WO2006132180A1

WO2006132180A1 - Antireflective laminate

Info

Publication number: WO2006132180A1
Application number: PCT/JP2006/311223
Authority: WO
Inventors: Hiroomi Shimomura; Shingo Itai; Ryosuke Iinuma; Tetsuya Yamamura; Hitoshi Kato; Eiichiro Urushihara; Kensuke Miyao; Takahiko Kurosawa
Original assignee: Jsr Corporation
Priority date: 2005-06-09
Filing date: 2006-06-05
Publication date: 2006-12-14
Also published as: KR20080012347A; TW200711847A; KR100917961B1; JPWO2006132180A1; JP5092744B2

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

Specification

Anti-reflection laminate

Technical field

[0001] The present invention relates to an antistatic laminate. More specifically, it has excellent curability and is made of various base materials such as plastic (polycarbonate, polymethylmetatalylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cell mouthwater resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, ceramic, slate, etc., surface coating with excellent antistatic properties, hardness, scratch resistance and transparency ( The present invention relates to an antistatic laminate comprising a cured film layer obtained by curing a liquid curable composition capable of forming a coating film.

Background art

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a radiation-curable composition has been used on the surface of the equipment to provide a scratch-resistant and adhesive coating (hard coat) and an antistatic function. Forming a coating film (antistatic film) having

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

In recent years, the development and general use of information communication equipment has been remarkable, and further improvements in performance and productivity of hard coats, antistatic films, antireflection films and the like have been demanded.

[0003] In particular, optical articles such as plastic lenses are required to prevent dust from being attached due to static electricity, and to improve the reduction in transmittance due to reflection. Therefore, prevention of dust adhesion due to static electricity and prevention of reflection on the screen has been demanded.

In response to these demands, a variety of radiation curable materials have been proposed, focusing on the fact that they can be cured at room temperature with high productivity.

[0004] As such a technique, for example, a composition containing a sulfonic acid and a phosphoric acid monomer as an ion conductive component (Patent Document 1), a composition containing a chain metal powder (Patent Document 1) Reference 2), tin oxide particles, polyfunctional acrylate, and a composition mainly composed of a copolymer of methyl methacrylate and polyether acrylate (Patent Document 3), a conductive material containing a pigment coated with a conductive polymer. Optical disk material (Patent Document 5), Silane coupler containing coating composition (Patent Document 4), trifunctional acrylic ester, monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator, and conductive powder Conductive paint containing hydrolyzate of antimony-doped tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent dispersed in (Patent Document 6), and polymerizable unsaturated group in the molecule Liquid curable resin composition containing a reaction product of an alkoxysilane and metal oxide particles, a trifunctional acrylic compound, and a radiation polymerization initiator (Patent Document 7), primary particles A conductive oxide fine powder having a diameter of ΙΟΟηm or less, an easily dispersible low boiling solvent of the conductive oxide fine powder, a hardly dispersible low boiling solvent of the conductive oxide fine powder, and a binder resin Examples thereof include a coating material for forming a transparent conductive film (Patent Document 8).

[0005] Further, in various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays, etc., in order to prevent reflection of external light and improve image quality, low refractive index, scratch resistance, coating, Therefore, there is a demand for an antireflection film including a low refractive index layer made of a cured product having excellent property and stain resistance.

These display panels are required to have scratch resistance that is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like. There is also a demand for contamination resistance that can easily wipe off attached fingerprints and dust.

In particular, in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate. In addition, as the base material, for example, triacetyl cellulose is used, but in the antireflection film using such a base material, in order to increase the adhesion when bonded to the polarizing plate, In general, it is necessary to carry out the quenching with an aqueous alkaline solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.

[0006] As a material for a low refractive index layer of an antireflection film, for example, a fluorine-based resin coating containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents 9 to 11).

However, in such a fluorine-based resin composition, a hydroxyl group-containing coating is used to cure the coating film. It is necessary to heat and crosslink the fluoropolymer and a curing agent such as melamine resin under an acid catalyst. Depending on the heating conditions, the curing time becomes excessively long, and the types of substrates that can be used are limited. There was a problem of being.

Also, the obtained coating film had excellent weather resistance, but was poor in scratch resistance and durability!

[0007] Therefore, in order to solve the above problems, 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 weight There has been proposed a coating composition containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting a polymer with an isocyanate group at a ratio of the number of isocyanate groups to the number of Z hydroxyl groups of 0.01 to 1.0. (For example, Patent Document 12).

[0008] However, in the above publication, when preparing an unsaturated group-containing fluorine-containing polymer, a sufficient amount of isocyanate group-containing monomer is allowed to react with all hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer. Without using a saturated compound, an unreacted hydroxyl group was actively left in the polymer.

For this reason, a coating composition containing such a polymer can be cured at a low temperature in a short time, but a curing agent such as melamine resin is further used to react the remaining hydroxyl groups. Needed to be cured. Furthermore, the coating film obtained in the above publication has a problem that it is sufficient in terms of coatability and scratch resistance.

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

Patent Document 2: JP-A-55-78070

Patent Document 3: JP-A-60-60166

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

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

Patent Document 6: JP-A-6-2644009

Patent Document 7: Japanese Unexamined Patent Publication No. 2000-143924

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

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

Patent Document 10: Japanese Patent Application Laid-Open No. 59-189108 Patent Document 11: Japanese Patent Laid-Open No. 60-67518

Patent Document 12: JP-A 61-296073

[0010] However, although these conventional techniques each exhibit a certain effect, they have fully provided all functions as a hard coat, an antistatic film, and an antireflection film in recent years. As a cured film that is required to be prepared, it was not always satisfactory.

[0011] For example, the conventional techniques as described in the above prior art documents have the following problems. The composition described in Patent Document 1 uses an ion conductive material, but its performance fluctuates due to drying when the antistatic performance is not sufficient. Since the composition described in Patent Document 2 disperses a chain-like metal powder having a large particle size, transparency is lowered. Since the composition described in Patent Document 3 contains a large amount of a non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 5 contains high-concentration chargeable inorganic particles, transparency is lowered. The paint described in Patent Document 6 has insufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic performance. When a transparent conductive film is formed by applying and drying the paint described in Patent Document 8, the organic matrix having a binder compounding power is not provided with a cross-linked structure, so that the organic solvent resistance is not sufficient.

[0012] Increasing the blending amount of the conductive particles in order to enhance the antistatic performance can be easily conceived, but in that case, the transparency is lowered due to the increase in the absorption of visible light by the cured film, and the UV transmittance is increased. As a result of this decrease, the problem that the curability decreased, the adhesion to the base material, and the repelling property of the coating solution could not be avoided. On the other hand, if the amount of the conductive particles is reduced, sufficient antistatic performance is not exhibited.

Disclosure of the invention

[0013] The present invention has been made in view of the above-mentioned problems, can exhibit sufficient antistatic performance, has excellent curability, and has antistatic properties, hardness, And an antistatic laminate having a cured film layer obtained by curing a liquid curable composition capable of forming a coating film (coating) having excellent scratch resistance and having both transparency and surface resistance, particularly charging. An object of the present invention is to provide an antireflection film laminate having an anti-reflection function. It is another object of the present invention to provide an antireflection laminate having excellent scratch resistance and stain resistance.

[0014] As a result of earnest research to solve the above-mentioned problems, the present inventor has found that conductive particles having a specific primary particle size, compounds having a specific polymerizable unsaturated group, and light having a specific light absorption characteristic. A laminate having a cured film layer obtained by curing a composition containing a polymerization initiator and a solvent can solve the above-mentioned problems related to antistatic performance and at the same time improve the scratch resistance and chemical resistance. In addition, excellent antireflection is achieved by combining a specific refractive index film obtained by curing a curable resin composition containing ethylenically unsaturated group-containing fluoropolymer and silica-based particles. The inventors have found that the properties are obtained and the scratch resistance and stain resistance of the antireflection laminate are improved, and the present invention has been completed.

That is, the present invention provides the following laminate and antireflection film.

[1] A laminate having a substrate, an antistatic layer and a low refractive index layer in this order, wherein the antistatic layer comprises the following components (A) to (C):

(A) Phosphorus-containing tin oxide particles

(B) Compound having two or more polymerizable unsaturated groups in the molecule

(C) a cured film layer obtained by curing a liquid curable composition containing a photopolymerization initiator having a molar extinction coefficient at 313 nm of 5, OOOLZmol'cm or less, and

The low refractive index layer comprises the following components (D) and (E):

(D) An ethylenically unsaturated group-containing fluoropolymer containing 40% by mass or more of fluorine

(E) Particles mainly composed of silica

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

[2] The laminate according to [1], wherein the antistatic layer has a thickness of 0.05 to 30 111.

[3] An ethylenically unsaturated group-containing fluoropolymer (D) containing 40% by mass or more of the fluorine,

A hydroxyl group-containing fluoropolymer,

The laminate according to the above [1] or [2], wherein the laminate is obtained by reacting a compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group.

[4] The hydroxyl group-containing fluoropolymer has a total of the following structural units (a), (b) and (c): When the 00 Monore ^_0/0, (&) 20-70 Monore%, (1)) 1-70 Monore% and _((:) comprises 5 to 70 Monore%, and,

The laminate according to [3] above, wherein the polystyrene-reduced number average molecular weight measured by gel permeation chromatography is 5,000 to 500,000.

(a) Structural unit represented by the following formula (1)

(b) Structural unit represented by the following formula (2)

(c) Structural unit represented by the following formula (3)

[Chemical 1]

FR ¹

-C— — C—— (1)

1 I

I I

F F

[In the formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OIT (R ² represents an alkyl group or a fluoroalkyl group)]

[Chemical 2]

[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, — (CH 2) —OR ^{5 or}

2

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 alkoxycarbo group]

[Chemical 3]

[In the formula (3), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is — (CH 2) —OR ²⁷ or —OCOR ′

2

(R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group, and V represents 0-2. Show the number of)]

[5] The following structure derived from the azo group-containing polysiloxane compound with respect to a total of 100 mol parts of the hydroxyl group-containing fluoropolymer (a), (b) and (c) The laminate according to [3] or [4] above, wherein the unit (d) contains 0.1 to 10 mol parts.

(d) Structural unit represented by the following general formula (4)

[Chemical 4]

R ⁸

—— Si—— 0—— (4)

R ⁹

[In the general formula (4), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

[6] Furthermore, the hydroxyl group-containing fluoropolymer contains 0.1 to 5 mole parts of the following structural unit (f) with respect to 100 mole parts in total of the (a), (b) and (c). A laminate according to any one of the above [3] to [5].

(f) A structural unit represented by the following general formula (5).

[Chemical 5]

[In the general formula ( ⁵ ), R ^1Q represents a group having an emulsifying action]

[7] The above-mentioned [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. Laminated body.

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

[9] Further, any of the above [1] to [8], wherein a hard coat layer is formed on the substrate The laminated body of description.

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

[0016] According to the present invention, a liquid curing that can form a coating film (film) having excellent curability and excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. It is possible to provide an antistatic laminate having a cured film obtained by curing an adhesive composition.

Conventionally, in order to obtain sufficient conductivity, it has been necessary to blend conductive particles at a high content. However, according to the present invention, sufficient conductivity can be exhibited even when the content of conductive particles is low. Thus, an antistatic laminate having a cured film excellent in antistatic performance can be obtained.

Further, according to the present invention, even if the content of the conductive particles is kept low, the transparency of the cured film and a sufficient surface resistance value can be achieved, and an optical component having an antistatic function, in particular, charging It is useful as an antireflection film having a prevention function.

Furthermore, by having a low refractive index layer having a specific configuration, an antireflection laminate excellent in scratch resistance and stain resistance can be obtained.

Brief Description of Drawings

FIG. 1 is a schematic diagram showing the most basic configuration (first embodiment) of a laminate of the present invention.

FIG. 2A is a schematic view showing a first form of an antireflection film with an antistatic function of the present invention.

FIG. 2B is a schematic diagram showing another form of the first form of the antireflection film with an antistatic function of the present invention.

FIG. 3 is a schematic view showing a basic configuration of a second embodiment of the antireflection film with an antistatic function of the present invention.

FIG. 4A] A schematic view showing another form of the second form of the antireflection film with an antistatic function of the present invention.

FIG. 4B] A schematic view showing another form of the second form of the antireflection film with an antistatic function of the present invention.

FIG. 5 is a schematic diagram showing a basic configuration of a third embodiment of the antireflection film with an antistatic function of the present invention.

FIG. 6A is a schematic diagram showing another form of the third form of the antireflection film with an antistatic function of the present invention. FIG.

FIG. 6B is a schematic view showing another form of the third form of the antireflection film with an antistatic function of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be specifically described.

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

The antistatic layer is characterized by having a cured film strength obtained by curing a liquid curable composition containing the following components (A) to (C).

[Liquid curable composition (hereinafter referred to as “antistatic layer-forming composition”)]

(A) Phosphorus-containing tin oxide particles

(C) A photopolymerization initiator having a molar extinction coefficient at 313 nm of 5, OOOLZmol'cm or less. [0019] Further, the low refractive index layer hardens a curable resin composition containing the following components (D) and (E): It is characterized by comprising a cured product.

[Liquid curable resin composition (hereinafter sometimes referred to as “low refractive index layer forming composition”)]

(E) Particles mainly composed of silica

[0020] I. Laminate

The most basic structure of the laminate of the present invention is shown in FIG. The laminate 1 of the present invention comprises a base material 10, an antistatic layer 12 obtained by curing the antistatic layer forming composition, and a low refractive index layer 18 obtained by curing the low refractive index layer forming composition. Have.

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 coat, and the laminate 1 of the present invention is antireflective. When used as a film, it is also useful as a high refractive index layer that exhibits high refractive index properties.

In addition, the laminate 1 of the present invention has an antistatic product by providing an antistatic layer 12 that imparts excellent conductivity on a substrate of various shapes such as a film, a plate, or a lens. Useful as a layered body. As an application example of the laminate of the present invention, for example, an antireflection film having an antistatic function for various display panels such as a CRT, a liquid crystal display panel, a plasma display panel, an electret luminescence display panel (hereinafter referred to as “antireflection film”) Use as an antireflection film with an antistatic function, such as a plastic lens, a polarizing film, and a solar battery panel.

Next, a configuration example of each layer when the laminate of the present invention is used as an antireflection film having an antistatic function will be described with reference to the drawings.

When providing an optical article with an antireflection function, a method of forming a low refractive index layer or a multilayer structure of a low refractive index layer and a high refractive index layer is formed on a base material or a hard-coated base material. It is known that the method to do is effective.

The most basic configuration (first embodiment) when the laminate of the present invention is used as an antireflection film with an antistatic function is as shown in FIG. The antireflection film 2 with an antistatic function is formed on the base material 10 by forming the antistatic layer 12 which is a cured film layer obtained by curing the antistatic layer forming composition, and further forming the low refractive index thereon. The low refractive index layer 18 which is a cured film layer formed by curing the composition for forming the refractive index layer is formed. In the first embodiment, the antistatic layer 12 has an antistatic function, a function as a hard coat layer, and a function as a high refractive index layer. In the most basic form, the refractive index of the antistatic layer 12 needs to be higher than the refractive index of the low refractive index layer 18.

As another form, the antistatic layer 12 of the antireflection film 2 of the present invention can also function as a hard coat layer, but a hard coat layer can be provided separately. In this case, the hard coat layer 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 coat layer 11 is provided between the antistatic layer 12 and the low refractive index layer 18, the refractive index of the hard coat layer 11 must be higher than the refractive index of the low refractive index layer 18. These embodiments are shown in FIGS. 2A and 2B.

FIG. 3 shows a second embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function. In the second embodiment, the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a substrate 10, and further thereon. The high refractive index layer 16 and the low refractive index layer 18 are formed in this order. Second In an embodiment, the antistatic layer 12 may have both an antistatic function, a function as a coating, and a function as a medium refractive index layer. In the second embodiment, in order for the antistatic layer 12 to function as a middle refractive index layer, the low refractive index layer 18 in which the refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16. It is necessary that the refractive index be higher.

[0025] In the second embodiment, as in the first embodiment, a configuration in which a hard coat layer is separately provided is also possible. The hard coat layer 11 can be provided either between the base material 10 and the antistatic layer 12 or between the antistatic layer 12 and the high refractive index layer 16. These forms are shown in FIGS. 4A and 4B.

FIG. 5 shows a third embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function. In the third embodiment, the antireflection film 2 with an antistatic function is formed on the base material 10 by forming the antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition, and further thereon. Further, a middle refractive index layer 14, a high refractive index layer 16 and a low refractive index layer 18 are formed in this order. In the third embodiment, the antistatic layer 12 has both an antistatic function and a hard coat function.

[0027] In the third embodiment, a hard coat layer can be separately provided as in the first embodiment. The hard coat layer 11 can be provided either between 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.

[0028] The first force of the antireflection film is also provided in the third embodiment. The antistatic layer and the low refractive index layer, each of which is essential for the laminate of the present invention and is obtained by curing a specific liquid curable composition, respectively. Each layer and base material provided as needed will be described.

The antistatic layer and the low refractive index layer in the following (1) and (2) are descriptions as layers that are optionally provided in addition to the antistatic layer and the low refractive index layer essential in the laminate of the present invention, The antistatic layer and the low refractive index layer essential in the laminate of the present invention will be described later.

[0029] (1) Antistatic layer

The antistatic layer imparts electrical conductivity to the laminate and prevents dust from adhering due to static electricity.

In the laminate of the present invention, a curable composition containing components (A) to (C) described later is used. The antistatic layer is essential, and the antistatic layer described here is an optional layer separately provided in addition to the essential antistatic layer.

Specific examples of the antistatic layer include phosphorus-containing acid tin (PTO) particles used in the present invention, antimony-doped tin oxide (ATO) particles, tin-doped indium oxide (ITO) particles, A1 Conductive metal oxide particles such as doped ZnO particles, or a curable film to which organic or organic conductive compounds are added, and the metal oxide is deposited! Examples of soot include metal oxide films obtained by sputtering and films made of conductive organic polymer. Examples of conductive organic polymers include polyacetylene conductive polymers, polyarine conductive polymers, polythiophene conductive polymers, polypyrrole conductive polymers, and polyphenylene vinylene conductive polymers. Can be illustrated.

[0030] (2) Low refractive index layer

The low refractive index layer is a layer having a thickness of 0.05 to 0.20 m and a refractive index of 1.30 to L45. The refractive index in the present invention means a refractive index of 589 nm at 25 ° C.

The material used for the low refractive index layer is not particularly limited as long as the desired properties are obtained. For example, a curable composition containing an fluorinated polymer, an acrylic monomer, and a fluorinated acrylic monomer. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds. In order to increase the strength of the low refractive index layer, silica fine particles and the like can be blended.

In the laminate of the present invention, a low refractive index layer formed using a curable resin composition containing the component (D) and the component (E) described below is essential, and the low refractive index described here is used. The layer is an optional layer separately provided in addition to the essential low refractive index layer.

[0031] (3) High refractive index layer

The high refractive index layer has a thickness in the range of 0.05 to 0.20 m 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 such as metal oxide particles can be mixed.

[0032] Specific examples of metal oxide particles include antimony-containing tin oxide (ATO) particles and tin-containing particles. Indium oxide (ITO) particles, acid-zinc (ΖηΟ) particles, antimony-containing ZnO, A1-containing Ζηθ particles ZrO particles, TiO particles, silica-coated TiO particles, Al O / ZrO-coated TiO particles,

2 2 2 2 3 2 2

Examples include CeO particles. Preferably, antimony-containing tin oxide (ATO) particles

2

These are tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, A1-containing ZnO particles, and Al 2 O 3 / ZrO-coated TiO particles. These metal oxide particles are one kind alone or

2 3 2 2

It can be used in a combination of two or more.

Further, the high refractive index layer can have a function of a hard coat layer.

[0033] (4) Medium refractive index layer

When combining layers having three or more refractive indexes, a layer having a refractive index of 1.50 to: L 90 and having a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer is set to the medium refractive index. Represents a layer. The refractive index of the middle refractive index layer is preferably 1.50 to L80, more preferably 1.50 to L75. The thickness of the medium refractive index layer is in the range of 0.05 to 0.20 / z m.

In order to form the middle refractive index layer, high refractive index inorganic particles such as metal oxide particles can be combined.

[0034] Specific examples of 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 particles, TiO Particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles, CeO particles

2 2 2 2 3 2 2 2 etc. can be mentioned. Preferably, antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, A1-containing ZnO particles, ZrO particles

2 children. These metal oxide particles can be used singly or in combination of two or more.

[0035] The reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be reduced by combining the low refractive index layer, the high refractive index layer, and the medium refractive index layer. Can be reduced and the glare can be reduced.

[0036] (5) Hard coat layer

Specific examples of the hard coat layer include SiO, epoxy resin, acrylic resin, melamine

2

It is also preferable to construct a material strength such as system rosin. In addition, silica particles may be blended with these rosins. The hard coat layer has the effect of increasing the mechanical strength of the laminate. The thickness of the hard coat layer is

Usually, it is in the range of 0.5-50 μm, preferably 1-30 μm. 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.

[0037] (6) Substrate

The substrate used in the laminate of the present invention is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., but as a material that can exhibit industrial productivity and high productivity of radiation curability, For example, it is preferably applied to a film or a fiber-like substrate. Particularly preferred materials are plastic film and plastic plate. Such plastics include, for example, polycarbonate, polymethylol methacrylate, polystyrene Z polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, diethylene glycol diallyl carbonate (CR — 39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin). When the laminate of the present invention is used as an antireflection film, polycarbonate, polystyrene Z polymethyl methacrylate copolymer, triacetyl cellulose resin, and cyclized polyolefin resin can be mentioned, which has high transparency. Furthermore, cyclic olefin fins such as norbornene-based resins are preferred.

[0038] The thickness of the substrate is not particularly limited, but is usually in the range of 30 to 300 µm, preferably 50 to 200 µm.

[0039] (7) Other layers

In the production of the laminate of the present invention, other functions such as non-glare effect, selective light absorption effect, weather resistance, durability, transferability, etc. are further added, for example, light of 1 μm or more. It is possible to add a layer containing scattering particles, add a layer containing a dye, add a layer containing an ultraviolet absorber, add an adhesive layer, add an adhesive layer and a release layer, etc. In addition, these function-imparting components can be added as one component of the antistatic layer forming composition and Z or the low refractive index layer forming composition used in the present invention.

[0040] The laminate of the present invention is, for example, a plastic optical component, a touch panel, or a film-type liquid crystal. Hard coating materials to prevent scratches and scratches on elements, plastic casings, plastic containers, flooring materials as architectural interior materials, wall materials, artificial stones, etc .; adhesives for various substrates, One ring material; can be suitably used as a binder material for printing ink.

[0041] These layers may be formed in only one layer, or two or more different layers may be formed.

The film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm, the film thickness of the hard coat layer is usually 1 to 20 111, and the film thickness of the antistatic layer is usually 0.05 to 30 / ζ πι. It is.

In the present invention, the layer can be produced by a known method such as coating and curing, vapor deposition, or sputtering.

[0042] II. Antistatic layer

The antistatic layer provided on the substrate of the laminate of the present invention is obtained by curing the composition for forming an antistatic layer, and the laminate has a function as a conductive, high refractive index film and A function as a coat coat can be imparted.

Hereinafter, each component of the liquid curable composition will be specifically described.

[0043] 1. Ingredient (Α)

The phosphorus-containing tin oxide particles (component (成分)) used in the liquid curable composition are essential components for expressing the conductivity of the cured film of the liquid curable composition to be obtained.

[0044] Examples of commercially available powders of such phosphorous-containing acid tin particles include, for example, ELCOM TL-30S (PTO) manufactured by Catalyst Kasei Kogyo Co., Ltd.

[0045] The phosphorus-containing tin oxide particles used as the component (A) can be used in a state of being dispersed in a powder or a solvent. However, since uniform dispersibility is easily obtained, they are used in a state of being dispersed in a solvent. I like it! /

[0046] Examples of commercially available products in which acid oxide particles used as component (A) are dispersed in a solvent include, for example, product name: ELCOM JX-1001PTV (produced by propylene glycol monomethyl ether dispersion). PTO).

[0047] When the shape is spherical, the primary particle diameter of component (A) is 10 to: LOOnm, more preferably 10 to 50 nm. The primary particle size is measured with a transmission electron microscope. If it is less than lOnm, the conductivity is insufficient, and if it exceeds lOOnm, sedimentation occurs in the composition or the smoothness of the coating film decreases. If the shape is elongated like a needle, dry powder As the values obtained by observing the powder with an electron microscope and obtaining the number average particle diameter, it is preferable that the minor axis average particle diameter force is SlO to 50 nm and the major axis number average particle diameter is 100 to 2000 nm. If the long axis particle diameter exceeds 2000 nm, sedimentation may occur in the composition.

[0048] The blending amount of component (A) is not particularly limited, but is preferably 25 to 85% by weight, more preferably 30 to 70% by weight in the total amount of solids of 100% by weight. If the blending amount is less than 25% by weight, the antistatic property may be inferior, and if it exceeds 85% by weight, the hardness of the coating film may be inferior. Here, the blending amounts of components (A), (B), and (C) refer to blending amounts as solid components.

[0049] 2. Component (B)

Component (B) used in the liquid curable composition is a compound having two or more polymerizable unsaturated groups in the molecule from the viewpoint of film formability and transparency of the cured film of the liquid curable composition to be obtained. It is a thing. By using such component (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

[0050] Specific examples of component (B) include (meth) acrylic esters and vinyl compounds.

(Meth) acrylic esters include trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene phthalate (meta ) Atalylate, 1,3-Butanedioldi (meth) atarylate, 1,4-Butanedioldi (meth) atalylate, 1,6-Hexanedioldi (meth) atalylate, Neopentylglycoldi (meth) Atalylate, diethyleneda Cold (meth) acrylate, triethylene dalcol di (meth) acrylate, dipropylene dalcol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis ( (Meth) alkanol (also called “(meth) acrylate”), and poly (meth) acrylate of the starting alcohols in the production of these compounds with ethylene oxide or propylene oxide , Oligoesters having two or more (meth) attalyloyl groups in the molecule (meth) acrylate, oligo ether (meth) acrylate, oligo urethane (meth) acrylate, and oligoepoxy (meth) acrylate And the like.

[0051] Examples of vinyl compounds include dibutene benzene, ethylene glycol dibutyl ether, diethylene glycol divinino ether, triethylene glycol divinino etherate 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) acrylate, bis ( (Meth) ataryloxymethyl) tricyclo [5. 2. 1. 0 ² ' ⁶ ] decane is preferred.

These (B) components may be used alone or in combination of two or more.

[0052] The blending amount of component (B) is preferably 10 to 74% by weight, more preferably 20 to 65% by weight in a total amount of 100% by weight of the solid content. If the blending amount of component (B) is less than 10% by weight, the hardness of the resulting cured product may be inferior. If it exceeds 74% by weight, the antistatic property may be inferior.

[0053] 3. Component (C)

Component (C) is a photopolymerization initiator having a molar extinction coefficient at 313 nm of 5, OOOLZmol'cm or less. Here, the molar extinction coefficient at 313 nm of the photopolymerization initiator means the ratio of the absorbance and molar concentration of the solution at 313 nm to the lcm absorption layer. By using a photopolymerization initiator having such light absorption characteristics, the surface resistance of the cured film can be sufficiently reduced. When a photopolymerization initiator having a molar extinction coefficient at 313 nm of more than 5, OOOLZmol'cm is used, sufficient antistatic performance cannot be obtained due to the high surface resistance of the resulting cured film.

[0054] The composition for forming an antistatic layer is cured only by irradiation with radiation, but the component (C) can further increase the curing rate in addition to the above functions.

In the present invention, radiation means visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, It means α ray, j8 ray, γ ray, etc.

[0055] Examples of the photopolymerization initiator that can be used as the component (C) include 1-hydroxycyclohexylphenyl ketone, 2, 4, 6 trimethylbenzoyldiphenylphosphine oxide, oligo (2 hydroxy- 1 2- Methyl-one-one (four-one (1-methylbeal) fuel) propanone

), 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1-2-methyl-1-phenolpropane 1-on, and the like.

[0056] The blending amount of component (C) is preferably 0.1 to 15 wt%, more preferably 0.5 to L0 wt% with respect to 100 wt% of the total solid content. Component (C) can be used singly or in combination of two or more.

[0057] 4. Solvent

The solvent used in the composition for forming an antistatic layer of the present invention is not particularly limited, but usually a solvent having a boiling point of 200 ° C. or less at normal pressure is preferred. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used alone or in combination of two or more. Specific examples include propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol and the like, and propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl. Ketones are preferred.

In the case of using a dispersion of phosphorus-containing acid-tin particles as the component (), the dispersion contains a solvent, but a solvent of this dispersion may be used, or a different solvent may be added. May be.

[0058] Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxhetano monoole, diethyleneglycololemonoethylenoatenore, benzenoreanoreconole, Examples include phenolic alcohol. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether and propylene glycol monoethyl ether acetate. Examples of the esters include ethyl acetate and petit acetate. , Ethyl lactate, methyl acetoacetate, ethyl acetoacetate and the like. Examples of hydrocarbons include toluene and xylene. Examples of amides include N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone and the like.

[0059] The amount of the solvent is not particularly limited, but is usually 50 to: LOOOO parts by weight, preferably 50 to 3000 parts by weight, with respect to 100 parts by weight of the total solid content.

[0060] 5. Other compounds having a polymerizable unsaturated group

The antistatic layer-forming composition may contain other compounds having a polymerizable unsaturated group (component (F)) as additives other than the above components (A) to (C) as necessary. it can . Here, the component (F) is a compound having one polymerizable unsaturated group in the molecule.

Specific examples of component (F) include N-vinylpyrrolidone, rat group-containing ratata such as N-bulu force prolactam, isobornyl (meth) acrylate, boryl (meth) acrylate, tricyclode force. -Mole (meth) acrylate, dicyclopental (meth) acrylate, dicyclopentale (meth) acrylate, cyclohexyl (meth) acrylate, etc. (meth) acrylate, benzyl ( (Meth) Atalylate, 4-Butylcyclohexyl (Meth) Atalylate, Ataliloylmorpholine, Bulimidazole, Bulpyridine, 2-Hydroxychetyl (Meth) Atalylate, 2-Hydroxypropyl (Meth) Atalylate, 2-Hydroxybutyl ( (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) Atalylate, isoamyl (meth) atarylate, hexyl (meth) atarylate, heptyl (meth) atarylate, octyl (meth) atalylate, isooctyl (meth) atalylate, 2-ethylhexyl (meth) atarylate, Nor (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Atalylate, isostearyl (meth) Atalylate, tetrahydrofurfuryl ( Data) Atari rate, Butokishechiru (meth) Atarire bets, ethoxy diethylene glycol (meth) Atari rate, benzyl (meth) Atari rate, Hue Nokishechiru (meth) Atari, polyethylene glycol mono (meth) Atari rate, polyps Lopylene glycol mono (meth) acrylate, methoxy ethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, iso Butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, 7-amino 3, 7-Dimethyloctyl (meth) atarylate, N, N- Jetyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Hydoxybutino levino reeenoate, Laurino levino rea Examples include tenole, cetinolevinoleetenole, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (10).

CH = C (R ¹⁵ ) -COO (R ¹⁶ 0) -Ph-R ¹⁷ (10)

2d

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

[0061] Commercially available components (F) include: ALONIX M-101, M-102, M-111, M-113, M-114, M-117 (above, manufactured by Toa Gosei Co., Ltd.); LA, STA, IBXA, 2 — MTA, # 192, # 193 (Osaka Organic Chemical Co., Ltd.); ¾: Esters AMP—10G, A MP—20G, AMP—60G (above, Shin-Nakamura Chemical Co., Ltd.); Light Atylate L—A, S—A, IB—XA, PO—A, PO—200A NP-4EA, NP-8EA (manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (manufactured by Hitachi Chemical Co., Ltd.).

[0062] 6. Additive

Antistatic layer forming compositions may contain other additives such as antioxidants, UV absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, and lubricants as necessary. Can be blended. Antioxidant agents are manufactured by Ciba Specialty Chemicals Co., Ltd. Trade name: Ilganox 1010, 1035, 1076, 1222, etc. Ultraviolet absorbers are manufactured by Ciba Specialty Chemicals Co., Ltd. Product names: Tinuvin P234, 320, 326 , 327, 328, 213, 329, manufactured by Siploy Kosei Co., Ltd. Product name: Seasorb 102, 103, 501, 202, 712, etc. As a light stabilizer, manufactured by Chino Specialty Chemicals Co., Ltd. Product name: Tinuvin 292, 1 44, 622LD, Sankyo Co., Ltd. trade name: Sanol LS770, LS440, Sumitomo Chemical Co., Ltd. trade name: Sumisorp TM-061.

[0063] The viscosity of the antistatic layer-forming composition thus obtained is usually 25 ° C.

1 to 20, OOOmPa, s, preferably 1 to 1, OOOmPa, s.

[0064] 7. Non-conductive particles

In the present invention, the non-conductive particles or the non-conductive particles and the alkoxysilane compound are reacted in an organic solvent within a range where the composition for forming an antistatic layer does not cause problems such as separation and gelling. You can also use the resulting particles together.

[0065] By using non-conductive particles in combination with phosphorus-containing tin oxide particles as component (A), the antistatic function, that is, the surface resistance when a cured film is set to a value of 1 X 10 ¹³ Ω or lower While maintaining the above, it is possible to improve the scratch resistance.

[0066] Such non-conductive particles are not particularly limited as long as they are particles other than the phosphorous-containing acid-tin particles as the component (IV). Preferred are acid oxide particles or metal particles other than the component (成分). Specifically, it is composed of oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, or silicon, aluminum, zirconium, titanium, and cerium. Group power Picks up oxide particles containing two or more selected elements.

[0067] The primary particle diameter of the nonconductive particles is preferably 0.1 m or less, more preferably 0.001 to 0.08 μm, as a value obtained by observation with a transmission electron microscope. . If it exceeds 0.1 μm, sedimentation may occur in the composition or the smoothness of the coating film may be reduced.

[0068] When blending the non-conductive particles in the composition for forming an antistatic layer, the non-conductive particles and the alkoxysilane compound may be hydrolyzed in an organic solvent and then mixed. This treatment improves the dispersion stability of the non-conductive particles.

[0069] Commercially available non-conductive particles include, for example, acid silica particles (eg, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA- ST, MEK—ST, NBA-ST, XBA—ST, DMAC—ST, ST—UP, ST—OUP ゝ ST—20, ST—40, ST—C, ST—N, ST—0, ST—50, ST—OL etc. I can make it. As powdered silica, Nippon Aerosil Co., Ltd. Product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil 0X50, Asahi Glass Co., Ltd.

H32, H51, H52, H121, H122, manufactured by Nippon Silica Kogyo Co., Ltd. Product name: E220A, E220, manufactured by Fuji Silysia Co., Ltd. Product name: SYL YSIA470, manufactured by Nippon Sheet Glass Co., Ltd. Product name: SG Flakes Etc. In addition, as the water dispersion of oxyaluminum (alumina), product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol 100, 1 200, 1 520; As the dispersion of zirconium oxide, Sumitomo Osaka Cement Co., Ltd. Product (toluene, methyl ethyl ketone-dispersed zircouazole); as cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. Product name: Nidral; Alumina, acid zirconium, acid titanium, Examples of such powders and solvent-dispersed products include trade name: Nanotec manufactured by CIA Kasei Co., Ltd.

[0070] 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 with respect to 100 parts by weight of the total amount of the component (A) and the component (B). is there.

[0071] 8. Method for preparing composition for forming antistatic layer

The antistatic layer-forming composition comprises (A) phosphorus-containing tin oxide particles, (B) a compound having two or more polymerizable unsaturated groups in the molecule, (C) a photopolymerization initiator, a solvent, and Accordingly, it can be prepared by adding (F) another compound having a polymerizable unsaturated group, an additive and non-conductive particles, and mixing them at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll.

[0072] 9. Method for forming antistatic layer

The antistatic layer of the laminate of the present invention can be obtained by applying the antistatic layer-forming composition described above to the substrate and drying it, and then irradiating it with radiation to cure the composition.

The surface resistance of the obtained antistatic layer is not more than 1 × 10 ¹³ Ω well, preferably not more than 1 × 10 ¹⁰ Ω / well, more preferably not more than IX 10 ⁸ Ω well. If the surface resistance exceeds 1 Χ 10 ¹³ Ω, the dust may not be easily removed or the dust may not be removed easily. [0073] The method for applying the composition for forming an antistatic layer is not particularly limited! /, But known methods such as roll coating, spray coating, flow coating, diving, screen printing, and ink jet printing are applied. be able to.

[0074] The radiation source used for curing the composition for forming an antistatic layer is not particularly limited as long as it can be cured in a short time after the composition is applied.

Examples of the visible ray source include direct sunlight, lamps, fluorescent lamps, and lasers. Examples of the ultraviolet ray source include mercury lamps, halide lamps, and lasers, and electron beam source. For example, a method using a thermoelectron generated from a commercially available tungsten filament, a cold cathode method in which a metal is generated through a high voltage pulse, and a collision between an ionized gaseous molecule and a metal electrode 2 Examples include secondary electron systems that use secondary electrons.

Examples of the source of α rays, j8 rays, and γ rays include fission materials such as ⁶ ° Co. For γ rays, vacuum tubes that collide accelerated electrons with the anode can be used. . These radiations may be irradiated alone or in combination of two or more kinds. Alternatively, one or more kinds of radiation may be irradiated for a certain period.

[0075] The film thickness of the antistatic layer is preferably 0.05 to 30 µm. For applications that place importance on scratch resistance on the outermost surface such as touch panels and CRTs, the thickness is relatively thick, preferably 2 to 15 / z m. On the other hand, when used as an antistatic film of an optical film, it is preferably 0.05 to: LO / z m.

Further, when used for an optical film, transparency is required, and the total light transmittance is preferably 85% or more.

[0076] 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 comprises (D) an ethylenically unsaturated group-containing fluoropolymer and (E) a composition for forming a low refractive index layer containing particles containing silica as a main component. Is a cured product.

Hereinafter, components (D) and (E) will be described.

[0077] 1. Component (D) (D) Ethylenically unsaturated group-containing fluoropolymer containing 40% by mass or more of fluorine The ethylenically unsaturated group-containing fluoropolymer used in the present invention comprises a hydroxyl group-containing fluoropolymer, a hydroxyl group It can be obtained by reacting a functional group capable of reacting with a compound containing an acetylenically unsaturated group. Here, the compound containing a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated group includes a compound containing one isocyanate group and at least one ethylenically unsaturated group, or an ethylenically unsaturated group. Examples thereof include saturated group-containing carboxylic acid compounds or derivatives thereof.

(1) Hydroxyl group-containing fluoropolymer

The hydroxyl group-containing fluorine-containing polymer has the following structural units (a), (b) and (c) as the sum of 100 mol%: (&) 20 to 70 mol%, (1) 1 to 70 mol % and (.) comprises 5 to 70 mol%, and gel permeation chromatography chromatography polystyrene reduced number average molecular weight force ^s 5 measured at, 000-500, Mashi it forces the child is 000! /ヽ.

(a) A structural unit represented by the following general formula (1).

(b) A structural unit represented by the following general formula (2).

(c) A structural unit represented by the following general formula (3).

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

[0079] [Chemical 6]

FR ¹ —— C—— C—— (1)

[In general 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)]

[0081] [Chemical 7]

[In general formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, (CH 3) OR ⁵

2 or a group represented by OCOR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group, X represents the number of 0 or 1), a carboxyl group, or an alkoxycarbo group]

[0083] [Chemical 8]

HR ⁶ —— C— C—— (3) HR ⁷

[In the general formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents — (CH 2) —OR ²⁷ or —OC

2

A group represented by OR ²⁷ (R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group, and V represents a number of 0 to 2)]

(1) Structural unit (a)

In the general formula (1), the fluoroalkyl groups of R ¹ and R ² are trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl. And a fluoroalkyl group having 1 to 6 carbon atoms such as a perfluorocyclohexyl group. Examples of the alkyl group for R ² include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.

[0085] The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing butyl 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 of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule. Perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc .; Perfluoro (alkoxyalkyl) such as propoxypropyl butyl ether (Bulether)) may be used singly or in combination of two or more.

Of these, hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferable.

[0086] The content of the structural unit (a) is preferably 20 to 70 mol% when the total of the structural units (a), (b) and (c) is 100 mol%. . This is because when the content is less than 20 mol%, the fluorine content of the fluoropolymer is low, and it is difficult to develop a low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention. On the other hand, if the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent, transparency, or adhesion to the substrate may be reduced. Because there is. For these reasons, the content of the structural unit (a) is more preferably from 30 to 65 mol%, and even more preferably from 40 to 60 mol%! /.

[0087] (2) Structural unit (b)

In the general formula (2), the alkyl group of R ⁴ or R ^{5 is} an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, or a lauryl group. Examples of the ITl alkoxycarbol group include a methoxycarbol group and an ethoxycarporo group, and examples of the fluoroalkyl group for R ⁵ include a trifluoromethyl group, a perfluoroethyl group, Perfluoropropyl, perfluorobutyl, perfluorohexyl, 2- (trifluoromethyl) ethyl, 2- (perfluoroethyl) ethyl, 2- (per Fluoropropyl) ethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluoropentyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluoroalkyl group) Octyl) ethyl group, 2- (perful Lono - Le) Echiru group, 2- (Pfaff Ruorodeshiru) Echiru group.

[0088] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such bur monomers include methyl vinyl ethere, ethino levinino le ethere, _n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert -Butyl vinyl etherenole, n-pentinolevinoreethenore, n-hexinorevininoreatenore, n-year-old cubinorebi-noreethenore, n-dodecinolevinorethenore, 2-ethinorehexinolevinorete Alkyl butyl ethers or cycloalkyl butyl ethers such as butyl butyl ether; aralkyl ethers such as ethyl allyl ether, butyl allyl ether; butyl acetate, butyl propionate, butyl butyrate, pivalate butyl, Carboxylic acid buesters such as bisprotonate, versatic bur, and stearate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate (Meth) acrylic acid esters such as acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate; (meth) acrylic Unsaturated carbohydrate such as acid, crotonic acid, maleic acid, fumaric acid, itaconic acid Acids; those with and following structural formulas are exemplified.

[Chemical 9]

HC: CR ²⁸

H, C = CR ^2e H ₂ C = C ^2e

0 (CH ₂ ) _v 0 (CH ₂ ) _w — C ₄ F ₉

H ₂ C = CR ²⁸ H ₂ C = CR ^2S

0 (CH ₂ ) Li C 5 ^r 11 0 (CH ₂ ) _w C ₆ F ₁₃

(Wherein R ²⁸ represents a hydrogen atom or a methyl group, and w represents a number of 0 to 2). These may be used alone or in combinations of two or more.

[0091] The content of the structural unit (b) is preferably 1 to 70 mol% when the total of the structural units (a), (b) and (c) is 100 mol%. . The reason for this is that when the content is less than 1 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be lowered. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.

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

[0092] (3) Structural unit (c)

In the general formula (3), the hydroxyalkyl group of R ^27, 2-hydroxy E butyl group, 2-hydroxypropyl, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydrate Rokishibuchiru group, 5-hydroxy Examples include pentyl group and 6-hydroxyhexyl group.

[0093] The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl. Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, etc., hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned.

In addition to the above, hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and force prolatatone ( (Meth) acrylate, polypropylene glycol (meth) atrelate, etc. can be used.

[0094] The content 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%. . This is because the content is 5 mol% This is because the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent may be reduced when the content is less than 70% by mole. On the other hand, if the content exceeds 70 mol%, the transparency of the hydroxyl group-containing fluoropolymer may be reduced. This is because optical characteristics such as low reflectivity may deteriorate.

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

[0095] (4) Structural unit (d) and structural unit (e)

The hydroxyl group-containing fluoropolymer comprises the following structural unit (d) derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a), (b) and (c). 0.1 to 10 mol parts are preferred.

(d) A structural unit represented by the following general formula (4).

[0096] [Chemical 10]

R ⁸

—— Si— 0—— (4) R ⁹

[In the general formula (4), R ⁸ and R ⁹ may be the same or different and may be a hydrogen atom or an alkyl group.

, Represents a halogenated alkyl group or an aryl group]

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

[0098] In addition, the ethylenically unsaturated group-containing fluoropolymer of the present invention has the above structural unit (d

) As part of the structural unit (e) below.

(e) A structural unit represented by the general formula (6).

[0099] [Chemical 11]

[In general formula (6), R ^{U to} R ¹⁴ represent a hydrogen atom, an alkyl group, or a cyan group, which may be the same or different, and R ^{15 to} R ¹⁸ are the same or different. A hydrogen atom or an alkyl group, a halogenated alkyl group, or an aryl group; p and q are numbers from 1 to 6, and s and t are 0 to 6 Y represents a number from 1 to 200. ]

[0101] Hereinafter, the structural units (d) and (e) will be described.

[0102] In general formula (4), the 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. As a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, etc. Examples thereof include a naphthyl group.

[0103] The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the general formula (4). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following general formula (7).

[0104] [Chemical 12]

[In the general formula (7), R ^{U to} R ", R ^{15 to} R ¹⁸ , p, q, s, t, and y are the same as in the general formula (6), and z is 1 to It is a number of 20.]

[0106] When the compound represented by the general formula (7) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e). In this case, in the general formula (7), as the alkyl group represented by R ^{U to} R ″, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group is exemplified. Examples of the alkyl group of R ^{15 to} R ¹⁸ include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

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

[0108] [Chemical 13]

[In the general formula (8), y and z are the same as those in the general formula (7). ]

[0110] The content of the structural unit (d) is preferably 0.1 to 10 mole parts with respect to 100 mole parts in total of the structural units (a), (b) and (c). . The reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing may be lowered, and the scratch resistance of the coated film may be lowered. If the amount exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.

For these reasons, the content of the structural unit (d) is more preferably 0.1 to 5 mol parts, and even more preferably 0.1 to 3 mol parts. For the same reason, it is desirable that the content of the structural unit (e) is determined so that the content of the structural unit (d) contained therein falls within the above range.

[0111] (5) Structural unit (f)

Further, the hydroxyl group-containing fluoropolymer preferably contains the following structural unit (f) 0.1 to 5 mol%.

(f) A structural unit represented by the following general formula (5).

[0112] [Chemical 14]

FR ¹⁰

——,

(— C—— (5)

F F

[0113] [In general formula (5), R ^1U represents a group having an emulsifying action]

[0114] By including the structural unit (f), coatability is improved.

[0115] Hereinafter, the structural unit (f) will be described.

In the general formula (5), the group having an emulsifying action of R ^1C> has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is polyethylene oxide, polypropylene oxide, etc. Preferred are groups that are polyether structures.

[0116] Examples of such a group having an emulsifying action include a group represented by the following general formula (9).

[0117] [Chemical 15]

[0118] [In general formula (9), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50.]

[0119] The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (10).

[0120] [Chemical 16]

[In general formula (10), n, m, and u are the same as in general formula (9) above]

[0122] The content of the structural unit (f) is preferably 0.1 to 5 mol parts with respect to 100 mol parts in total of the structural units (a), (b) and (c). . The reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol parts, the curable resin composition This is because the stickiness of the object does not increase excessively, it is easy to handle, and the moisture resistance does not decrease even when used as a coating material.

For these reasons, the content of the structural unit (f) is more preferably 0.1 to 3 mole parts with respect to the total amount of the hydroxyl group-containing fluoropolymer. A force of 3 mole parts S is more preferable.

[0123] (6) Molecular weight

Hydroxyl group-containing fluorine-containing polymers are obtained by gel permeation chromatography (hereinafter referred to as “GP C”) and measured by using tetrahydrofuran (hereinafter referred to as “Ding 1 ^”) as a solvent. The number average molecular weight in terms of ren is preferably 5,000 to 500,000. The reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be reduced. On the other hand, when the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the curable resin composition becomes high and thin film coating may be difficult.

For these reasons, the hydroxyl group-containing fluoropolymer has a polystyrene-reduced number average molecular weight of preferably 10,000 to 300,000, more preferably 10,000 to 100,000.

[0124] (2) Compound containing one isocyanate group and at least one ethylenically unsaturated group

As a compound containing one isocyanate group and at least one ethylenically unsaturated group, a compound containing one isocyanate group and at least one ethylenically unsaturated group in the molecule If so, it will not be particularly limited.

If two or more isocyanate groups are contained, gelling may occur when reacting with a hydroxyl group-containing fluoropolymer.

In addition, as the ethylenically unsaturated group, a curable rosin composition to be described later can be hardened more easily, and therefore a compound having a (meth) atallyloyl group is more preferable. Examples of such a compound include 2- (meth) atalylooxychetyl isocyanate and 2- (meth) atalylooxypropylisocyanate alone or in combination of two or more.

[0125] Such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.

In this case, examples of diisocyanates 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, 1-dimethyl-4,4'-diphenylmethane diisocyanate, 4, 4'-diphenyl- Dimethane diisocyanate, 3,3,1 dimethyl phenol-diisocyanate, 4,4, -biphenol-diisocyanate, 1,6 hexane diisocyanate, isophorone Isocyanate, methylenebis (4-cyclohexenoylisocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanateethyl) fumarate, 6-isopropyl-1, 3-phenol diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane , Tetramethylxylylene diisocyanate, 2,5 (or 2,6) -bis (isocyanatemethyl) -bicyclo [2.2.1] heptane, or a combination of two or more.

Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1, 3-bis (isocyanate) Nate methyl) cyclohexane is particularly preferred!

[0126] Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, force prolatatone (meth) acrylate, polypropylene glycol (meth) acrylate, dipentaerythritol penta ( Examples thereof include one or a combination of two or more of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, isocyanuric acid EO-modified di (meth) acrylate.

Of these, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are particularly preferred!

Examples of commercially available hydroxyl group-containing polyfunctional (meth) atalylate include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA, Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30, Toagosei ( Product name Alonics M-215, M-233, M-305, M-400, etc.

[0127] When synthesizing from a diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, the addition amount of the hydroxyl group-containing polyfunctional (meth) acrylate is 1 to 1.2 mol per 1 mol of diisocyanate. preferable.

[0128] As a method for synthesizing such a compound, a method in which diisocyanate and a hydroxyl group-containing (meth) acrylate are charged together and reacted, a method in which a diisocyanate is dropped and reacted in a hydroxyl group-containing (meth) acrylate Etc. (3) Ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof

Examples of the ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof include a compound having an ethylenically unsaturated group and a carboxylic acid in the molecule, or an acid halide, acid anhydride, etc. The compound is not particularly limited as long as it is a compound that forms an ester with a coalescence.

Further, as the ethylenically unsaturated group, a compound having a (meth) atallyloyl group is more preferable because the curable resin composition can be more easily cured.

Examples of such a compound include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid promide, and (meth) acrylic anhydride.

[0130] (4) Reaction molar ratio

The ethylenically unsaturated group-containing fluoropolymer of the present invention comprises the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer. It is preferable that the isocyanate group Z hydroxyl group is reacted at a molar ratio of 0.1 to 1.9. The reason for this is that if the molar ratio is less than 0.1, the scratch resistance and durability may be lowered. On the other hand, if the molar ratio exceeds 1.9, the coating film of the curable resin composition may be used. This is because the scratch resistance after immersion in an alkaline aqueous solution may be reduced. For this reason, the molar ratio of the isocyanate group Z hydroxyl group is preferably 0.3 to 1.5, more preferably 0.5 to 1.5.

For the same reason, the molar ratio of the ethylenically unsaturated group-containing carboxylic acid compound or derivative thereof and the hydroxyl group-containing fluoropolymer to the ethylenically unsaturated group-containing carboxylic acid compound or derivative Z hydroxyl group thereof is set to 0. The reaction is preferably carried out at a ratio of 1 to 1.9. However, when the rubonic acid derivative is an acid anhydride, it can react with two hydroxyl groups per molecule, so the molar ratio of the acid anhydride Z hydroxyl group of the ethylenically unsaturated group-containing carboxylic acid compound Is preferably set to a ratio of 0.05 to 0.95.

[0131] The amount of the ethylenically unsaturated group-containing fluoropolymer (D) added to the composition for forming a low refractive index phase is not particularly limited, but is relative to the total amount of the composition other than the organic solvent. Usually 1 to 95% by mass. The reason for this is that when the addition amount is less than 1% by mass, the refractive index of the cured coating film of the curable resin composition becomes high and sufficient antireflection effect cannot be obtained. On the other hand, if the addition amount exceeds 95% by mass, the scratch resistance of the cured coating film of the curable resin composition may not be obtained.

Further, for such reasons, the addition amount of the component (E) is more preferably 2 to 90% by mass, and further preferably 3 to 85% by mass.

[0132] 2. Ingredients)

(1) Particles mainly composed of silica

In the composition for forming a low refractive index layer used in the present invention, particles containing silica as a main component can be blended, and the scratch resistance of the cured product of the composition for forming a low refractive index layer, particularly steel wool resistance. Can be improved. As the particles having silica as a main component, particles having silica having a number average particle diameter of 1 to lOOnm as a main component are preferable. The particle size is measured with a transmission electron microscope. The particle size of the component (E) is preferably 5 to 80 nm, more preferably 10 to 60 nm. As the particles mainly composed of silica, known particles can be used, and the shape is not particularly limited. As long as it is spherical, it is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Further, it is not limited to a spherical shape, and may be an amorphous particle. Of these, a colloidal shear force having a solid content of 10 to 40% by weight is preferred.

[0133] In addition, the dispersion medium is water! /, And an organic solvent is preferred. Examples of the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene. Hydrogens; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, γ-butalate ratatones; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

[0134] Commercially available particles mainly composed of silica include, for example, colloidal silica manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ΜΕΚ— ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— ST-O-ST-20, ST-40, ST-C, ST-N, ST-0, ST-50, ST-OL, and the like.

[0135] In addition, the surface of colloidal silica that has been subjected to surface treatment such as chemical modification can be used. For example, it contains a hydrolyzable key compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. Can be reacted. Examples of such hydrolyzable silicon compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxy. Silane, 1,1,1-trimethoxy-1,2,2,2 Trimethylmonodisilane, hexamethyl-1,3 disiloxane, 1,1,1-trimethoxy 3,3,3 trimethyl-1,3 disiloxane, α-trimethylsilyl ω -Dimethylmethoxysilyl-polydimethylsiloxane, (X-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3 disilazane, etc. In addition, it has one or more reactive groups in the molecule. Use hydrolyzable key compounds Also. Molecular hydrolyzable Kei-containing compound having one or more reactive groups in the as having ΝΗ group as the reactive group In example embodiment, urea propyltrimethoxysilane, Nyu-

2

(2 aminoethyl) 3-aminopropyltrimethoxysilane and the like having a ΟΗ group, bis (2 hydroxyethyl) 3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanate propyltrimethyl Methoxysilane, such as those having a thiocyanate group, 3-thiocyanatepropyltrimethoxysilane, etc., such as those having an epoxy group (3 glycidoxypropyl) trimethoxysilane, 2- (3,4 epoxy hexyl) Examples of those having a thiol group, such as ethyltrimethoxysilane, include 3-mercaptopropyltrimethoxysilane. A preferred compound is 3-mercaptopropyltrimethoxysilane.

[2136] (2) Preferred mode (silica particles having an ethylenically unsaturated group on the surface)

The silica particles used in the present invention preferably have an ethylenically unsaturated group (hereinafter referred to as “reactive silica particles”). The method for producing reactive silica particles is not particularly limited. For example, the reactive silica particles can be obtained by reacting the silica particles having a number average particle size of 10 to LOONm and a reactive surface treatment agent. . Here, examples of the surface treatment agent include alkoxysilane compounds, tetrabutoxytitan, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.

[0138] Specific examples of the surface treatment agent include compounds having an unsaturated double bond in the molecule such as y-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, Examples include compounds represented by the following general formula (11).

In the formula, R ¹⁹ is a methyl group, R ² 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 of 1 to 5, and R ²² is a carbon number. 1 to 6 divalent alkylene group, R ²³ is a bivalent to hexavalent chain, cyclic or branched divalent hydrocarbon group having 2 to 14 carbon atoms, R ²⁴ is a chain, cyclic or branched (K + 1) -valent hydrocarbon group having 3 to 14 carbon atoms. R ²⁴ may contain an ether bond.

Since the silica particles have an ethylenically unsaturated group, they can be co-crosslinked with a UV curable acrylic monomer, and scratch resistance is improved.

[0139] (3) Preferred embodiment (porous silica particles)

As silica particles (E) used in the composition for forming a low refractive index layer, porous silica particles are also preferable.

More preferably, the first porous silica particles (E1) or the second porous silica particles (F2) are used as the porous silica particles. The first porous silica particles (F1) are obtained by hydrolysis and Z or hydrolysis condensation of a key compound represented by the following formula (12) and a key compound represented by the following formula (13). . That is, by subjecting the key compound represented by the formula (12) to water hydrolysis and Z or hydrolytic condensation, and hydrolyzing and converting the key compound represented by the formula (13) to Z or hydrolytic condensation. can get. Key elemental compound expressed by equation (12) And the key compound represented by formula (13) may be mixed and subjected to hydrolysis and Z or hydrolytic condensation at the same time, or the key compound represented by formula (12) may be hydrolyzed and converted to Z. Alternatively, carolysis may be carried out by water hydrolysis, followed by hydrolysis and Z or hydrolysis condensation by adding a key compound represented by formula (13). The second porous silica particles (E2) are a key compound represented by the following formula (12), a key compound represented by the following formula (13), and a key compound represented by the following formula (14). Obtained by hydrolysis of Z and Z or hydrolytic condensation. That is, hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (12), and hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (13), and the formula It can be obtained by hydrolysis and Z or hydrolysis condensation of the silicon compound represented by (14). The key compound represented by formula (12), the key compound represented by formula (13), and the key compound represented by formula (14) are mixed and simultaneously hydrolyzed and Z or hydrolyzed. Alternatively, the key compound represented by the formula (12) is hydrolyzed and Z or hydrolyzed and condensed, and V is the key compound represented by the formula (13) and the formula (14). Further hydrolysis and Z or hydrolytic condensation may be performed by adding a key compound.

SiX (12)

Four

R ²⁵ SiX (13)

a 4— a

R ²⁶ SiX, (14)

b 4-b

[0140] In the formulas (12), (13) and (14), each X is independently an alkoxy group having 1 to 4 carbon atoms, a hydrogen group, a logeno group, an isocyanate group, a carboxyl group, or an alkyl group having 2 to 4 carbon atoms. It is a xycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, more preferably an alkoxy group. In the formulas (12), (13) and (14), X may be the same or different.

Examples of the compound represented by the formula (12) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane.

[0141] In the formula (13), R ²⁵ is an alkyl group having 2 to 8 carbon atoms, an allyloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably These are a bur group, an aryl group, an attaryloxychetyl group, an attaryloxypropyl group, an attaryloxybutyl group, a methacryloxycetyl group, a methacryloxypropyl group, and a methacryloxybutyl group. In the formula (13), a is an integer of 1 to 3, preferably 1 to 2.

Examples of the compound represented by the formula (13) include vinyltrimethoxysilane, butyltrioxysilane, vinyltrichlorosilane, talyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.

By using the compound represented by the formula (13), the porous silica particles can contain an ethylenically unsaturated group. By containing an ethylenically unsaturated group, the scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the curable composition is improved.

[0142] In the 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, more preferably a fluorine having 3 to 10 carbon atoms. Substituted alkyl group.

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, and 2-perfluorohexylsilyltrimethoxy. Silane, 2-Perfluorooctyltrimethylsilane, 2-Perfluorooctyltriethoxysilane, 3,3-di (trifluoromethyl) -3-Fluoropropyltriethoxysilane, etc. Can be mentioned.

By using the compound represented by the formula (14), the porous silica particles can contain fluorine-containing alkyl groups. By including the fluorine-containing alkyl group, the stain resistance of the cured film obtained by curing the curable composition can be improved.

Two or more kinds of the key compound represented by the formula (12), the key compound represented by the formula (13), and the key compound represented by the formula (14) may be used.

[0143] In the first porous silica particle (E1), when the total of the key compound represented by the formula (12) and the key compound represented by the formula (13) is 100 mol%, the formula ( the Kei-containing compound represented by Kei-containing compound Z formula represented by 12) (13), preferably, 67～99Zl～33 (mol%), more preferably 70～98Z2～30 (mol ^_0/0) Hydrolysis and Z or hydrolytic condensation at a ratio of

In the second porous silica particle (E2), the total of the key compound represented by the formula (12), the key compound represented by the formula (13) and the key compound represented by (14) is 100. Mol% and The key compound represented by the formula (12), the key compound represented by the formula (13), and the key compound represented by the formula (14) are preferably 60 to 9871 to 30 1. It is hydrolyzed and / or hydrolyzed and condensed at a rate of ˜20 (mol%), preferably 65 to 962 to 202 to 15 (mol%).

[0144] The first and second porous silica particles (El) and (E2) used in the present invention have an average particle size force of ~ 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm. The average particle diameter is a number average particle diameter, and is measured with a transmission electron microscope image. The term “porous” means that the specific surface area is 50 to: L000m ² Zg, preferably 50 to 800 m ² Zg, and more preferably 100 to 800 m ² / g. The specific surface area is measured by the BET method.

If the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed. Moreover, due to being porous, the density is lowered and the refractive index of the film containing such porous silica particles is lowered.

[0145] The porous silica particles (E) are obtained by the production method described below.

The first or second porous silica particles (El) and (E2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and semi-ethers of diols. In the presence of a species, the key compound represented by the formula (12) and the key compound represented by the formula (13), or the key compound represented by the formula (12), the formula (13 ) And the compound represented by formula (14) can be produced by hydrolysis and Z or hydrolysis condensation.

[0146] As the basic compound, for example, an amine compound is used, and specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethylanolamine, dimethylmonoethanol. Amamine, Monomethyljetanolamine, Triethanolamine, Diazabicycloocrane, Diazabicyclononane, Diazabicycloundecene, Tetramethylammo-umhide mouth oxide, Tetraethylammo-muhide mouth oxide, Tetrapropylammo -Umhide mouth oxide, tetraptylammonium -umhydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-jetylamine, N, N-dipropylamine, N, N-dibu Examples include tyramine, trimethylamine, triethylamine, tripropylamine, and tributylamine. Preferably, ammonia, ethanolamine, hydroxy-tetramethylamine or the like is used.

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

[0147] The acid amide, diol or diol half-ether is preferably compatible with water and an alcohol.

As the acid amide, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. are used, preferably N, N-dimethylformamide, N, N-dimethylacetamide is used. .

[0148] 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. For example, ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used as the half ether of the diol.

The porous silica particles used in the present invention can be made porous by the coexistence of acid amide, diol or diol half ether during synthesis.

[0149] The total concentration of the key compound of formula (12) and the key compound of formula (13) or the key compounds of formulas (12) to (14) in the reaction solution is usually 0 in terms of complete hydrolysis condensate. 5 to 10% by mass, preferably 1 to 8% by mass. Here, “complete hydrolyzed condensate conversion” is a theoretical value calculated on the assumption that the key compound was completely hydrolyzed and condensed, and the key compound of formula (12) and This corresponds to the mass when X in the key compound of (13) or the key compounds of formulas (12) to (14) is replaced with 1 mol of 2 moles of oxygen. By making the concentration of the key compound at the time of particle synthesis within the above range, the coarsening of the particles is prevented, and the average particle size is 5 to 50 nm.

The compound of formula (12) and the compound of formula (13), or the compound of formula (12), the compound of formula (13) and the compound of formula (14) are mixed simultaneously. Hydrolysis and Z or hydrolytic condensation may also be used. Water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols and diols and diol semi-ether forces are present. Below, the key compound represented by the formula (12) is hydrolyzed and Z or hydrolyzed. Decondensation, followed by further hydrolysis by adding a key compound represented by formula (13), or a key compound represented by formula (13) and a key compound represented by formula (14), respectively. And Z or hydrolytic condensation.

[0150] The reaction temperature of hydrolysis and Z or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acidamide to be used. Reaction time is represented by formula (12), compound (13) and compound (14), reaction rate, type and amount of base, etc. The optimum value varies depending on the value, and is not limited.

By adding an organic solvent to the obtained hydrolysis and Z or hydrolysis-condensation reaction liquid, and further removing unnecessary components by a method such as distillation or liquid-liquid extraction as necessary, the porous silica particles become organic. A dispersion liquid dispersed in a solvent can be obtained.

[0151] The dispersion medium is water! /, And organic solvents are preferred. Examples of the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene. Hydrogens; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, γ-butalate ratatones; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

[0152] The amount of the porous silica particles (Ε) in the composition for forming a low refractive index layer is usually 5 to 99% by mass, and 10 to 98% by mass with respect to the total amount of the composition other than the organic solvent. 15 to 97% by mass is more preferable. If it is less than 5% by mass, the hardness of the cured film may be insufficient, and if it exceeds 99% by mass, sufficient film strength may not be obtained. The amount of particles means a solid content, and when the particles are used in the form of a solvent dispersion, the amount of the solvent does not include the amount of solvent.

[0153] 3. A polyfunctional (meth) attareito to compound containing at least two (meth) attaroyl groups and fluorinated (meth) containing at least one or more (meth) attaloyl groups A Tallylate compound (component (G))

In the composition for forming a low refractive index layer, if necessary, a polyfunctional (meth) attareito toy compound containing at least two or more (meth) attayryl groups and Z or at least one or more It is also possible to add a fluorine-containing (meth) ataretoy compound containing a (meth) ataryloyl group.

[0154] (1) A polyfunctional (meth) ataretoy compound containing at least two (meth) atalyloyl groups

The compound is not particularly limited as long as it is a compound containing at least two (meth) atallyloyl groups in the molecule. Examples include neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta erythritol tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta erythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, force prolatatatone modified dipentaerythritol hex (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, "U-15HAJ (trade name) Manufactured by Shin-Nakamura I 匕学 Co., Ltd.) is alone or in combinations of two or more such.

Of these, neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and force prolatatatone. Modified dipentaerythritol hexa (meth) acrylate is particularly preferred.

[0155] (2) Fluorine-containing (meth) atareto toy compound containing at least one (meth) atalyloyl group

The compound is not particularly limited as long as it is a fluorine-containing (meth) ataretoy compound containing at least one or more (meth) atalyloyl groups. Examples thereof include perfluorooctyl cetyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These are either alone or Can be used in combination of two or more.

[0156] The amount of component (G) to be added is not particularly limited, but is usually 0 to 90% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount exceeds 90% by mass, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained.

Further, for such reasons, it is more preferable to add the amount of the component (G) to 80% by mass or less, and more preferable to add 60% by mass or less.

[0157] 4. Compounds that generate active species upon irradiation with active energy rays or heat

In the present invention, a compound that generates active species by irradiation of active energy rays or heat can also be added. A compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.

[0158] (1) Compounds that generate active species upon irradiation with active energy rays

Examples of compounds that generate active species upon irradiation with active energy rays (hereinafter referred to as “photopolymerization initiators”) include photoradical generators that generate radicals as active species.

The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, j8 rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.

[0159] (i) Kind

Examples of photo radical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenol) 2 hydroxy-1-methylpropanone 1-on, carbazole, xanthone, 4-clobenbenzophenone. 4, 4'-mino minobenzophenone, 1, 1-dimethoxydeoxybenzoin, 3, 3, 1-dimethyl-4-methoxybenzophenone, dianthus xanthone, 2, 2-dimethoxy-2-phenacetophenone, 1- (4-Dodecylphenol) 2-hydroxy-1-2-methylpropane-1-one, 2-methyl-11- [4- (methylthio) phenol] 2 morpholinopropane 1-one, trif Eramine, 2, 4, 6 Trimethyl benzoyl diphosphine phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy 2-methyl-1-phenylpropan 1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether Ter, benzoinpropyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3, 3 ', 4, 4'-tetra (tert-butylperoxycarbol) benzophenone (BTTB), 2- (dimethylamino) — 1— [4 — (Morpholol) —2—Fel Methyl) 1-butanone, 4 Benzoro 4'-Methyldiphenyl sulfide, benzyl, or BTTB and xanthene, thixanthene, coumarin, ketocoumarin, other dyes The combination with a sensitizer etc. can be mentioned.

[0160] Among these photopolymerization initiators, 2, 2 dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 (methylthio) phenol] 2 Morpholinopropane 1-one, 2 (dimethylamino) 1 4 (morpholinyl) phenol] 2 methanol 1) -butanone and the like are more preferable, 1-hydroxycyclohexylphenylketone, 2-methyl-11 [4 (methylthio) phenol] 2 morpholinopropane 1-ion, 2- (dimethylamino) ) -1- [4- (morpholol) phenol] -2 phenolmethyl) -1-butanone and the like.

[0161] (ii) Amount added

The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, if the addition amount of the photopolymerization initiator exceeds 20% by mass, the refractive index of the cured film may increase and the antireflection effect may decrease.

For this reason, the addition amount of the photopolymerization initiator is more preferably 0.05% by mass to 0.115% by mass with respect to the total amount of the composition other than the organic solvent. Is more preferable. [0162] (2) Compounds that generate active species by heat

Examples of the compound that generates an active species by heat (hereinafter referred to as “thermal polymerization initiator”) include a thermal radical generator that generates a radical as the active species.

[0163] (i) Types

Examples of thermal radical generators include benzoyl peroxide, tert-butyloxybenzoate, azobisisobutyoxy-tolyl, acetylyl peroxide, lauryl peroxide, tert-butyl peracetate, tamil peroxide, tert-butyl peroxide, tert-butyl hydride Oral peroxide, 2,2, -azobis (2,4-dimethylvale-tolyl), 2,2, -azobis (4-methoxy-2,4-dimethylvale-tolyl), etc., alone or in combination of two or more Can be mentioned.

[0164] (ii) Addition amount

The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the amount of added calories is less than 0.01% by mass, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, if the amount of addition of the photopolymerization initiator exceeds S20 mass%, the refractive index of the cured film increases and the antireflection effect may decrease.

For these reasons, it is more preferable to add the thermal polymerization initiator to 0.05 to 15% by mass with respect to the total amount of the composition other than the organic solvent. It is more preferable that the value be within the range.

[0165] 5. Organic solvent

It is preferable to further add an organic solvent to the “low refractive index layer forming composition”. By adding an organic solvent in this way, a thin antireflection film can be formed uniformly. As such an organic solvent, an alcohol solvent having 1 to 8 carbon atoms, a carbon atom having 3 to carbon atoms: an ketone solvent having 3 to carbon atoms, or an ester solvent having 3 to carbon atoms having an carbon number of 3 can be preferably used. Tilketone, methyl amyl ketone, methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. are particularly preferred. Take as an example. These organic solvents can be used singly or in combination of two or more.

[0166] The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by mass with respect to 100 parts by mass of the composition other than the organic solvent. This is because when the addition amount is less than 100 parts by mass, it may be difficult to adjust the viscosity of the curable resin composition. On the other hand, when the addition amount exceeds 100,000 parts by mass, the curable resin composition is hardened. This is because the storage stability of the composition may be decreased, or the viscosity may be excessively decreased to make handling difficult.

[0167] 6. Additive

In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, an acceptable agent are used as long as the objects and effects of the present invention are not impaired. Plasticizer, UV absorber, antioxidant, antistatic agent, silane coupling agent, inorganic filler other than (E) component

[0168] 7. Method for preparing composition for forming low refractive index layer

The curable resin composition used in the present invention comprises the (D) ethylenically unsaturated group-containing fluorine-containing polymer and the (E) component, or, if necessary, the (G) component and active energy rays. It can be prepared by adding a compound that generates active species by irradiation or heat, an organic solvent, and an additive, respectively, and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

[0169] 8. Method of curing composition for forming low refractive index layer

Although there is no particular limitation on the curing conditions of the composition for forming a low refractive index layer, for example, when active energy rays are used, the exposure dose is within the range of 0.01 to 10 j / cm ² . The value is preferred.

This is because when the exposure amount is less than 0. OljZcm ² , curing failure may occur, whereas when the exposure amount exceeds lOjZcm ² , the curing time may become excessively long. . For these reasons, it is more preferable to set the exposure amount within a range of 0.1 to 5 jZcm ² , and it is more preferable to set a value within a range of 0.3 to ³ j / cm ² .

[0170] When the composition for forming a low refractive index layer is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 0.5 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.

For this reason, it is more preferable to heat for 1 to 120 minutes at a temperature in the range of 50 to 180 ° C. Heating for 1 to 60 minutes at a temperature in the range of 80 to 150 ° C. Is even better.

[Example]

[0171] Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these Examples. In the following, parts and% respectively represent parts by weight and% by weight unless otherwise specified.

[0172] Production Example 1: Preparation of composition 1 for forming an antistatic layer

Phosphorus-containing tin oxide dispersion (ELCOM JX-1001PTV manufactured by Catalytic Chemical Industry Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30% by weight, average primary particle size) 80 parts, dipentaerythritol hexaatalylate (trade name: KAYARA D DPHA, manufactured by Nippon Shakuyaku Co., Ltd., may be referred to as B-1 below) 15. 6 parts Bis (Atylyloxymethyl) tricyclo [5. 2. 1. 0 ² ' ⁶ ] decane (NK Nakamura NK ester A—DCP: “Tricyclodecandiyldimethanol ditalylate” 1 5. 6 parts, 1-hydroxycyclohexyl phenyl ketone (Tiroku 'Specialty' Chemicals Co., Ltd. Irgacure 184, molar extinction coefficient at 313 nm: 80LZmol'cm, In the following C 1 1 4) and 50 parts of propylene glycol monomethyl ether were stirred at 50 ° C. for 2 hours to obtain a uniform antistatic layer forming composition 1. 2 g of this antistatic layer forming composition 1 was weighed on an aluminum dish, dried on a hot plate at 140 ° C. for 1 hour, and weighed to obtain a solid content of 35% by weight.

Production Example 2 Preparation of Composition 2 for Forming Antistatic Layer Phosphorus-containing tin oxide dispersion (ELCOM JX-1001PTV manufactured by Catalytic Chemical Industry Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30% by weight, average primary particle size) 20 parts, 20%, 2.17% by weight dispersant) 200 parts, dipentaerythritol hexaatalylate (trade name KAYARA D DPHA, manufactured by Nippon Shakuyaku Co., Ltd.) Bis (Atylyloxymethyl) tricyclo [5. 2. 1. 0 ² ' ⁶ ] decane (NK Nakamura NK ester A—DCP: “Tricyclodecandiyldimethanol ditalylate” 1-5 6 parts, 2-methyl-1 (4 (methylthio) phenol) -2 morpholinopropane 1-on (Chinoku 'Specialty' Chemicals Co., Ltd.) Irgacure molar absorption at 907 and 313 nm : 17, OOOL / mol-cm, hereinafter referred to as C'2)) 4. Stabilization of uniform solution by stirring 5 parts and 50 parts of propylene glycol monomethyl ether at 50 ° C for 2 hours A layer forming composition 2 was obtained. 2 g of this antistatic layer forming composition 2 was weighed in an aluminum dish, dried on a hot plate at 140 ° C. for 1 hour, and weighed to obtain a solid content of 35% by weight.

Production Example 3: Synthesis of an organic compound having a polymerizable unsaturated group

To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, add 222 parts of isophorone diisocyanate at 50 ° C with stirring for 1 hour, then at 70 ° C. The mixture was heated and stirred for 3 hours. It consists of a new Nakamura I匕学Ltd. NK Ester A -TMM- 3LM- N (pentaerythritol Atari rate 60 weight ^_0/0 and pentaerythritol Lumpur tetra Atari rate 40% by weight. Among them, involved in the reaction It is only pentaerythritol tritalylate having a hydroxyl group.) After adding 549 parts dropwise at 30 ° C over 1 hour, and then stirring with heating at 60 ° C for 10 hours, the organic compound having a polymerizable unsaturated group A compound was obtained. When the amount of isocyanate remaining in the reaction solution was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peak characteristic 2260 cm ^{_ 1} to the absorption peak and the raw material Isoshianetoi匕合of characteristic 2550 cm ^_1 mercapto group in the starting material, new urethane bond and S (C = 0) peak characteristic 1720 cm ^_1 peak and Atarirokishi group characteristic 1660 cm ^_1 to the NH group was observed, Atarirokishi group and S (C = O as a polymerization unsaturated group) NH-, It was shown that oxy-oxy group-modified alkoxysilane having both urethane bonds was formed. As a result, a total of 773 parts of the compounds represented by the following formulas (15) and (16) were obtained (hereinafter, this compound may be referred to as “alkoxysilane (1)”) and involved in the reaction. There was a mixture of 220 parts of pentaerythritol tetraatalylate.

[Chemical 18]

[In the formulas (15) and (16), “Acryl” represents an attaryloyl group, and “Me” represents a methyl group. Production Example 4: Production of a compound represented by the following formula (17)

[Chemical 20]

[In the formula (17), “Acryl” represents an allyloyl group. ]

A solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer was added to NK Estel A-TMM-3LM-N (Shin Nakamura Chemical Co., Ltd.). (Only pentaerythritol triatalylate having a hydroxyl group is added.) 93 parts are added dropwise at 10 ° C for 1 hour, and then stirred at 60 ° C for 6 hours. A liquid was used.

When the amount of residual isocyanate in this reaction solution was measured by FT-IR in the same manner as in Production Example 3, it was 0.1% by weight or less, confirming that the reaction was almost quantitative. In addition, it was confirmed that the molecule contains a urethane bond and an taliloyl group (polymerizable unsaturated group).

As a result, 75 parts of the compound represented by the formula (17) was obtained, and 37 parts of pentaerythritol tetraatalylate which was not involved in the reaction were mixed.

[0179] Production Example 5: Preparation of silica particle-containing coating composition

Solution of alkoxysilane (1) produced in Production Example 3 2. 32 parts, silica particle sol (methyl ethyl ketone silica sol, MEK-ST, Nissan Chemical Industries, Ltd., number average particle size 0.022, silica concentration 30% ) 91.3 parts (27 parts as silica particles), 0.112 parts of ion-exchanged water, and 0.01 part of p-hydroxyphenol monomethyl ether were stirred at 60 ° C for 4 hours, and then orthoformate 1. 36 parts of methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive silica particle dispersion. The solid content was determined in the same manner as in Production Example 1 and found to be 31% by weight.

98.6 g of this dispersion, 3.4 g of a solution containing the compound represented by the formula (17) obtained in Production Example 4, 1-hydroxycyclohexyl phenol ketone (C-1) 2. lg, 2-methyl 1— [4— (Methylthio) phenol] 2—morpholinopropane 1 ON (C—2) 1.2 g, dipentaerythritol hexaatalylate 33.2 g, and cyclohexanone 7 g are mixed and stirred. 145 g of a composition for containing a node coat layer (solid content concentration: 50%) was obtained.

[0180] Production Example 6: Production of reactive silica particle sol bonded with an organic compound having a polymerizable unsaturated group

Silica particle sol (Methyl ethyl ketone silica sol, MEK-ST — L, Nissan Chemical Industries, Ltd., number average particle size 0.05 μm, silica concentration 30%) 143g (43g as silica particles), Production Example 3 2.8 g of the alkoxysilane (1) solution prepared in 1 above, 0.1 g of distilled water and 0. Olg of hydroquinone monomethyl ether were mixed and heated and stirred at 65 ° C. After 4 hours, 1.0 g of methyl orthoformate was added, and the mixture was further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%. [0181] Production Example 7: Production of hydroxyl-containing fluoropolymer (d-1)

Internal volume 3. After replacing the OL autoclave with a magnetic stirrer sufficiently with nitrogen gas, 1800 g of ethyl acetate, 607.3 g of perfluoro (propylbutyl ether) (FPVE), (perfluorooctyl) ethyl vinyl ether 111 9 g, hydroxyethyl vinyl ether (HEVE) 180.8 g, and peroxylauroyl 4.5 g were charged, and oxygen in the system was removed again with nitrogen gas.

Next, the temperature was raised and the reaction was continued with stirring at 70 ° C. for 20 hours, and then the autoclave was cooled with water to stop the reaction.

After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and the reaction solution was added dropwise to 30 kg of methanol Z water mixed solution (mixing weight ratio 80Z20). The precipitate was taken out and dried under reduced pressure at 40 ° C to obtain a hydroxyl group-containing fluoropolymer (d-1).

[0182] Production Example 8: Production of hydroxyl-containing fluoropolymer (d-2)

Internal volume 3. After replacing the OL autoclave with a magnetic stirrer with nitrogen gas, 1600 g of ethyl acetate, perfluoro (propylbutyl ether) (FPVE) 59.8 g, (perfluorooctyl) ethyl vinyl ether 99 5 g, hydroxyethyl vinyl ether (HEVE) 16.7 g, peroxylauroyl 4 g, VPS1001, 24 g, NE-30 160 g were charged, and oxygen in the system was removed again with nitrogen gas.

After the temperature of the reaction solution reached room temperature, the autoclave was opened, the reaction solution was recovered, and the reaction solution was added dropwise to 30 kg of methanol Z water mixed solution (mixing weight ratio 80Z20). The precipitate was taken out and dried under reduced pressure at 40 ° C. to obtain a hydroxyl group-containing fluoropolymer (d-2).

Here, VPS1001 is an azo group-containing polydimethylsiloxane represented by the above general formula (8) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier in which n is 9, m is 1, and u is 30 in the above general formula (10).

[0183] Production Example 9: Production of ethylenically unsaturated group-containing fluoropolymer solution (D-1)

Electromagnetic stirrer, glass cooling tube, glass Dean-Stark tube, glass dropping funnel and Into a 5 liter separable flask equipped with a thermometer, 400 g of the hydroxyl group-containing fluoropolymer (d-1) obtained in Production Example 7 and 12 OOg of methyl isobutyl ketone (MIBK) as a solvent were poured. Stirring was performed at room temperature to dissolve the hydroxyl group-containing polymer in a solvent. Next, 64. Og of acrylic acid was added and stirred at room temperature to visually confirm that the solution was uniform. A solution obtained by dissolving 8.8 g of sulfuric acid in 160 g of MIBK was added dropwise while stirring at room temperature using a glass dropping funnel. After completion of the dropwise addition, the system was heated using an oil bath under dry air 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 10% aqueous ammonia solution was added, and the pH of the reaction solution was confirmed to be 6-7 using a pH indicator. The obtained reaction solution was dropped into 20 kg of a mixed solution of methanol Z water (mixing weight ratio 80Z20) to precipitate a polymer. The precipitated polymer is dissolved in MIBK so that the solid content concentration is 20% by weight, and then water is removed from the system with magnesium sulfate, followed by filtration, and fluorine containing ethylenically unsaturated groups with a solid content concentration of 20%. A polymer solution (D-1) was obtained. The composition of the obtained ethylenically unsaturated group-containing fluoropolymer was analyzed by ¹³ C-NMR, and the fluorine content obtained for the compositional power was 54% by weight.

[0184] Production Example 10: Production of ethylenically unsaturated group-containing fluoropolymer solution (D-2)

In a separable flask with a capacity of 3 liters equipped with a magnetic stirrer, a glass cooling tube and a thermometer, 400 g of the hydroxyl group-containing fluoropolymer (d 2) obtained in Production Example 8 was used as a polymerization inhibitor. t Add 0.017 g of butylmethylphenol and 18 51 g of MIBK as a solvent and 62.6 g of 2-methacryloyloxychetyl isocyanate, stir until the solution is uniform, then dibutyltin dilaurate 0. 9 g was added to start the reaction, the temperature of the system was maintained at 55 to 65 ° C., and stirring was continued for 5 hours under dry air, so that the hydroxyl group-containing fluoropolymer (d-2) and 2-methacryloyl A reaction solution (D-2) (solid content concentration: 20% by weight) with xichetyl isocyanate was obtained. The composition of the obtained ethylenically unsaturated group-containing fluoropolymer was analyzed by 13C-NMR, and the fluorine content determined from the composition was 45% by weight.

[0185] Production Example 11: Preparation of composition 1 for forming a low refractive index layer

Reactive silica particle sol 86.7 g (26.9 g as reactive particles) obtained in Production Example 6 Ethylenically unsaturated group-containing fluoropolymer obtained in Preparation Example 9 (D-1) 204. Og (40.8 g as an ethylenically unsaturated group-containing fluoropolymer), ethylene polymer obtained in Production Example 10 Unsaturated unsaturated group-containing fluoropolymer (D-2) 100. Og (20 Og as an ethylenically unsaturated group-containing fluoropolymer), dipentaerythritol pentaatalylate 6.8 g, the formula obtained in Production Example 4 2.9 g of a composition containing (17), 2-methyl-1-one [4 (methylthio) phenol] 2 morpholinopropane 1-on 4.8 g as a photopolymerization initiator, alitaroyl-modified polydimethylsiloxane (FM0725, Chisso Corporation) (Company) 3.0 g, organic copolymer-containing special silicon (Floren AC-901, Kyoeisha Chemical Co., Ltd.) 0.7 g, methyl isobutyl ketone 2239 g was added, and stirred at room temperature for 1 hour, composition for forming a low refractive index layer I got thing 1. The solid content was determined in the same manner as in Production Example 1 and found to be 4% by weight.

Production Example 12: Synthesis of porous silica particles

In a quartz separable flask, 22.24 g of tetraethoxysilane, 841.97 g of methanol, and 30.00 g of propylene glycol were added and mixed uniformly, and then 101.00 g of a 1% aqueous solution of ammonia was added. Then, the solution was allowed to react at 40 ° C for 8 hours with stirring. Furthermore, 0.92 g of butyltrimethoxysilane and methacryloxypropyltrimethoxysilane (Toray Dow Counging Co., Ltd., Silicone SZ-6030) 1. 54 g Was added and reacted at 40 ° C for 1 hour. Next, 2.33 g of 2-perfluorohexoxyltrimethoxysilane (GE Toshiba Silicone Co., Ltd. TSL8257) was added and reacted at 40 ° C. for 1 hour. After the reaction solution was cooled to room temperature, 1000.00 g of methinoisobutinolecan and 1000.00 g of a 0.1% aqueous solution of oxalic acid were added, stirred and allowed to stand. The upper layer separated into two layers was separated and concentrated to a solid content concentration of 5% using a rotary evaporator to obtain a porous silica particle solution.

After adding 10 g of ethanol to lg of the porous silica particle solution obtained above and mixing, 1 drop was dropped on a carbon grid for a transmission electron microscope and then dried at room temperature for 24 hours at JEOL Ltd. Observation was made using a field emission electron microscope EM-2010F, and the particle size of the porous silica particles was measured. The average particle size was 20 nm.

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

[0187] Production Example 13: Preparation of composition 2 for forming a low refractive index layer

Ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 9 (D-1) 12.5 g (2.5 g as an ethylenically unsaturated group-containing fluoropolymer), ethylene polymer obtained in Production Example 10 12.5 g of an unsaturated group-containing fluoropolymer (2.5 g as an ethylenically unsaturated group-containing fluoropolymer), and the porous silica particle dispersion obtained in Production Example 12 was lOOOg (porous Siri force particles (5 Og), photopolymerization initiator 2-methyl 1- [4- (methylthio) phenol] 2 morpholinopropane 1-one 0.4 g, MIBK 134.6 g, with stirrer The mixture was placed in a glass separable flask and stirred at 23 ° C for 1 hour to obtain a composition 2 for forming a low refractive index layer. The solid content was determined in the same manner as in Production Example 1 and found to be 4% by weight.

[0188] Example 1

Manufacture of antireflection laminate 1

Coating composition 1 for forming an antistatic layer obtained in Production Example 1 on ARTON film G7810 (norbornene resin film manufactured by JSR Corporation, film thickness 188 μm) using wire bar coater # 12 And dried in an oven at 80 ° C. for 3 minutes. Next, the coating film was cured with UV light in the atmosphere using a metal halide lamp under the light irradiation conditions of UZcm ² to produce a film having a hard coat layer. When the film thickness of the hard coat layer was measured with a stylus type surface shape measuring instrument, it was 3 m. On this film with a hard coat, the composition 1 for forming a low refractive index layer obtained in Production Example 11 was applied using a wire bar coater # 3, and then in an oven at 80 ° C for 1 minute. Dried. Next, using a metal halide lamp in a nitrogen atmosphere, the coating film was UV-cured under a light irradiation condition of UZcm ² to form a low refractive index layer, thereby producing an antireflection laminate 1. The film thickness of the low refractive index layer was calculated from the reflectance of the obtained antireflection laminate 1 and found to be 0 .: m.

[0189] Example 2

Manufacture of antireflection laminate 2

An antireflection laminate 2 was prepared 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. . When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0 .: Lm. [0190] Example 3

Manufacture of antireflection laminate 3

The composition for the node coat layer containing silica particles obtained in Production Example 5 was coated on ARTON film G7810 (norbornene resin film manufactured by JSR Corporation, film thickness 188 m) using wire bar coater # 6. And dried in an oven at 80 ° C. for 3 minutes. Next, the film was UV-cured under the light irradiation conditions of UZcm ² using a metalno and ride lamp in the atmosphere to produce a film having a hard coat layer. When the film thickness of the hard coat layer was measured with a stylus type surface profile measuring instrument, it was 3 m. On this hard-coated film, the antistatic layer-forming composition 1 obtained in Production Example 1 was diluted to 5% solid content with propylene glycol monomethyl ether, and a wire bar coater # 6 was used. It was coated and dried in an oven at 80 ° C for 1 minute. Next, the coating film was UV-cured under a light irradiation condition of UZcm ² using a metal halide lamp in a nitrogen atmosphere to form a high refractive index layer. When the film thickness of the high refractive index layer was calculated in the same manner as in Example 1, it was 0 .: m. The resulting laminate was coated with the composition 1 for forming a low refractive index layer obtained in Production Example 11 using a wire bar coater # 3, and dried in an oven at 80 ° C. for 1 minute. . Next, the coating film was UV-cured under a light irradiation condition of UZcm ^{2 in} a nitrogen atmosphere using a metal lamp and a ride lamp to form a low-refractive index layer, thereby producing an antireflection laminate 3. The film thickness of the low refractive index layer was calculated from the reflectance of the obtained antireflection laminate 3 and found to be 0.1 μm.

[0191] Comparative Example 1

Manufacture of antireflection laminate 4

An antireflection laminate 4 was prepared in the same manner as in Example 1 except that the antistatic layer forming composition 2 obtained in Production Example 2 was used instead of the antistatic layer forming composition 1. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0 .: Lm.

[0192] Comparative Example 2

Manufacture of antireflection laminate 5

Example 1 except that the composition for forming a silica particle-containing node coat layer obtained in Production Example 5 was used in place of the composition 1 for forming an antistatic layer and the wire bar coater # 6 was applied. In the same manner as described above, an antireflection laminate 5 was produced. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 m.

[0193] Comparative Example 3

Manufacture of antireflection laminate 6

In the same manner as in Example 2, except that the composition for forming a silica particle-containing node coat layer obtained in Production Example 5 was used in place of Composition 1 for forming an antistatic layer and a wire bar coater # 6 was applied. Thus, an antireflection laminate 6 was produced. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 1, it was 0.1 m.

[0194] Evaluation example

The following characteristics of the antireflection laminates 1 to 6 obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated.

[0195] (a) Total light transmittance and haze

The total light transmittance (%) and haze (%) of the cured film were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). Table 1 shows the results obtained.

[0196] (b) Pencil hardness

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

[0197] (c) Surface resistance

The surface resistance (Ω / mouth) of the cured film was measured using a high resistance meter (Agilent Technologies Corp. Agilent 4339B) and a resiliency cell 16008B (Agilent Technology Co., Ltd.) The measurement was performed under an applied voltage of 100V. The results obtained are shown in Table 1.

[0198] (d) Reflectance

The reflectance of the obtained antireflection laminate was measured with a spectral reflectance measuring device (automatic spectrophotometer U—3410 incorporating Hitachi Sample Chamber Integrating Sphere 150-09090, manufactured by Hitachi, Ltd.). The reflectance was measured and evaluated in the range of ˜700 nm. Specifically, using the reflectance of aluminum deposited film as the standard (100%), the antireflection product at each wavelength The reflectance of the layered body (antireflection film) was measured. Table 1 shows the reflectance at a wavelength of 550 nm.

[0199] (e) Scratch resistance test 1 (steel wool resistance)

The steel wool resistance test of the antireflection laminate was performed by the following method. In other words, steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with a load of 500 g. Under the conditions described above, rubbing was repeated 10 times, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.

◯: Almost no peeling or scratching of the cured film is observed.

Δ: Fine and scratches are observed in the cured film.

X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film.

The results obtained are shown in Table 1.

[0200] (f) Scratch resistance test 2 (cloth abrasion resistance)

The cloth rubbing resistance test of the antireflection laminate was carried out by the following method. That is, a non-woven fabric (B EMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is subjected to a load lOOOg. By rubbing repeatedly 20 times, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria.

◯: Almost no peeling or scratching of the cured film is observed.

Δ: Fine and scratches are observed in the cured film.

The results obtained are shown in Table 1.

[0201] (g) Chemical resistance test (ethanol resistance test)

The ethanol resistance test of the cured film was performed by the following method. That is, a non-woven fabric soaked with ethanol (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.) Was repeatedly rubbed 20 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. ◯: Almost no peeling or scratching of the cured film is observed.

Δ: Fine and scratches are observed in the cured film.

X: Peeling occurred on a part of the cured film, or streak scratches occurred on the surface of the cured film. The results obtained are shown in Table 1.

[table 1]

ε

1 O ○ ○

Comparative Example Comparative Example Example Proportional 32321 X

Anti-slip anti-slip anti-stop anti-stop anti-stop

! «Layered body layered body« Browth body layered body layered body layered body 654321

Grain-containing assembly (film) thickness of 1cm ε--tc

t 1 ○ ○ ○

Antistatic layer forming composition (film) assembly thickness 1

X

Antistatic layer forming composition (film) fixing thickness 2 ο

Folding low refractive index layered assembly (film) thickness 1 e

E Folding low bending layer assembly (film) thickness 2

1 1 o X: ○ ○ ○

Anti-laminar layer properties evaluation anti X

() All-line transmission (light excess%) a

() Zu ()% Hea

ε O o

1 ○ ○ ○

(Anti) surface resistance () surface Ω / mouth Xc

o (M () emissivity (anti-%) d

E Scratch () Resistance 卜 test 1e

B

1 1 1) Scratch resistance Tet 2

σ¾ o 〇 o 〇

X () Chemical resistance product Tetos g

o so

ε

a O

O

1 1 ○ o ○

X

From the results in Table 1, the liquid curable composition (antistatic layer formation) containing the photopolymerization initiator (C) having a molar extinction coefficient at 313 nm of 5, OOOLZmol 'cm or less, which constitutes the laminate of the present invention, is shown in Table 1. The antireflective laminate having an antistatic layer formed from the composition for use) has an excellent antistatic performance with a small surface resistance. In contrast, Comparative Example 1 using the antistatic layer-forming composition 2 containing a photopolymerization initiator other than the component (C) contains a large amount of phosphorus-containing acid-tin particles. First, if an antistatic layer is provided, the surface resistance value is the same level as in Comparative Examples 2 and 3.

Industrial applicability

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

The laminate of the present invention mainly includes, for example, a protective film for touch panels, a transfer foil, a hard coat for optical disks, a window film for automobiles, an antistatic protective film for lenses, and a surface protective film for high-design containers such as cosmetic containers. Anti-static function for various display panels such as CRT, liquid crystal display panel, plasma display panel, electrification luminescence display panel, etc. as a hard coat for the purpose of preventing surface scratches and dust from static electricity. As an attached antireflection film, it can be used as an antireflection film with an antistatic function for plastic lenses, polarizing films, solar battery panels and the like.

The laminate of the present invention prevents scratches (scratches) such as plastic optical parts, touch panels, film-type liquid crystal elements, plastic casings, plastic containers, flooring materials as building interior materials, wall materials, artificial stones, etc. It can be suitably used as a hard coating material for preventing contamination, an adhesive for various substrates, a sealing material, a binder material for printing ink, and the like.

Claims

The scope of the claims

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

The antistatic layer comprises the following components (A) to (C):

(A) Phosphorus-containing tin oxide particles

The low refractive index layer comprises the following components (D) and (E):

(E) Particles mainly composed of silica

2. The laminate according to claim 1, wherein the antistatic layer has a thickness of 0.05 to 30 111.

[3] Ethylenically unsaturated group-containing fluorine-containing polymer containing 40% by mass or more of the fluorine (D

)But,

A hydroxyl group-containing fluoropolymer,

The laminate according to claim 1 or 2, wherein the laminate is obtained by reacting a compound containing a functional group capable of reacting with a hydroxyl group and an acetylenically unsaturated group.

[4] The hydroxyl group-containing fluoropolymer is represented by the following structural units (a), (b) and when the total of (c) is 100 mol ^_0/0, the following structural units (a) 20 to 70 mole ⁰ / ₀ , (1)) 1 to 70 mol% and (ji) 5 to 70 mol%, and

The laminate according to claim 3, which has a polystyrene-reduced number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography.

(a) Structural unit represented by the following formula (1)

(b) Structural unit represented by the following formula (2)

(c) Structural unit represented by the following formula (3)

[Chemical 21]

[In the 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)]

[Chemical 22]

HR ³ —— C— C—— (2) HR ⁴

2

[Chemical 23]

[In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents — (CH ² ) — OR ² ′ or — OCOR ²⁷

2

(R ²⁷ represents a hydrogen atom, a hydroxyalkyl group or a glycidyl group, and V represents a number of 0 to 2)]

The hydroxyl group-containing fluoropolymer is further derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a), (b) and (c). The laminate according to claim 3 or 4, wherein the unit (d) contains 0.1 to L0 mol part.

(d) Structural unit represented by the following general formula (4)

[Chemical 24]

Further, the hydroxyl group-containing fluoropolymer contains 0.1 to 5 mole parts of the following structural unit (f) with respect to 100 mole parts in total of the structural units (a), (b) and (c). The laminated body according to any one of claims 3 to 5, which is contained.

(f) A structural unit represented by the following general formula (5).

[Chemical 25]

F R

C- — C

F F

[In general formula (5), R ^1Q 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 an isocyanate group, a carboxyl group, an acid halide, and an acid anhydride group. body.

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

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

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