primary particle size of the component (A) is preferably 10 to 100 nm, more preferably 10 to 50 nm when the shape is spherical. Primary particle diameter is measured by a transmission electron microscope. If it is less than 10 nm, electroconductivity will run out, and if it exceeds 100 nm, sedimentation will arise in a composition or the smoothness of a coating film will fall. When the shape is thin and long like a needle, the dry powder is observed with an electron microscope, and the value obtained as the number average particle diameter is preferably a uniaxial average particle diameter of 10 to 50 nm and a long axis number average particle diameter of 100 to 2000 nm. When the major axis particle size exceeds 2000 nm, sedimentation may occur in the composition.

Although the compounding quantity of a component (A) in particular is not restrict | limited, Preferably it is 25 to 85 weight%, More preferably, it is 30 to 70 weight% in 100 weight% of total amounts of solid content. If the compounding amount is less than 25% by weight, the antistatic property may be inferior, and if the amount exceeds 85% by weight, the hardness of the coating film may be inferior. Here, the compounding quantity of component (A), (B), and (C) means the compounding quantity as its solid content.

2. Ingredient (B)

The component (B) used for a liquid curable composition is a compound which has a 2 or more polymerizable unsaturated group in a molecule | numerator from the film formability and transparency aspect of the cured film of the liquid curable composition obtained. By using such a component (B), the hardened | cured material which has the outstanding scratch resistance and organic solvent tolerance is obtained.

As a specific example of a component (B), (meth) acrylic ester and vinyl compounds are mentioned, for example.

Examples of the (meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurey Di (meth) acrylate, bis-tricyclo [5.2.1.0 ^2,6] decane ((meth) acryloyl-yloxymethyl) ( "tricyclodecane di ildi methanol di (meth) acrylate" also known), and mixtures thereof Poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols when preparing a compound, oligoester (meth) acrylates having two or more (meth) acryloyl groups in a molecule, oligoether (Meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, etc. are mentioned.

Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) Preference is given to acrylates and bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane.

These (B) components may be used individually by 1 type, and may use 2 or more types together.

The compounding quantity of component (B) is in 100 weight% of total amounts of solid content, Preferably it is 10-74 weight%, More preferably, it is 20-65 weight%. When the compounding quantity of a component (B) is less than 10 weight%, the hardness of the hardened | cured material obtained may fall, and when it exceeds 74 weight%, antistatic property may be inferior.

3. Ingredient (C)

Component (C) is a photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less. Here, the molar extinction coefficient at 313 nm of a photoinitiator means the ratio of the absorbance of a solution at 313 nm with respect to an absorbing layer of 1 cm, and molar concentration. By using the photoinitiator which has such a light absorption characteristic, the surface resistance of a cured film can fully be lowered. When the photoinitiator whose molar extinction coefficient in 313 nm exceeds 5,000 L / mol * cm is used, the surface resistance of the cured film obtained is high and sufficient antistatic performance is not obtained.

Although the composition for antistatic layer formation hardens | cures only by irradiating a radiation, component (C) can further raise hardening rate other than the said function.

In addition, in this invention, radiation means visible light, an ultraviolet-ray, an ultraviolet-ray, X-ray, an electron beam, (alpha) ray, (beta) ray, (gamma) ray, etc.

As a photoinitiator which can be used as a component (C), 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, oligo (2-hydroxy-2-methyl-1- (4) -(1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one Etc. can be mentioned.

The compounding quantity of a component (C) is 0.1 to 15 weight% with respect to 100 weight% of total amounts of solid content, More preferably, it is 0.5 to 10 weight%. A component (C) can be used individually by 1 type or in combination of 2 or more type.

4. Solvent

Although the solvent used for the composition for antistatic layer formation of this invention is not specifically limited, Usually, the solvent whose boiling point in normal pressure is 200 degrees C or less is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used individually by 1 type or in combination of 2 or more types. Specifically, propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, etc. are mentioned, for example, propylene glycol monomethyl ether (PGME), cyclohexanone, methyl Ethyl ketone is preferred.

On the other hand, when using the dispersion of phosphorus containing tin oxide particle as a component (A), although a solvent is contained in a dispersion, the solvent of this dispersion may be used and another solvent may be added.

Examples of the alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol, and the like. Can be. As ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned, for example. As ethers, dibutyl ether, propylene glycol monoethyl ether acetate, etc. are mentioned, for example. As esters, ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, ethyl acetoacetate, etc. are mentioned, for example. As hydrocarbons, toluene, xylene, etc. are mentioned, for example. Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

Although the compounding quantity of a solvent is not specifically limited, It is 50-10000 weight part normally with respect to 100 weight part of total amounts of solid content, Preferably it is 50-3000 weight part.

5. Compounds having other polymerizable unsaturated groups

The composition (component (F)) which has another polymerizable unsaturated group can be mix | blended with the composition for antistatic layer formation as an additive other than the said components (A)-(C) as needed. Here, component (F) is a compound which has one polymerizable unsaturated group in a molecule | numerator.

As a specific example of component (F), vinyl group containing lactams, such as N-vinylpyrrolidone and N-vinyl caprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclo deca, for example. Alicyclic structure-containing (meth) acrylates, benzyl (meth) acryl, such as nil (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and cyclohexyl (meth) acrylate Latex, 4-butylcyclohexyl (meth) acrylate, acryloyl morpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) Acrylate, isobutyl (meth) acrylic Late, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl ( Meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene Glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth ) Acrylate, ethoxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylic Amide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyl Octyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethyl Hexyl vinyl ether, the compound represented by following formula (10), etc. are mentioned.

CH ₂ = C (R ¹⁵ ) -COO (R ¹⁶ O) _d -Ph-R ¹⁷

(In the formula, R ¹⁵ represents a hydrogen atom or a methyl group, R ¹⁶ is 2 to 6 carbon atoms, preferably 2 to alkyl represents an alkylene of 4, R ¹⁷ is 1 to have the hydrogen atom or a group having 1 to 12 carbon atoms, preferably 9 represents an alkyl group, Ph represents a phenylene group, and d represents a number from 0 to 12, preferably 1 to 8)

As a commercial item of the component (F), Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, Toagosei Co., Ltd. product); Biscotti LA, STA, IBXA, 2-MTA, # 192, # 193 (manufactured by Osaka Yuki Chemical Co., Ltd.); NK ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd. make); Light acrylates L-A, S-A, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (above, Hitachi Kasei Kogyo Co., Ltd. product) etc. are mentioned.

6. Additive

As an additive, antioxidant, a ultraviolet absorber, a light stabilizer, a thermal polymerization inhibitor, a leveling agent, surfactant, a lubricating agent, etc. can be mix | blended with the composition for antistatic layer formation as needed. As antioxidant, brand name of Ciba Specialty Chemicals Co., Ltd. make: Irganox 1010, 1035, 1076, 1222, etc. As a ultraviolet absorber, brand name of Ciba Specialty Chemicals Co., Ltd. make: Tinuvin P234, 320, 326, 327, 328, 213, 329, the brand name of Cipro Kasei Co., Ltd .: As a light stabilizer, such as Sisov 102, 103, 501, 202, 712, brand name of Shiva Specialty Chemicals Co., Ltd. make: Tinuvin 292, 144, 622LD And Sankyo Co., Ltd. product name: Sunol LS770, LS440, Sumitomo Chemical Co., Ltd. brand name: Sumisob TM-061, etc. are mentioned.

The viscosity of the composition for antistatic layer formation thus obtained is usually 1 to 20,000 mPa · s at 25 ° C., preferably 1 to 1,000 mPa · s.

7. Non-Conductive Particles

In this invention, the particle | grains obtained by making nonelectroconductive particle or nonelectroconductive particle and an alkoxysilane compound react in an organic solvent can be used together in the range which the composition for antistatic layer formation does not produce defects, such as a separation and gelation.

By using the non-conductive particles in combination with the phosphorus-containing tin oxide particles as the component (A), the scratch resistance is improved while maintaining an antistatic function, that is, a value of 1 × 10 ¹³ Ω / □ or less as a surface resistance when the cured film is used. You can.

As such nonelectroconductive particle, if it is particle | grains other than the phosphorus containing tin oxide particle which is a component (A), it will not specifically limit. Preferably, these are oxide particles or metal particles other than the component (A). Specifically, oxide particles containing oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, or two or more elements selected from the group consisting of silicon, aluminum, zirconium, titanium, and cerium are mentioned. Can be.

The primary particle diameter of nonelectroconductive particle is a value calculated | required by transmission electron microscope observation, Preferably it is 0.1 micrometer or less, More preferably, it is 0.001-0.08 micrometer. If it exceeds 0.1 µm, sedimentation may occur in the composition, or the smoothness of the coating film may decrease.

When mix | blending nonelectroconductive particle with the composition for antistatic layer formation, a nonelectroconductive particle and an alkoxysilane compound can be mixed after hydrolyzing in an organic solvent. By this treatment, the dispersion stability of the nonelectroconductive particle becomes favorable.

As a commercial item of a nonelectroconductive particle, For example, as a silicon oxide particle (for example, a silica particle), it is a colloidal silica and brand name of Nissan Chemical Industries, Ltd. make: methanol silicazol, IPA-ST, MEK-ST , NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. Can be mentioned. In addition, as powder silica, the Nippon Aerosil Co., Ltd. brand name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. brand name: Sealdex H31, H32 , H51, H52, H121, H122, The brand name of Nippon Silica Co., Ltd. make: E220A, E220, The brand name of Fuji Silicia Co., Ltd. make: SYLYSIA 470, The Nippon Itagaras Co., Ltd. brand name: SG flakes, etc. Can be mentioned.

In addition, as a water dispersion of aluminum oxide (alumina), Nissan Chemical Industries, Ltd. brand name: Alumina sol-100, -200, -520; As a dispersion of zirconium oxide, Sumitomo Osaka Cement Co., Ltd. make (toluene, zirconia sol of methyl ethyl ketone dispersion); As a cerium oxide aqueous dispersion, the brand name of Taki Chemical Co., Ltd. make: Nidral; As powders, such as alumina, a zirconium oxide, and titanium oxide, and a solvent dispersion, the brand name of Nano Kasei Co., Ltd. product: Nanotech etc. are mentioned.

The blending ratio of the non-conductive particles is preferably 0.1 to 70 parts by weight, more preferably 1 to 50 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B).

8. Manufacturing method of composition for antistatic layer formation

The composition for forming an antistatic layer comprises (A) phosphorus-containing tin oxide particles, (B) a compound having two or more polymerizable unsaturated groups in a molecule, (C) a photopolymerization initiator, a solvent, and (F) other polymerizable unsaturated, if necessary. It can manufacture by adding each compound, additive, and nonelectroconductive particle which have group, and mixing at room temperature or heating conditions. Specifically, it can manufacture using mixers, such as a mixer, a kneader, a ball mill, and a triaxial roll.

9. Formation method of antistatic layer

The antistatic layer of the laminate of the present invention can be obtained by applying the above-mentioned composition for forming an antistatic layer to the base material and drying, followed by irradiation with radiation to cure the composition.

The surface resistance of the obtained antistatic layer is 1x10 <^13> ohm / square or less, Preferably it is 1x10 <^10> ohm / square or less, More preferably, it is 1x10 <^8> ohm / square or less. When surface resistance exceeds 1x10 <^{13> (} ohm) / (square), antistatic performance may not be enough and it may become easy to adhere dust or the attached dust may not be easy to remove.

There is no restriction | limiting in particular as a coating method of the composition for antistatic layer formation, For example, well-known methods, such as roll coating, spray coating, flow coating, immersion, screen printing, inkjet printing, are applicable.

There is no restriction | limiting in particular as a source of radiation used for hardening of the composition for antistatic layer formation, as long as it can harden | cure in a short time after apply | coating a composition.

As a source of visible light, for example, direct sunlight, a lamp, a fluorescent lamp, a laser, and the like, and as a source of ultraviolet light, for example, a mercury lamp, a halide lamp, a laser, and the like, and a commercial source as an electron beam, for example, are commercially available. A cold cathode method that generates a high voltage pulse through a metal, and a secondary electron method that uses secondary electrons generated by a collision between ionized gaseous molecules and a metal electrode. have.

As a source of alpha rays, beta rays, and gamma rays, for example, fission materials such as ⁶⁰ Co may be used. For gamma rays, a vacuum tube may be used to impinge the accelerated electrons to the anode. These radiations can be irradiated individually by 1 type or 2 types or more simultaneously, and can also irradiate 1 or more types of radiation over a fixed period.

It is preferable that the film thickness of an antistatic layer is 0.05-30 micrometers. It is comparatively thick in the use which places importance on scratch resistance in outermost surfaces, such as a touch panel and CRT, Preferably it is 2-15 micrometers. On the other hand, when using as an antistatic film of an optical film, Preferably it is 0.05-10 micrometers.

Moreover, when using for an optical film, transparency is needed and it is preferable that total light transmittance is 85% or more.

III. Low refractive index layer

In order to use the laminate of the present invention as an antireflection film, it is necessary to form a low refractive index layer on at least the antistatic layer. The low refractive index layer formed in the laminate of the present invention is a cured product including a composition for forming a low refractive index layer containing particles (D) containing an ethylenically unsaturated group-containing fluorine-containing polymer and (E) silica as a main component.

Hereinafter, component (D) and (E) are demonstrated.

1. Ingredient (D)

(D) Ethylenic unsaturated group containing fluorine-containing polymer containing 40 mass% or more of fluorine

The ethylenically unsaturated group-containing fluorine-containing polymer used in the present invention is obtained by reacting a hydroxyl group-containing fluorine-containing polymer with a compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. Here, as a compound containing the functional group and ethylenically unsaturated group which can react with a hydroxyl group, the compound containing 1 isocyanate group and 1 or more ethylenically unsaturated group, or ethylenically unsaturated group containing carboxylic acid compound, or its derivative (s) is mentioned.

(1) hydroxyl-containing fluorine-containing polymer

The hydroxyl group-containing fluorine-containing polymer has (a) 20 to 70 mol%, (b) 1 to 70 mol% and (c) when the total of the following structural units (a), (b) and (c) is 100 mol%. ), And the polystyrene reduced number average molecular weight measured by gel permeation chromatography is preferably 5,000 to 500,000.

(a) The structural unit represented by following formula (1).

(b) The structural unit represented by following formula (2).

(c) The structural unit represented by following formula (3).

By configuring in this way, the coating film excellent in low refractive index, scratch resistance, coating property, and durability can be obtained.

<Formula 1>

[In Formula 1, R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ² (R ² represents an alkyl group or a fluoroalkyl group.)

<Formula 2>

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ^5, or a group represented by -OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

<Formula 3>

In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by-(CH ₂ ) _v -OR ²⁷ or -OCOR ²⁷ (R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group. And v represents a number from 0 to 2).

(1) structural unit (a)

In the general formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorocyclohexyl group And fluoroalkyl groups having 1 to 6 carbon atoms. Moreover, as an alkyl group of R <^2> , C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, are mentioned.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as the polymerization component. The fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; Alkyl perfluorovinyl ether or alkoxyalkyl perfluorovinyl ether; Perfluoros such as perfluoro (methylvinylether), perfluoro (ethylvinylether), perfluoro (propylvinylether), perfluoro (butylvinylether), perfluoro (isobutylvinylether) (Alkyl vinyl ether) s; 1 type of single or 2 or more types of perfluoro (alkoxy alkyl vinyl ether), such as perfluoro (propoxy propyl vinyl ether), is mentioned.

Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxy alkyl vinyl ether) are more preferable.

On the other hand, when the content rate of a structural unit (a) makes 100 mol% the sum total of the said structural unit (a), (b) and (c), it is preferable to set it as 20-70 mol%. The reason for this is that when the content is less than 20 mol%, the fluorine content of the fluorine-containing polymer is low, and the low refractive index, which is an optical feature of the fluorine-containing material, as intended by the present invention may be difficult. It is because the solubility, transparency, or adhesiveness to a base material of a hydroxyl-containing fluorine-containing polymer in the organic solvent may fall when content rate exceeds 70 mol%.

For this reason, the content of the structural unit (a) is more preferably 30 to 65 mol%, more preferably 40 to 60 mol%.

(2) structural unit (b)

In formula (2), examples of the alkyl group of R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and lauryl group, and examples of the alkoxycarbonyl group of R ⁴ include A oxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned, As a fluoroalkyl group of R <^5> , a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro butyl group, a perfluorohexyl group, 2- ( Trifluoromethyl) ethyl group, 2- (perfluoroethyl) ethyl group, 2- (perfluoropropyl) ethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluoropentyl) ethyl group, 2- ( Perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 2- (perfluorononyl) ethyl group, 2- (perfluorodecyl) ethyl group, etc. are mentioned.

The structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether and n- Alkyl vinyl ethers or cycloalkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; Allyl ethers such as ethyl allyl ether and butyl allyl ether; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl pivalate, a vinyl caproate, a vinyl versatate, and a vinyl stearate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) (Meth) acrylic acid esters such as acrylate and 2- (n-propoxy) ethyl (meth) acrylate; Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; And those having the following structural formulas.

(Wherein R ²⁸ is a hydrogen atom or a methyl group, w represents a number from 0 to 2)

These can be used individually by 1 type or in combination of 2 or more types.

On the other hand, when the content rate of a structural unit (b) makes 100 mol% the sum total of the said structural unit (a), (b), and (c), it is preferable to set it as 1-70 mol%. The reason is that the solubility of the hydroxyl group-containing fluorine-containing polymer in the organic solvent may be lowered if the content is less than 1 mol%. On the other hand, if the content is more than 70 mol%, the transparency of the hydroxyl-containing fluoropolymer This is because optical characteristics such as, and low reflectivity may be degraded.

For this reason, the content of the structural unit (b) is more preferably 2 to 65 mol%, more preferably 3 to 60 mol%.

(3) structural unit (c)

In the general formula (3), as the hydroxyalkyl group of R ²⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxy A pentyl group, 6-hydroxyhexyl group, etc. are mentioned.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5- Hydroxyl group-containing allyl ethers such as hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, and allyl Alcohol etc. are mentioned.

Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and caprolactone (meth) acrylate , Polypropylene glycol (meth) acrylate and the like can be used.

On the other hand, the content rate of the structural unit (c) is preferably 5 to 70 mol% when the total of the structural units (a), (b) and (c) is 100 mol%. The reason for this is that the solubility of the hydroxyl group-containing fluorine-containing polymer in the organic solvent may be lowered if the content is less than 5 mol%. On the other hand, the transparency of the hydroxyl group-containing fluorine-containing polymer is more than 70 mol%. This is because optical characteristics such as, and low reflectivity may be degraded.

For this reason, the content of the structural unit (c) is more preferably 5 to 65 mol%, more preferably 5 to 60 mol%.

(4) structural units (d) and structural units (e)

It is preferable that the said hydroxyl-containing fluorine-containing polymer contains 0.1-10 mol part of the following structural units (d) derived from an azo group containing polysiloxane compound with respect to 100 mol parts of said structural units (a), (b), and (c) in total. Do.

(d) The structural unit represented by following formula (4).

<Formula 4>

[In Formula 4, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group, or an aryl group.]

By including the structural unit (d), scratch resistance is improved.

Moreover, in the ethylenically unsaturated group containing fluorine-containing polymer of this invention, it is preferable to include the said structural unit (d) as a part of following structural unit (e).

(e) The structural unit represented by following formula (6).

In Formula 6, R ¹¹ to R ¹⁴ may be the same or different, and represent a hydrogen atom, an alkyl group, or a cyano group, R ¹⁵ to R ¹⁸ may be the same or different, a hydrogen atom or an alkyl group, a halogenated alkyl group, Or an aryl group, p, q represents a number from 1 to 6, s, t represents a number from 0 to 6, and y represents a number from 1 to 200;

Hereinafter, the structural units (d) and (e) will be described.

In the general formula (4), an alkyl group of R ⁸ or R ⁹ is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluoro group as the halogenated alkyl group A phenyl group, a benzyl group, a naphthyl group etc. are mentioned as an aryl group etc. as a C1-C4 fluoroalkyl group, such as a robutyl group, respectively.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following general formula (7).

[In Formula 7, R ^{11 To} R ¹⁴ , R ^{15 To} R ¹⁸ , p, q, s, t and y are the same as the above Formula 6, z is a number of 1 to 20]

In the case of using the compound represented by the formula (7), the structural unit (d) is included in the hydroxyl group-containing fluorine-containing polymer as part of the structural unit (e). In this case, in the formula (7), examples of the alkyl group of R ¹¹ to R ¹⁴ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group and cyclohexyl group, and examples of the alkyl group of R ¹⁵ to R ¹⁸ C1-C3 alkyl groups, such as a methyl group, an ethyl group, and a propyl group, are mentioned.

In the present invention, the compound represented by the following formula (8) is particularly preferable as the azo group-containing polysiloxane compound represented by the formula (7).

[In Formula 8, y and z are the same as those of Formula 7]

In addition, it is preferable to make content rate of a structural unit (d) into 0.1-10 mol part with respect to a total of 100 mol parts of said structural unit (a), (b), and (c). The reason is that if the content is less than 0.1 mole part, the surface slip resistance of the coating film after curing may be lowered, and the scratch resistance of the coating film may be reduced. On the other hand, if the content is more than 10 mole parts, the hydroxyl group-containing fluorine-containing polymer This is because the transparency of the resin is poor, and when used as a coating material, craters are likely to occur during coating.

For this reason, the content of the structural unit (d) is more preferably from 0.1 to 5 moles, more preferably from 0.1 to 3 moles. For the same reason, the content rate of the structural unit (e) is preferably determined so that the content rate of the structural unit (d) contained therein is within the above range.

(5) structural unit (f)

Moreover, it is preferable that the said hydroxyl-containing fluorine-containing polymer contains 0.1-5 mol% of following structural units (f).

(f) The structural unit represented by following formula (5).

<Formula 5>

In formula (5), R ¹⁰ represents a group having an emulsifying action.

By including the structural unit (f), the coatability is improved.

Hereinafter, the structural unit (f) will be described.

In the formula (5), as the group having an emulsifying action of R ¹⁰ , a group having both a hydrophobic group and a hydrophilic group and a hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide is preferable.

Examples of the group having such an emulsifying action include groups represented by the following formula (9).

[Wherein n represents a number from 1 to 20, m represents a number from 0 to 4, and u represents a number from 3 to 50]

The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. As such a reactive emulsifier, the compound represented by following formula (10) is mentioned.

<Formula 10>

[In Formula 10, n, m and u are the same as in Formula 9]

In addition, it is preferable to make content rate of a structural unit (f) into 0.1-5 mol part with respect to a total of 100 mol parts of said structural unit (a), (b), and (c). The reason is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluorine-containing polymer in the solvent is improved. On the other hand, when the content is less than 5 mole parts, the adhesiveness of the curable resin composition does not increase excessively, and handling becomes easy. It is because moisture resistance does not fall even if it uses it as a coating material.

For this reason, the content of the structural unit (f) is more preferably 0.1 to 3 moles, more preferably 0.2 to 3 moles with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(6) molecular weight

The hydroxyl group-containing fluorine-containing polymer preferably has a polystyrene-reduced number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography (hereinafter referred to as "GPC") using tetrahydrofuran (hereinafter referred to as "THF") as a solvent. Do. The reason is that the mechanical strength of the hydroxyl group-containing fluorine-containing polymer may decrease when the number average molecular weight is less than 5,000. On the other hand, when the number average molecular weight exceeds 500,000, the viscosity of the curable resin composition to be described later becomes high and the thin film This is because the coating may be difficult.

For this reason, the polystyrene reduced number average molecular weight of the hydroxyl group-containing fluorine-containing polymer is more preferably 10,000 to 300,000, more preferably 10,000 to 100,000.

(2) a compound containing one isocyanate group and one or more ethylenically unsaturated groups

The compound containing one isocyanate group and at least one ethylenically unsaturated group is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule.

On the other hand, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluorine-containing polymer.

Moreover, as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable at the point which can harden | cure the curable resin composition mentioned later more easily.

As such a compound, single 1 type or 2 or more types of combination of 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate is mentioned.

In addition, such a compound can also be synthesize | combined by making a diisocyanate and hydroxyl-containing (meth) acrylate react.

In this case, examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- Naphthalene diisocyanate, 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, methylenebis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexa Methylene diisocyanate, bis (2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3 -Bis (Iso City One kind alone or a combination of two or more kinds such as anatemethyl) cyclohexane, tetramethylxylylene diisocyanate, and 2,5 (or 2,6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane Can be mentioned.

Of these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are particularly preferable.

Moreover, as an example of hydroxyl group containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) Acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid Single 1 type, or 2 or more types of combinations, such as EO modified di (meth) acrylate, are mentioned.

Among these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferable.

On the other hand, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, For example, brand name HEA of Osaka Yuki Chemical Co., Ltd. make, brand name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. make. (Trade name) Aronix M-215, M-233, M-305, M-400 etc. are available.

When synthesize | combining from diisocyanate and hydroxyl group containing polyfunctional (meth) acrylate, it is preferable to make the addition amount of a hydroxyl group containing polyfunctional (meth) acrylate 1-1.2 mol with respect to 1 mol of diisocyanate.

As a synthesis | combining method of such a compound, the method of adding a diisocyanate and a hydroxyl group containing (meth) acrylate collectively, and making it react, the method of dropping and reacting diisocyanate in a hydroxyl group containing (meth) acrylate etc. are mentioned.

(3) an ethylenically unsaturated group-containing carboxylic acid compound or a derivative thereof

The ethylenically unsaturated group-containing carboxylic acid compound or a derivative thereof may be a compound having an ethylenically unsaturated group and a carboxylic acid in a molecule, or an acid halide, an acid anhydride or the like thereof, so long as the compound forms an ester with a hydroxyl group-containing fluorine-containing polymer. It is not limited.

Moreover, as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable at the point which can harden curable resin composition more easily.

As such a compound, (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid bromide, (meth) acrylic anhydride, etc. are mentioned.

(4) reaction molar ratio

The ethylenically unsaturated group-containing fluorine-containing polymer of the present invention is a compound containing one isocyanate group and one or more ethylenically unsaturated groups and a hydroxyl group-containing fluorine-containing polymer in a molar ratio of isocyanate group / hydroxyl group of 0.1 to 1.9. It is preferable to make it react. The reason is that if the molar ratio is less than 0.1, the scratch resistance and durability may decrease. On the other hand, if the molar ratio exceeds 1.9, the scratch resistance after immersion of the aqueous alkali solution of the coating film of the curable resin composition may decrease. to be.

For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 0.3 to 1.5, and more preferably 0.5 to 1.5.

For the same reason, it is preferable that the molar ratio of the ethylenically unsaturated group-containing carboxylic acid compound or its derivative and the hydroxyl group-containing fluorine-containing polymer react with the ethylenically unsaturated group-containing carboxylic acid compound or its derivative / hydroxyl group at a ratio of 0.1 to 1.9. desirable. However, when the carboxylic acid derivative is an acid anhydride, it is possible to react with two hydroxyl groups in one molecule, so that the molar ratio of the acid anhydride / hydroxyl group of the ethylenically unsaturated group-containing carboxylic acid compound is in the ratio of 0.05 to 0.95. It is preferable.

Although it does not restrict | limit especially about the addition amount of an ethylenically unsaturated group containing fluoropolymer (D) in the composition for low refractive index layer formation, It is 1-95 mass% normally with respect to the composition whole quantity other than an organic solvent. This is because the refractive index of the cured coating film of curable resin composition may become high that the addition amount is less than 1 mass%, and sufficient antireflection effect may not be obtained. On the other hand, when addition amount exceeds 95 mass%, curable resin composition This is because the scratch resistance of the cured coating film may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (E) component into 2 to 90 mass%, and it is still more preferable to set it as the value within 3 to 85 mass% range.

2. Ingredient (E)

(1) Particles based on silica

In the composition for forming the low refractive index layer used in the present invention, particles containing silica as a main component can be blended, and the scratch resistance, particularly steel wool resistance, of the cured product of the composition for forming the low refractive index layer can be improved. As particle | grains which have silica as a main component, the particle | grains which have silica as a main component with a number average particle diameter of 1-100 nm are preferable. The particle diameter is measured by a transmission electron microscope. 5-80 nm is preferable and, as for the particle diameter of (E) component, 10-60 nm is more preferable.

As particle | grains which have these silica as a main component, a well-known thing can be used and its shape is not specifically limited, either. If it is spherical, it is not limited to normal colloidal silica, It may be a hollow particle, a porous particle, core-shell type particle, etc. Moreover, it is not limited to spherical form, Amorphous particle may be sufficient. Of these, colloidal silica having a solid content of 10 to 40% by weight is preferable.

In addition, the dispersion medium is preferably water or an organic solvent. As an organic solvent, Alcohol, such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Organic solvents, such as ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned, Among these, alcohol and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

As a commercial item of the particle containing a silica as a main component, it is a colloidal silica, for example, Nissan Chemical Co., Ltd. brand name: methanol silicazol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST -L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50 , ST-OL, and the like.

Moreover, the thing which surface-treated, such as chemical modification, can be used for the colloidal silica surface, For example, what contains the hydrolyzable silicon compound which has one or more alkyl groups, or its hydrolyzate etc. can be made to react. Examples of such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxy silane and dodecyl tree. Methoxysilane, 1,1,1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3 -Trimethyl-1,3-disiloxane, α-trimethylsilyl-ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxanehexamethyl-1,3-disila A glass etc. can be mentioned. It is also possible to use hydrolyzable silicon compounds having at least one reactive group in the molecule. Hydrolyzable silicon compound having at least one reactive group in the molecule, for example, a reactive group as having an NH _2, elements trimethoxysilane, N- (2- aminoethyl) -3-aminopropyltrimethoxysilane, etc. And 3-thiocyanate propyl as having a thiocyanate group such as 3-isocyanate propyltrimethoxysilane as having an isocyanate group such as bis (2-hydroxyethyl) -3 aminotripropylmethoxysilane as having an OH group 3-mercaptopropyl as having a thiol group, such as (3-glycidoxypropyl) trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as having an epoxy group, such as trimethoxysilane Trimethoxysilane etc. are mentioned. As a preferable compound, 3-mercaptopropyl trimethoxysilane is mentioned.

(2) Preferred Embodiment (Silica Particles Having Ethylenically Unsaturated Group on the Surface)

It is preferable that the silica particle used for this invention has an ethylenically unsaturated group (henceforth "reactive silica particle"). Although the manufacturing method of a reactive silica particle is not specifically limited, For example, it can obtain by making the above-mentioned number average particle diameter silica particle and the reactive surface treating agent 10-10 nm react.

Here, as a surface treating agent, an alkoxysilane compound, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, etc. are mentioned, for example. These can be used individually by 1 type or in combination of 2 or more types.

As a specific example of a surface treating agent, The compound which has a unsaturated double bond in molecules, such as (gamma)-methacryloxypropyl trimethoxysilane, (gamma) -acryloxypropyl trimethoxysilane, and vinyl trimethoxysilane, is represented by following formula (11). The compound which becomes.

Wherein, R ¹⁹ is a methyl group, R ²⁰ is an alkyl group having 1 to 6 carbon atoms, R ²¹ is a hydrogen atom or a methyl group, j is 1 or 2, k is an integer from 1 to 5, R ²² is a divalent group having 1 to 6 carbon atoms Alkylene group, R ²³ is a divalent hydrocarbon group having 2 to 14 carbon atoms of any one of 2 to 6-valent chain, cyclic, branched, R ²⁴ is (k + 1) having any of 3 to 14 carbon atoms of a chain, cyclic, branched ) Is a hydrocarbon group. Ether bonds may be included in R ²⁴ .

When a silica particle has an ethylenically unsaturated group, it can co-crosslink with a UV curing acrylic monomer, and abrasion resistance improves.

(3) Preferred Embodiments (Porous Silica Particles)

As silica particle (E) used for the composition for low refractive index layer formation, porous silica particle is also preferable.

As the porous silica particles, it is more preferable to use the first porous silica particles (E1) or the second porous silica particles (F2). The first porous silica particles (F1) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (12) and a silicon compound represented by the following formula (13). That is, it is obtained by hydrolyzing and / or hydrolytically condensing the silicon compound represented by the formula (12), and further hydrolyzing and / or hydrolyzed condensation of the silicon compound represented by the formula (13). The silicon compound represented by the formula (12) and the silicon compound represented by the formula (13) may be mixed and hydrolyzed and / or hydrolytically condensed at the same time, and the silicon compound represented by the formula (12) is hydrolyzed and / or hydrolytically condensed, Subsequently, a silicon compound represented by the formula (13) may be added to further hydrolyze and / or hydrolyze condensation. The second porous silica particles (E2) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (12), a silicon compound represented by the following formula (13) and a silicon compound represented by the following formula (14). That is, hydrolysis and / or hydrolytic condensation of the silicon compound represented by the formula (12), hydrolysis and / or hydrolytic condensation of the silicon compound represented by the formula (13), and hydrolysis of the silicon compound represented by the formula (14) And / or hydrolytic condensation. The silicon compound represented by the formula (12), the silicon compound represented by the formula (13), and the silicon compound represented by the formula (14) may be mixed and hydrolyzed and / or hydrolyzed condensed at the same time. Decomposition and / or hydrolysis condensation may be performed, followed by further hydrolysis and / or hydrolysis condensation by addition of the silicon compound represented by the formula (13) and the silicon compound represented by the formula (14).

SiX ₄

R ²⁵ _a SiX _{4 -a}

R ²⁶ _b SiX _{4 -b}

In the formulas (12), (13) and (14), each X is independently an alkoxy group, a halogeno group, an isocyanate group, a carboxyl group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, preferably Is an alkoxy group and a halogeno group, More preferably, it is an alkoxy group. In addition, X in Formulas 12, 13 and 14 may be the same or different.

As a compound represented by General formula (12), tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane, etc. are mentioned, for example.

In formula (13), R ²⁵ is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a vinyl group, allyl group, acryloxyethyl group, or acryloxy Propyl group, acryloxybutyl group, methacryloxyethyl group, methacryloxypropyl group, and methacryloxybutyl group.

In general formula (13), a is an integer of 1-3, Preferably it is 1-2.

As a compound represented by General formula (13), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, acryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, etc. are mentioned, for example.

By using the compound represented by General formula (13), porous silica particle can be made to contain an ethylenically unsaturated group. By including an ethylenically unsaturated group, the scratch resistance of the antireflection film of this invention which has the cured film which hardened | cured the curable composition improves.

In formula (14), R ²⁶ is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, and more preferably a fluorine-substituted alkyl group having 3 to 10 carbon atoms.

In formula (14), b is an integer of 1-3, Preferably it is 1-2.

Examples of the compound represented by the formula (14) include 3,3,3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, 2-perfluorohexylethyltrimethoxysilane, 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 3,3-di (trifluoromethyl) -3-fluoropropyltriethoxysilane, etc. are mentioned. .

By using the compound represented by General formula (14), porous silica particle can be made to contain a fluorine-containing alkyl group. By containing a fluorine-containing alkyl group, the stain resistance of the cured film which hardened the curable composition can be improved.

Meanwhile, the silicon compound represented by the formula (12), the silicon compound represented by the formula (13), and the silicon compound represented by the formula (14) may each be used two or more kinds.

In the first porous silica particles (E1), when the total of the silicon compound represented by the formula (12) and the silicon compound represented by the formula (13) is 100 mol%, the silicon compound represented by the formula (12) / silicon represented by the formula (13) The compound is preferably hydrolyzed and / or hydrolyzed condensed at a ratio of 67 to 99/1 to 33 (mol%), more preferably 70 to 98/2 to 30 (mol%).

In the second porous silica particles (E2), when the total of the silicon compound represented by the formula (12), the silicon compound represented by the formula (13), and the silicon compound represented by the formula (14) is 100 mol%, the silicon represented by the formula (12) The silicon compound represented by the compound / Formula 13 / the silicon compound represented by the formula 14 is preferably 60 to 98/1 to 30/1 to 20 (mol%), more preferably 65 to 96/2 to 20/2 Hydrolysis and / or hydrolysis condensation at a ratio of from 15 (mol%).

The first and second porous silica particles (E1) and (E2) used in the present invention have an average particle diameter of 5 to 50 nm, preferably 5 to 45 nm, and more preferably 5 to 40 nm. An average particle diameter is a number average particle diameter, and is measured by a transmission electron microscope observation image. In addition, "porous" means that the specific surface area is 50 to 1000 m ² / g, preferably 50 to 800 m ² / g, and more preferably 100 to 800 m ² / g. The specific surface area is measured by the BET method.

When average particle diameter is in the said range, scattering in the visible light region of the coating film obtained can be suppressed. Moreover, by making it porous, a density falls and the refractive index of the film | membrane containing such porous silica particles becomes low.

Porous silica particle (E) is obtained by the manufacturing method demonstrated below.

The first or second porous silica particles (E1), (E2) are each represented by the above formula in the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and half ethers of acid amides, diols, and diols. Hydrolysis and / or hydrolysis condensation of a silicon compound represented by 12 and a silicon compound represented by Formula 13, or a silicon compound represented by Formula 12, a silicon compound represented by Formula 13, and a silicon compound represented by Formula 14 Can be prepared.

As the basic compound, for example, an amine compound is used, and as specific examples, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Ammonia, methylamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, tri Ethylamine, tripropylamine, tributylamine, and the like. Preferably, ammonia, ethanolamine, tetramethylamine hydroxide and the like are used.

These basic compounds can use 1 type (s) or 2 or more types simultaneously.

Acid amides, diols or half ethers of diols are preferably compatible with water and alcohols.

As the acid amide, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are used, and preferably N, N-dimethylformamide, N, N-dimethyl Acetamide is used.

As the diol, for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used. As the half ether of the diol, for example, ethylene glycol monomethyl ether and propylene glycol monomethyl ether are used.

The porous silica particles used in the present invention can make the particles porous by coexisting acid amides, diols or semi-ethers of diols in the synthesis.

The total concentration of the silicon compound of the formula (12) and the silicon compound of the formula (13) or the silicon compound of the formulas (12) to (14) in the reaction solution is usually 0.5 to 10 mass%, preferably 1 to 8 mass% in terms of complete hydrolysis condensate. Here, "completely hydrolyzed condensate conversion" is a theoretical value calculated on the assumption that the silicon compound is completely hydrolyzed condensed, and X of the silicon compound of formula 12 and the silicon compound of formula 13 or the silicon compounds of formulas 12 to 14 Corresponds to the mass in the case of substituting with a 1/2 mole oxygen atom of X. By making the density | concentration of the silicon compound at the time of particle | grain synthesis into the said range, coarsening of a particle is prevented and it can be set as the particle | grains of 5-50 nm of average particle diameters.

The silicon compound of formula 12 and the silicon compound of formula 13, or the silicon compound of formula 12, the silicon compound of formula 13 and the silicon compound of formula 14 may be simultaneously mixed to hydrolyze and / or hydrolyze condensate, and may also be water, In the presence of at least one selected from alcohols, basic compounds, and half ethers of acid amides, diols and diols, the silicon compounds represented by formula (12) are hydrolyzed and / or hydrolyzed condensed, and then respectively The silicon compound represented by 13, or the silicon compound represented by Formula 13 and the silicon compound represented by Formula 14 may be added to further hydrolyze and / or hydrolytic condensation.

The reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of alcohol and acid amides to be used. The reaction time depends on the kind of silicon compound represented by the formula (12), the silicon compound represented by the formula (13), and the silicon compound represented by the formula (14), the reaction rate, the type and amount of the base, and the like. It doesn't work.

An organic solvent is added to the obtained hydrolysis and / or hydrolysis condensation reaction liquid, and further, if necessary, the unnecessary components are removed by a method such as distillation or liquid extraction to obtain a dispersion liquid in which the porous silica particles are dispersed in the organic solvent. .

In addition, the dispersion medium is preferably water or an organic solvent. As an organic solvent, Alcohol, such as methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Organic solvents, such as ethers, such as tetrahydrofuran and a 1, 4- dioxane, are mentioned, Among these, alcohol and ketones are preferable. These organic solvents can be used individually or in mixture of 2 or more types as a dispersion medium.

The blending amount of the porous silica particles (E) in the composition for forming the low refractive index layer is usually 5 to 99 mass%, preferably 10 to 98 mass%, and preferably 15 to 97 mass%, based on the total amount of the composition other than the organic solvent. More preferred. If it is less than 5 mass%, the hardness at the time of setting it as a cured film may become inadequate, and if it exceeds 99 mass%, sufficient film strength may not be obtained. In addition, the quantity of particle means solid content, and when particle | grains are used in the form of a solvent dispersion liquid, the compounding quantity does not contain the quantity of a solvent.

3. A polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group ((G ) ingredient)

The composition for low refractive index layer formation contains a polyfunctional (meth) acrylate compound containing at least two or more (meth) acryloyl groups and / or fluorine containing at least one or more (meth) acryloyl groups, if necessary. You may add a (meth) acrylate compound.

(1) a polyfunctional (meth) acrylate compound containing at least two or more (meth) acryloyl groups

The compound is not particularly limited as long as it is a compound containing at least two or more (meth) acryloyl groups in the molecule. Examples thereof include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, "U-15HA" (trade name, Shinnakamura Chemical Industries, Ltd.) 1 type single, or 2 or more types of combinations, such as manufacture) is mentioned.

Meanwhile, among these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone modified di Pentaerythritol hexa (meth) acrylate is particularly preferred.

(2) Fluorine-containing (meth) acrylate compound containing at least one or more (meth) acryloyl groups

The compound is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group. As such an example, a perfluoro octyl ethyl (meth) acrylate, an octafluoro pentyl (meth) acrylate, a trifluoroethyl (meth) acrylate, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Although it does not restrict | limit especially about the addition amount of these (G) components, It is 0-90 mass% normally with respect to composition whole quantity other than the organic solvent. The reason for this is that when the added amount exceeds 90 mass%, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained.

Moreover, for this reason, it is more preferable to make the addition amount of (G) component into 80 mass% or less, and it is still more preferable to set it as the addition amount of 60 mass% or less.

4. Compounds that generate active species by irradiation or heat of active energy rays

In this invention, the compound which generate | occur | produces an active species by irradiation or heat of an active energy ray can also be added. The compound which generate | occur | produces an active species by irradiation of an active energy ray or heat is used for hardening curable resin composition.

(1) Compounds that Generate Active Species by Irradiation of Active Energy Rays

As a compound which generate | occur | produces an active species by irradiation of an active energy ray (henceforth a "photoinitiator"), the radical radical generator etc. which generate | occur | produce a radical as an active species are mentioned.

On the other hand, an active energy ray is defined as an energy ray which can generate | occur | produce an active species by decomposing the compound which produces an active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. However, it is preferable to use ultraviolet rays in view of having a constant energy level, a fast curing speed, and a relatively inexpensive and compact irradiation apparatus.

(i) Type

As an example of an optical radical generating agent, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydioxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2- Dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propylether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra (tert- Butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenyl Til) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other color sensitizers; Can be.

Among these photoinitiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4,6 -Trimethylbenzoyldiphenylphosphineoxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (mor Polyyl) phenyl] -2-phenylmethyl) -1-butanone and the like, and more preferably 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino propane-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, etc. are mentioned.

(ii) added amount

Although the addition amount of a photoinitiator is not specifically limited, It is preferable to set it as 0.01-20 mass% with respect to the composition whole quantity other than the organic solvent. This is because when the addition amount is less than 0.01% by mass, the curing reaction may be insufficient, and the scratch resistance and the scratch resistance after immersion in the aqueous alkali solution may decrease. On the other hand, when the addition amount of a photoinitiator exceeds 20 mass%, it is because the refractive index of a cured film may increase and the antireflection effect may fall.

Moreover, for this reason, it is more preferable to make 0.05-15 mass% of addition amount of a photoinitiator with respect to composition whole quantity other than the organic solvent, and it is still more preferable to set it as 0.1-15 mass%.

(2) Compounds that generate active species by heat

As a compound which generate | occur | produces an active species by heat (henceforth a "thermal polymerization initiator"), the thermal radical generator etc. which generate | occur | produce a radical as an active species are mentioned.

(i) Type

Examples of the thermal radical generator include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide tert-butylhydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Single 1 type or combination of 2 or more types is mentioned.

(ii) added amount

Although it does not restrict | limit in particular also about the addition amount of a thermal polymerization initiator, It is preferable to set it as 0.01-20 mass% with respect to composition whole quantity other than an organic solvent. This is because when the addition amount is less than 0.01% by mass, the curing reaction may be insufficient, and the scratch resistance and the scratch resistance after immersion in the aqueous alkali solution may decrease. On the other hand, when the addition amount of a photoinitiator exceeds 20 mass%, it is because the refractive index of a cured film may increase and the antireflection effect may fall.

Moreover, it is more preferable to make the addition amount of a thermal polymerization initiator into 0.05-15 mass% with respect to the composition whole quantity other than an organic solvent for this reason, and it is still more preferable to set it as the value within 0.1-15 mass% range.

5. Organic solvent

It is preferable to add an organic solvent further to "the composition for low refractive index layer formation." By adding an organic solvent in this way, the anti-reflection film of a thin film can be formed uniformly. As such an organic solvent, the organic solvent of a C1-C8 alcohol system, a C3-C10 ketone system, and a C3-C10 ester system can be used preferably, Methyl isobutyl ketone, Methyl ethyl ketone, Methyl amyl ketone , Methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol monopropyl ether and the like are particularly preferred examples. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

Although it does not restrict | limit especially also about the addition amount of an organic solvent, It is preferable to set it as 100-100,000 mass parts with respect to 100 mass parts of compositions other than an organic solvent. This is because the viscosity adjustment of curable resin composition may become difficult when the addition amount is less than 100 mass parts, On the other hand, when the addition amount exceeds 100,000 mass parts, the storage stability of curable resin composition will fall or a viscosity will become It is because it may fall too much and handling becomes difficult.

6. Additive

In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, and a silane within a range that does not impair the object or effect of the present invention. Coupling agents, inorganic fillers other than (E) component, etc. can be mix | blended.

7. Manufacturing method of composition for low refractive index layer formation

Curable resin composition used by this invention produces | generates active species by the said (D) ethylenically unsaturated group containing fluorine-containing polymer and said (E) component, or the said (G) component, active energy ray, or heat as needed. It can manufacture by adding a compound, an organic solvent, and an additive, respectively, and mixing on room temperature or heating conditions. Specifically, it can manufacture using mixers, such as a mixer, a kneader, a ball mill, and a triaxial roll. However, when mixing under heating conditions, it is preferable to carry out below the decomposition start temperature of a thermal polymerization initiator.

8. Hardening method of composition for low refractive index layer formation

Although it does not restrict | limit especially about the hardening conditions of the composition for low refractive index layer formation, For example, when an active energy ray is used, it is preferable to make an exposure amount into the value within 0.01-10 J / cm <^2> .

This is because when the exposure amount is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure amount exceeds 10 J / cm ² , the curing time may be excessively long.

For this reason, it is more preferable to make the exposure amount a value within the range of 0.1 to 5 J / cm ² , and even more preferably to a value within the range of 0.3 to 3 J / cm ² .

In addition, when heating and hardening the composition for low refractive index layer formation, it is preferable to heat for 0.5 to 180 minutes at the temperature within the range of 30-200 degreeC. By heating in this way, an antireflection film excellent in scratch resistance can be obtained more efficiently without damaging the substrate or the like.

Further, for this reason, it is more preferable to heat 1 to 120 minutes at a temperature in the range of 50 to 180 ° C, and more preferably 1 to 60 minutes at a temperature in the range of 80 to 150 ° C.

EXAMPLE

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples. In addition, in the following, parts and% represent each weight part and weight% unless there is particular notice.

Preparation Example 1 Preparation of Composition 1 for Antistatic Layer Formation

Phosphorus-containing tin oxide dispersion liquid (ELCOM JX-1001PTV manufactured by Shokubai Kasei Kogyo Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30 wt%, average primary particle size 20 nm) , Dispersant 2.17% by weight) 80 parts, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., may be hereinafter referred to as B-1) 15.6 parts, bis (acryloyloxymethyl 12.5 parts of tricyclo [5.2.1.0 ^2,6 ] decane (NK ester A-DCP by Shin-Nakamura Chemical Co., Ltd .: "tricyclodecanediyl dimethanol diacrylate", hereafter called B-2) , 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc., molar extinction coefficient at 313 nm: 80 L / mol · cm, hereinafter sometimes referred to as C-1) 4.5 Part and 50 parts of propylene glycol monomethyl ether at 50 ° C. By stirring for 2 hours to obtain a composition 1 for the antistatic layer with a uniform solution formed. After weighing 2g of this composition 1 for antistatic layer formation on the aluminum plate, it dried for 1 hour and weighed on the 140 degreeC hotplate, and calculated | required solid content, and it was 35 weight%.

Preparation Example 2 Preparation of Composition 2 for Antistatic Layer Formation

Phosphorus-containing tin oxide dispersion liquid (ELCOM JX-1001PTV, manufactured by Shokubai Kasei Kogyo Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30 wt%, average primary particle size 20) Nm, containing a dispersant 2.17% by weight) 200 parts, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., may be referred to hereinafter as B-1) 15.6 parts, bis (acryloyloxy Methyl) tricyclo [5.2.1.0 ^2,6 ] decane (NK ester A-DCP manufactured by Shinnakamura Chemical Industries, Ltd .: "tricyclodecanediyl dimethanol diacrylate", hereinafter sometimes referred to as B-2) 15.6 Molar extinction coefficient in 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one (Irgacure 907, 313 nm of Ciba Specialty Chemicals, Inc.) : 17,000 L / mol · cm, hereinafter may be referred to as C′-2) 4.5 parts, and propylene glycol monome Ether 50 parts by stirring for 2 hours at 50 ℃ to obtain a second for the antistatic layer of the uniform solution to form the composition. After weighing 2g of this composition 2 for antistatic layer formation to the aluminum dish, it dried for 1 hour and weighed on the 140 degreeC hotplate, and calculated | required solid content, and it was 35 weight%.

Preparation Example 3 Synthesis of Organic Compound Having Polymeric Unsaturation

To the solution containing 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate were dripped at 50 degreeC over 1 hour, stirring at 70 degreeC, The mixture was heated and stirred for 3 hours. It contains NK ester A-TMM-3LM-N (60 weight% of pentaerythritol triacrylate and 40 weight% of pentaerythritol tetraacrylates) by Shin-Nakamura Chemical Co., and among these, a hydroxyl group is involved in reaction. Only 549 parts of pentaerythritol triacrylate having a d) was added dropwise at 30 ° C over 1 hour, and then heated and stirred at 60 ° C for 10 hours to obtain an organic compound having a polymerizable unsaturated group. Analysis of the amount of remaining isocyanate in the reaction solution by FT-IR showed 0.1% or less, indicating that the reaction was almost quantitatively terminated. The infrared absorption spectrum of the product is that the absorption peak of 2550 cm ^-1 characteristic of the mercapto group in the raw material and the absorption peak of 2260 cm ^-1 characteristic of the raw material isocyanate compound are lost, and the urethane bond and S (C = 0) NH- A peak of 1660 cm ⁻¹ characteristic to the group and a 1720 cm ⁻¹ characteristic characteristic of the acryloxy group were observed, and an acryl jade having an acryloxy group as the polymerizable unsaturated group and —S (C═O) NH— and a urethane bond It was shown that a time modified alkoxysilane was produced. By the above, other than 773 parts of the compounds represented by following formula (15) and (16) were obtained in total (hereinafter, this compound may be called "alkoxysilane (1)"), the pentaerythritol tetraacryl which was not involved in reaction 220 parts of rates are mixed.

[In Formula 15 and Formula 16, "Acryl" represents an acryloyl group and "Me" represents a methyl group.]

Preparation Example 4 Preparation of a Compound Represented by Formula 17

[In Formula 17, "Acryl" represents an acryloyl group.]

NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (manufacturer involved in the reaction) is a solution containing 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container with a stirrer. Only 93 parts of pentaerythritol triacrylate having the same was added dropwise under the condition of 10 ° C and 1 hour, and then stirred under the condition of 60 ° C and 6 hours to obtain a reaction liquid.

The amount of residual isocyanate in this reaction solution was measured in the same manner as in Production Example 3 and measured by FT-IR, and it was confirmed that the reaction was almost quantitatively performed at 0.1 wt% or less. In addition, it was confirmed that the molecule contains a urethane bond and acryloyl group (polymerizable unsaturated group).

As mentioned above, 37 parts of pentaerythritol tetraacrylate which did not participate in reaction were mixed besides 75 parts of compounds represented by the said Formula (17) were obtained.

Preparation Example 5 Preparation of Silica Particle-Containing Hard Coating Layer Composition

2.32 parts of the solution of the alkoxysilane (1) manufactured in the manufacture example 3, silica particle sol (methyl ethyl ketone silica sol, MEK-ST by Nissan Chemical Industries, Ltd., number average particle diameter 0.022 micrometer, silica concentration 30%) After stirring the mixture liquid of 91.3 parts (27 parts as silica particles), 0.12 parts of ion-exchange water, and 0.01 parts of p-hydroxyphenyl monomethyl ether at 60 degreeC for 4 hours, 1.36 parts of methyl ortho formates are added, and it is further 1 The reactive silica particle dispersion was obtained by heating and stirring at the same temperature for a time. It was 31 weight% as a result of calculating solid content similarly to the manufacture example 1.

98.6 g of this dispersion, 3.4 g of a solution containing the compound represented by formula (17) obtained in Production Example 4, 2.1 g of 1-hydroxycyclohexylphenylketone (C-1), 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholinopropane-1-one (C-2) 1.2g, dipentaerythritol hexaacrylate 33.2g, and cyclohexanone 7g were mixed and stirred, and the composition for hard-coat layers containing a silica particle ( 145 g of solid content concentration 50%) were obtained.

Preparation Example 6 Preparation of Reactive Silica Particle Sols with Organic Compounds Having Polymeric Unsaturation

143 g of silica particle sol (methyl ethyl ketone silica sol, MEK-ST-L manufactured by Nissan Chemical Industries, Ltd., 0.05 µm in number average particle diameter, 30% silica concentration) (43 g as silica particles), in Production Example 3 2.8 g of the prepared solution of alkoxysilane (1), 0.1 g of distilled water, and 0.01 g of p-hydroquinone monomethyl ether were mixed and stirred at 65 ° C by heating. After 4 hours, 1.0 g of orthoformate methyl ester was added, and further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%.

Production Example 7: Preparation of hydroxyl-containing fluorine-containing polymer (d-1)

After fully replacing a 3.0 L stainless steel autoclave with an electronic stirrer with nitrogen gas, 1800 g of ethyl acetate, 607.3 g of perfluoro (propylvinylether) (FPVE), and (perfluorooctyl) ethylvinylether 111.9 180.8 g of hydroxyethyl vinyl ether (HEVE) and 4.5 g of lauroyl peroxide were added thereto, and oxygen in the system was removed again with nitrogen gas.

Subsequently, after raising temperature and continuing reaction under stirring at 70 degreeC for 20 hours, autoclave was cooled by water and reaction was stopped.

After the temperature of the reaction solution reached room temperature, the autoclave was opened to recover the reaction solution, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixed weight ratio 80/20). The precipitate was taken out and dried under reduced pressure at 40 ° C to obtain a hydroxyl group-containing fluorine-containing polymer (d-1).

Production Example 8: Preparation of hydroxyl-containing fluorine-containing polymer (d-2)

After fully replacing a 3.0 L stainless steel autoclave with an electronic stirrer with nitrogen gas, 1600 g of ethyl acetate, 539.8 g of perfluoro (propylvinylether) (FPVE), and (perfluorooctyl) ethylvinylether 99.5 g, hydroxyethyl vinyl ether (HEVE) 160.7 g, lauroyl peroxide 4 g, 24 g of VPS1001 and 160 g of NE-30 were put, and oxygen in the system was removed again by nitrogen gas.

Subsequently, after raising temperature and continuing reaction under stirring at 70 degreeC for 20 hours, autoclave was cooled by water and reaction was stopped.

After the temperature of the reaction solution reached room temperature, the autoclave was opened and the reaction solution was recovered, and then the reaction solution was added dropwise to 30 kg of a methanol / water mixed solution (mixed weight ratio 80/20). The precipitate was taken out and dried under reduced pressure at 40 ° C to obtain a hydroxyl-containing fluorine-containing polymer (d-2).

Here, VPS1001 is an azo-group containing polydimethylsiloxane represented by the said Formula (8) whose number average molecular weight is 7-90,000, and the molecular weight of a polysiloxane part is about 10,000. NE-30 is a nonionic reactive emulsifier in formula 10, wherein n is 9, m is 1, and u is 30.

Preparation Example 9 Preparation of Ethylenic Unsaturation-Containing Fluoropolymer Solution (D-1)

400 g of a hydroxyl group-containing fluorine-containing polymer (d-1) obtained in Production Example 7 and a methyl isoform as a solvent in a separate 5-liter flask equipped with an electronic stirrer, a glass cooling tube, a glass Dean stark tube, a glass dropping funnel and a thermometer. 1200 g of butyl ketones (MIBK) were added, and the mixture was stirred at room temperature to dissolve the hydroxyl group-containing polymer in the solvent. Next, 64.0g of acrylic acid was added, it stirred at room temperature, and it confirmed visually that the solution became uniform. The solution which melt | dissolved 8.8g sulfuric acid in 160g MIBK was dripped, stirring at room temperature using the glass dropping funnel. After completion of the dropwise addition, the mixture was warmed by using an oil bath so that the temperature of the system became 120 to 127 ° C, and stirred for 5 hours while removing water accumulated in the Dean Stark tube. After cooling to room temperature, 32 g of a 10% aqueous ammonia solution was added, and it was confirmed using a pH indicator that the pH of the reaction solution was 6-7. The obtained reaction liquid was dripped at 20 kg of methanol / water (mixing weight ratio 80/20) mixed solution, and the polymer was deposited. The precipitated polymer was dissolved in MIBK so as to have a solid content of 20% by weight, and then water was removed from the system by magnesium sulfate, followed by filtration to obtain an ethylenically unsaturated group-containing fluoropolymer solution having a solid content of 20% (D-1). Got. The composition analysis of the obtained ethylenically unsaturated group containing fluoropolymer was performed by ¹³ C-NMR, and the fluorine content calculated | required from the composition was 54 weight%.

Preparation Example 10 Preparation of Ethylenically Unsaturated Group-Containing Fluoropolymer Solution (D-2)

400 g of the hydroxyl group-containing fluorine-containing polymer (d-2) obtained in Production Example 8, and 2,6-di-t- as a polymerization inhibitor, in a three-liter separation flask equipped with an electronic stirrer, a glass cooling tube, and a thermometer. 0.07 g of butylmethylphenol and 1851 g of MIBK and 62.6 g of 2-methacryloyloxyethyl isocyanate are added as a solvent, and stirred until the solution becomes uniform, followed by 0.9 g of dibutyltin dilaurate. The reaction was started, the temperature of the system was maintained at 55 to 65 ° C, and stirring was continued for 5 hours under dry air, whereby a reaction solution of a hydroxyl-containing fluorine-containing polymer (d-2) and 2-methacryloyloxyethyl isocyanate (D-2) (solid content concentration 20weight%) was obtained. The composition analysis of the obtained ethylenically unsaturated group containing fluoropolymer was performed by ¹³ C-NMR, and the fluorine content calculated | required from the composition was 45 weight%.

Preparation Example 11 Preparation of Composition 1 for Forming Low Refractive Index Layer

86.7 g of reactive silica particle sol obtained in Production Example 6 (26.9 g as reactive particles), 204.0 g of ethylenically unsaturated group-containing fluorine-containing polymer (D-1) obtained in Production Example 9 (40.8 g as ethylenically unsaturated group-containing fluoropolymer) ), 100.0 g of ethylenically unsaturated group-containing fluoropolymer (D-2) obtained in Production Example 10 (20.0 g as ethylenically unsaturated group-containing fluoropolymer), 6.8 g of dipentaerythritol pentaacrylate, and the chemical formula obtained in Production Example 4. 2.9 g of a composition comprising 17, 4.8 g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one as a photopolymerization initiator, acryloyl modified polydimethylsiloxane (FM0725, 3.0 g of Chisso Corp., 0.7 g of special copolymer containing organic copolymer (Florene AC-901, Kyoeisha Chemical Co., Ltd.) and 2239 g of methyl isobutyl ketone are added, and it is stirred at room temperature for 1 hour, and low refractive index is added. The composition 1 for layer formation was obtained. Solid content was calculated | required similarly to the manufacture example 1, and it was 4 weight%.

Preparation Example 12 Synthesis of Porous Silica Particles

22.24 g of tetraethoxysilane, 841.97 g of methanol, and 30.00 g of propylene glycol were added and mixed uniformly in the quartz separatory flask, and 101.00 g of 1% aqueous solution of ammonia was added. Thereafter, the solution was reacted at 40 ° C. for 8 hours while stirring, and 0.92 g of vinyltrimethoxysilane and 1.54 g of methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Toray Dow Corning Silicon Co., Ltd.) were further added. It was made to react at 40 degreeC for 1 hour. Next, 2.33 g of 2-perfluorohexylethyltrimethoxysilane (TSL8257 manufactured by GE Toshiba Silicone Co., Ltd.) was added, and the mixture was reacted at 40 ° C for 1 hour. After cooling the reaction liquid to room temperature, 1000.00 g of methyl isobutyl ketone and 1000.00 g of 0.1% aqueous solution of oxalic acid were added, followed by stirring and standing. The upper layer separated into two layers was aliquoted and concentrated by rotary evaporation until it reached 5% of solid content, and the porous silica particle solution was obtained.

After adding 10 g of ethanol to 1 g of the porous silica particle solution obtained above and mixing, one drop was dropped on a carbon grid for transmission electron microscope, and then dried at room temperature for 24 hours, followed by a field emission electron microscope manufactured by Nippon Denshi Co., Ltd. The particle size of the porous silica particles was measured using JEM-2010F, and the average particle diameter was 20 nm.

10 g of the porous silica particle solution was taken in an aluminum dish, and dried on a hot plate at 150 ° C. for 1 hour to obtain a powder sample of the porous silica particle 1. The BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 manufactured by Quantachrome Instruments, and the specific surface area was 200 m ² / g.

Preparation Example 13 Preparation of Composition 2 for Forming Low Refractive Index Layer

12.5 g of ethylenically unsaturated group containing fluoropolymer (D-1) obtained by manufacture example 9 (2.5 g as ethylenically unsaturated group containing fluoropolymer), ethylenically unsaturated group containing fluoropolymer (D-2) obtained by manufacture example 10 12.5 g (2.5 g as ethylenically unsaturated group-containing fluoropolymer), 1000 g (5.0 g as porous silica particles) of the porous silica particle dispersion obtained in Production Example 12, 2-methyl-1- [4- (methyl as a photoinitiator 0.4 g of thio) phenyl] -2-morpholinopropane-1-one and 134.6 g of MIBK were put into the glass separation flask with a stirrer, and it stirred at 23 degreeC for 1 hour, and obtained the composition 2 for low refractive index layer formation. Solid content was calculated | required similarly to the manufacture example 1, and it was 4 weight%.

Example 1

Preparation of Anti-Reflective Laminates (1)

The composition 1 for antistatic layer formation obtained in the manufacture example 1 was coated on the ATON film G7810 (Norbornene resin film, JSR Corporation make, film thickness 188 micrometers) using the wire bar coater # 12, It dried in 80 degreeC and the conditions of 3 minutes in oven. Subsequently, in air | atmosphere, the coating film was ultraviolet-hardened on 1 J / cm <^2> light irradiation conditions using the metal halide lamp, and the film which has a hard-coat layer was manufactured. It was 3 micrometers when the film thickness of the hard coat layer was measured by the stylus type surface shape measuring instrument. On the film with a hard coat, the composition 1 for low refractive index layer formation obtained by the manufacture example 11 was coated using wire bar coater # 3, and it dried in 80 degreeC and the conditions for 1 minute in oven. Subsequently, under nitrogen atmosphere, the coating film was ultraviolet-cured by the light irradiation conditions of 1 J / cm <^2> using a metal halide lamp, the low refractive index layer was formed, and the antireflective laminated body 1 was manufactured. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer from the reflectance of the obtained antireflective laminated body (1).

Example 2

Preparation of Anti-Reflective Laminates (2)

In the same manner as in Example 1, except that the low refractive index layer-forming composition 2 obtained in Production Example 13 was used instead of the low refractive index layer-forming composition 1, an antireflective laminate 2 was prepared. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 1.

Example 3

Preparation of Anti-Reflective Laminates 3

The composition for the silica particle-containing hard coat layer obtained in Production Example 5 was coated on Aton Film G7810 (Norbornene resin film manufactured by JSR Co., Ltd., film thickness of 188 µm) using a wire bar coater # 6, and then opened in It dried at 80 degreeC by the conditions of 3 minutes. Subsequently, in air | atmosphere, the coating film was ultraviolet-hardened on 1 J / cm <^2> light irradiation conditions using the metal halide lamp, and the film which has a hard-coat layer was manufactured. It was 3 micrometers when the film thickness of the hard coat layer was measured by the stylus type surface shape measuring instrument. On this film with a hard coat, the composition 1 for antistatic layer formation obtained in the manufacture example 1 was diluted to 5% of solid content concentration with propylene glycol monomethyl ether, and it coats using wire bar coater # 6, and is 80 degreeC in oven. And dried for 1 minute. Subsequently, under nitrogen atmosphere, the coating film was ultraviolet-cured by the light irradiation conditions of 1 J / cm <^2> using a metal halide lamp, and the high refractive index layer was formed. It was 0.1 micrometer as a result of calculating the film thickness of the high refractive index layer similarly to Example 1. The composition 1 for low refractive index layer formation obtained by the manufacture example 11 was coated on the obtained laminated body using the wire bar coater # 3, and it dried in 80 degreeC and the conditions for 1 minute in oven. Subsequently, under nitrogen atmosphere, the coating film was ultraviolet-cured by the light irradiation conditions of 1 J / cm <^2> using a metal halide lamp, the low refractive index layer was formed, and the antireflective laminated body 3 was manufactured. It was 0.1 micrometer when the film thickness of the low refractive index layer was computed from the reflectance of the obtained antireflective laminated body (3).

Comparative Example 1

Preparation of Anti-Reflective Laminates 4

An antireflective laminate 4 was prepared in the same manner as in Example 1, except that the composition 2 for antistatic layer formation obtained in Production Example 2 was used instead of the composition 1 for antistatic layer formation. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 1.

Comparative Example 2

Preparation of Anti-Reflective Laminates 5

The antireflective laminate (5) was prepared in the same manner as in Example 1 except that the composition for silica particle-containing hard coating layer obtained in Preparation Example 5 was used instead of the composition 1 for antistatic layer formation, and was applied using wire bar coater # 6. ) Was prepared. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 1.

Comparative Example 3

Preparation of Anti-Reflective Layer 6

The antireflective laminate (6) was prepared in the same manner as in Example 2 except that the composition for the silica particle-containing hard coating layer obtained in Preparation Example 5 was used instead of the composition 1 for antistatic layer formation and was applied using wire bar coater # 6. ) Was prepared. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 1.

Evaluation example

The following characteristics were evaluated about the antireflective laminated bodies (1)-(6) obtained in Examples 1-3 and Comparative Examples 1-3.

(a) Total light transmittance and haze

The total light transmittance (%) and haze (%) of the cured film were measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Shikeki Co., Ltd.). The results obtained are shown in Table 1 below.

(b) pencil hardness

The cured film was placed on a glass substrate, and the pencil hardness was evaluated based on JIS K5600-5-4. The obtained results are shown in Table 1.

(c) surface resistance

The surface resistance (Ω / □) of the cured film was measured under conditions of an applied voltage of 100 V using a high resistance meter (Agilent 4339B manufactured by Agilent Technologies, Inc.) and a resistance cell 16008B (manufactured by Agilent Technologies, Inc.). It was. The obtained results are shown in Table 1.

(d) reflectance

The reflectance of the obtained antireflective laminated body was made into the wavelength 340-700 by the spectral reflectance measuring apparatus (magnetic spectrophotometer U-3410 which manufactured the large sample chamber integrating apparatus attached to 150-09090, manufactured by Hitachi Seisakusho Co., Ltd.). The reflectance was measured and evaluated in the nm range. Specifically, the reflectance of the antireflective laminate (antireflection film) at each wavelength was measured with the reflectance in the aluminum vapor deposition film as a reference (100%). The reflectance at wavelength 550 nm is shown in Table 1.

(e) Scratch Resistance Test 1 (Steel Wool Resistance)

The steel wool resistance test of the antireflective laminate was conducted by the following method. That is, a steel wool (Bonstar No.0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Hakjin type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film has a load of 500 g. Ten times was repeated under conditions, and the presence or absence of the flaw generation on the surface of the said cured film was visually confirmed on the following references | standards.

○: Almost no peeling or scratching of the cured film was observed.

(Triangle | delta): Fine scratches are seen in a cured film.

X: Peeling generate | occur | produces in a part of cured film, or a stripe-shaped flaw generate | occur | produces on the surface of a cured film.

The obtained results are shown in Table 1.

(f) Scratch Resistance Test 2 (cloth friction resistance)

The cloth frictional resistance test of the antireflective laminate was carried out by the method shown below. That is, a nonwoven fabric (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a school-type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is repeated 20 times under a load of 1000 g. As a result, the presence or absence of scratches on the surface of the cured film was visually confirmed based on the following criteria.

○: Almost no peeling or scratching of the cured film was observed.

(Triangle | delta): Fine scratches are seen in a cured film.

X: Peeling generate | occur | produces in a part of cured film, or a stripe-shaped flaw generate | occur | produces on the surface of a cured film.

 The obtained results are shown in Table 1.

(g) Chemical resistance test (ethanol resistance test)

The ethanol tolerance test of the cured film was implemented by the method shown next. That is, a nonwoven fabric (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) infiltrated with ethanol was attached to a school-type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was subjected to a load of 500 g. After 20 times of repeated abrasions, the presence or absence of the occurrence of scratches on the surface of the cured film was visually confirmed by the following criteria.

○: Almost no peeling or scratching of the cured film was observed.

(Triangle | delta): Fine scratches are seen in a cured film.

X: Peeling generate | occur | produces in a part of cured film, or a stripe-shaped flaw generate | occur | produces on the surface of a cured film.

The obtained results are shown in Table 1.

From the result of Table 1, (C) formed from the liquid curable composition (composition for antistatic layer formation) containing the photoinitiator whose molar extinction coefficient in 313 nm (5,000 L / mol * cm or less) which comprises the laminated body of this invention is formed. It can be seen that an antireflective laminate having an antistatic layer has a low surface resistance and excellent antistatic performance.

In contrast, in Comparative Example 1 using the composition 2 for forming an antistatic layer containing a photopolymerization initiator other than the component (C), in spite of containing a large amount of phosphorus-containing tin oxide particles, Comparative Example 2, which did not provide an antistatic layer, It can be seen that the surface resistance is the same level as 3.

According to the present invention, it is possible to provide an antistatic laminate having excellent curability and a cured film having excellent antistatic property, hardness, scratch resistance, and transparency on the surface of various substrates.

The laminate of the present invention mainly contains a surface of a product such as a surface protective film of a high-tension container such as a protective film for a touch panel, a transfer foil, a hard coating for an optical disk, a window film for an automobile, an antistatic protective film for a lens, and a cosmetic container. As a hard coating provided for the purpose of preventing scratches and preventing dust from adhering to static electricity, and as an anti-reflection film having an antistatic function for various display panels such as a CRT, a liquid crystal display panel, a plasma display panel, and an electroluminescent display panel. And an antireflection film having an antistatic function such as a plastic lens, a polarizing film, and a solar cell panel.

The laminate of the present invention is hard for preventing scratches or stains of plastic optical components, touch panels, film-like liquid crystal elements, plastic housings, plastic containers, floorings as building interior materials, wall materials, artificial marble and the like, for example. Coating material; Adhesives and sealants of various substrates; It can use suitably as a binder material of printing ink, etc.

Claims (10)

It is a laminated body which has a base material, an antistatic layer, and a low refractive index layer in this order, The antistatic layer is (A) phosphorus-containing tin oxide particles, (B) a compound having two or more polymerizable unsaturated groups in a molecule, and (C) The photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less. It is a cured film layer which hardens the liquid curable composition containing, The low refractive index layer (D) an ethylenically unsaturated group-containing fluorine-containing polymer containing 40% by mass or more of fluorine, and (E) Particles based on silica The laminated body which is a cured film layer formed by hardening | curing the liquid curable resin composition containing. The laminated body of Claim 1 whose thickness of the said antistatic layer is 0.05-30 micrometers. The ethylenically unsaturated group-containing fluorine-containing polymer (D) according to claim 1 or 2, which contains 40% by mass or more of the fluorine. Hydroxyl group-containing fluorine-containing polymer, and Compound containing functional group and ethylenically unsaturated group which can react with hydroxyl group It is obtained by making it react, The laminated body characterized by the above-mentioned. The 20-70 mol% of following structural units (a) of Claim 3, when the said hydroxyl-containing fluoropolymer made the sum total of the following structural units (a), (b), and (c) 100 mol%, ( b) 1 to 70 mol%, and (c) 5 to 70 mol%, A polystyrene reduced number average molecular weight of 5,000 to 500,000, as measured by gel permeation chromatography. (a) The structural unit represented by following formula (1) (b) a structural unit represented by the following formula (2) (c) a structural unit represented by the following formula (3) <Formula 1>

[In Formula 1, R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ² (R ² represents an alkyl group or a fluoroalkyl group.) <Formula 2>

In Formula 2, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group,-(CH ₂ ) _x -OR ^5, or a group represented by -OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group] <Formula 3>

In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a group represented by-(CH ₂ ) _v -OR ²⁷ or -OCOR ²⁷ (R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group. And v represents a number from 0 to 2). The following structural unit according to claim 3 or 4, wherein the hydroxyl group-containing fluorine-containing polymer is further derived from an azo group-containing polysiloxane compound based on 100 mol parts in total of the structural units (a), (b) and (c). The laminated body containing 0.1-10 mole part of (d). (d) a structural unit represented by the following formula (4) <Formula 4>

[In Formula 4, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.] The hydroxyl group-containing fluorine-containing polymer according to any one of claims 3 to 5, wherein the hydroxyl group-containing fluorine-containing polymer is based on 100 mole parts of the total of the structural units (a), (b) and (c). A laminate comprising 0.1 to 5 mole parts). (f) The structural unit represented by following formula (5) <Formula 5>

In formula (5), R ¹⁰ represents a group having an emulsifying action. The laminate according to any one of claims 3 to 6, wherein the functional group capable of reacting with the hydroxyl group is selected from the group consisting of isocyanate groups, carboxyl groups, acid halides and acid anhydride groups. The laminate according to any one of claims 1 to 7, wherein a refractive index of the antistatic layer is higher than that of the low refractive index layer. The laminate according to any one of claims 1 to 8, wherein a hard coat layer is further formed on the substrate. The antireflection film containing the laminated body in any one of Claims 1-9.

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