WO2006134834A1

WO2006134834A1 - Liquid hardenable composition, hardened film and antistatic laminate

Info

Publication number: WO2006134834A1
Application number: PCT/JP2006/311599
Authority: WO
Inventors: Shingo Itai; Noriyasu Shinohara; Takayoshi Tanabe; Hiroomi Shimomura; Takaro Yashiro; Tetsuya Yamamura; Ryoji Tatara; Shin Hatori
Original assignee: Jsr Corporation
Priority date: 2005-06-13
Filing date: 2006-06-09
Publication date: 2006-12-21
Also published as: TW200712113A

Abstract

A laminate comprising at least a base material and a hardened film layer obtained by hardening of a liquid hardenable composition containing the following components: (A) particles composed mainly of tin-containing indium oxide (ITO) wherein the primary particle diameter thereof is 20 nm or less and the secondary particle diameter 50 nm or less, (B) compound having two or more polymerizable unsaturated groups in each molecule, (C) photopolymerization initiator, and (D) solvent.

Description

Specification

Liquid curable composition, cured film and antistatic laminate

Technical field

[0001] The present invention relates to a liquid curable composition, a cured film thereof, and an antistatic laminate. More specifically, it has excellent curability and various substrates such as plastics (polycarbonate, polymethylmetatalylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cell mouthwater resin, ABS, etc. Coatings with excellent antistatic properties, hardness, scratch resistance, and transparency on the surfaces of resin, AS resin, norbornene resin, etc., metal, wood, paper, glass, ceramics, slate, etc. The present invention relates to an antistatic laminate comprising a liquid curable composition capable of forming (A) and a cured film layer obtained by curing the composition.

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-described problems, and is a coating film excellent in curability and excellent in antistatic property, hardness, scratch resistance, and transparency on the surface of various base materials. It is an object of the present invention to provide a liquid curable composition capable of forming a coating) and a cured film thereof.

[0014] The present invention can also exhibit sufficient antistatic performance even when the amount of the conductive particles is small, is excellent in curability, and has antistatic properties on the surface of various substrates. Hardness, and An antistatic laminate having a cured film layer obtained by curing a liquid curable composition that has excellent scratch resistance and can form a coating film (film) having both transparency and surface resistance, and in particular, antistatic An object is to provide an antireflection film laminate having a function.

It is another object of the present invention to provide an antireflection laminate having excellent scratch resistance and stain resistance.

As a result of earnest research to solve the above-mentioned problems, the present inventor has found that a tin-containing indium oxide particle having a specific particle size, a compound having two or more polymerizable unsaturated groups in the molecule, and photopolymerization initiation By using a composition containing an agent and a solvent, the antistatic performance is exhibited even when the amount of the conductive particles is small compared to the conventional one, and the transparency is not impaired! /, And a cured film can be obtained. The present invention has been completed by finding out what can be done.

The inventor has also found that the above object can be achieved by a laminate having a cured film layer obtained by curing the composition, and has completed the present invention.

Furthermore, this cured film layer is combined with a low refractive index film obtained by curing a specific ethylenically unsaturated group-containing fluoropolymer and a curable resin composition containing silica particles, thereby providing an antireflection laminate. The present invention was completed by finding that the abrasion resistance and contamination resistance of the body were improved.

That is, the present invention provides the following liquid curable composition, cured film, method for producing the cured film, laminate, and method for producing the laminate.

1. The following components (A), (B), (C) and (D):

(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less

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

(C) Photopolymerization initiator

(D) Solvent

A liquid curable composition containing

2. Content power of the component (A) The liquid curable composition according to the above 1, which is 5 to 40% by weight in the total solid components.

3. The component (A) is tin-containing indium oxide (ITO) surface-treated with a surface treatment agent. 3. The liquid curable composition as described in 1 or 2 above, wherein the liquid curable composition is a particle mainly composed of.

4. The surface treatment agent according to 3 above, wherein the surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. Liquid curable composition.

X— C (= Y) — NH— (1)

[In the formula, X represents NH, 0 (oxygen atom) or S (ion atom), and Y represents O or S. ]

5. A cured film obtained by curing the liquid curable composition according to any one of 1 to 4 above.

6. The cured film as described in 5 above, having a surface resistance value of 1 × 10 ¹³ Ω or lower.

7. A method for producing a cured film, which comprises a step of irradiating the liquid curable composition according to any one of 1 to 4 above with radiation to cure the composition.

8. At least the base material,

A laminate comprising: a cured film layer obtained by curing the liquid curable composition according to any one of 1 to 4 above.

9. The laminate according to 8 above, which is an optical component having an antistatic function.

10. The laminate according to 9 above, which is an antireflection film.

11. The laminate according to any one of 8 to LO above, having a surface resistance value of IX 10 ¹³ Ω or less.

12. The laminated body is an antireflection film in which at least an antistatic layer and a low refractive index layer are laminated on a base material in this order in the order of V and side force,

12. The laminate according to 10 or 11 above, wherein the cured film layer is an antistatic layer.

13. The laminate as described in 12 above, wherein a refractive index of the antistatic layer is higher than a refractive index of the low refractive index layer.

14. Further, the laminate according to any one of 8 to 13 above, wherein a hard coat layer is formed on a substrate.

15. The low refractive index layer is

The following ingredients (G) and (及び):

(G) i containing at least one isocyanate group and at least one ethylenically unsaturated group With compound,

A hydroxyl group-containing fluoropolymer,

An ethylenically unsaturated group-containing fluoropolymer obtained by reacting

(H) particles based on silica,

15. The laminated body according to any one of 12 to 14 above, which is a cured product of a curable resin composition containing:

16. When the total of the following structural units (a) to (c) is 100 mol%, (&) 20 to 70 mol%, (1)) 10 to 70 mol% And (.) 5 to 70 mol%, and

16. The laminate according to the above 15, 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 (11)

(b) Structural unit represented by the following formula (12)

(c) Structural unit represented by the following formula (13)

[Chemical 1]

[Wherein R ¹¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ”(R represents an alkyl group or a fluoroalkyl group)]

[Chemical 2]

HR ¹³

C C— (12)

HR ¹⁴

[Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is an alkyl group,-(CH) —OR ¹⁵

2 c

Is a group represented by OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group] [Chemical 3]

HR ¹⁶

― C― † ― (13)

H (CH ₂ ) _v OR ¹⁷

[Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ¹⁷ represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]

17.The hydroxyl group-containing fluoropolymer is further added to the following structural units (d) derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a) to (c). The laminate according to the above 15 or 16, comprising 0.1 to 10 mole parts.

(d) Structural unit represented by the following general formula (14)

[Chemical 4]

_R 18 Si 0 (14)

R ¹⁹

[Wherein R ¹⁸ and R ¹⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenialkyl group or an aryl group]

18. The laminate according to any one of 15 to 17 above, wherein the component (H) is silica particles having an ethylenically unsaturated group on the surface.

19.The component (H) is

A porous material having an average particle diameter of 5 to 50 nm, comprising a hydrolyzate and a Z or hydrolyzed condensate of a key compound represented by the following formula (22) and a key compound represented by the following formula (23): Silica particles (HI)

SiX (22)

Four

R ²⁹ SiX (23)

j 4-j

(X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ Is an alkenyl group having 2 to 8 carbon atoms, an talyloxyalkyl group having 4 to 8 carbon atoms, or A methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3; X in formula (22) and X in formula (23) may be the same or different. )

The laminate according to any one of 15 to 18 above.

20.The component (H) is

Is the key compound represented by the following formula (22), the key compound represented by the following formula (23), and the hydrolyzate and Z or hydrolysis condensate of the key compound represented by the following formula (24)? Porous silica particles (H2) with an average particle size of 5 to 50 nm

SiX (22)

Four

R ²⁹ SiX (23)

j 4-j

R ³⁰ SiX (24)

k 4-k

(X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ Is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, j is an integer of 1 to ^3. R ³ is 1 carbon number -12 fluorine-substituted alkyl group, k represents an integer of 1 to 3. X in formula (22), X in formula (23) and X in formula (24) may be the same or different. May be.)

The laminate according to any one of 15 to 18 above.

21. When the porous silica particles (HI) have a total of 100 mol% of the key compound represented by the formula (22) and the key compound represented by the formula (23), the hydrolysis And Z or a hydrolysis-condensation product have a reactant power of 67 to 99 mol% of the key compound represented by the formula (22) and 33 to 1 mol% of the key compound represented by the formula (23). 20. The laminate according to 19 above.

22. The porous silica particle (H2) force of the key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) When the total is 100 mol%, the hydrolyzate and Z or the hydrolysis condensate are 60 to 98 mol% of the key compound represented by the formula (22) and the key compound represented by the formula (23). 21. The laminate according to the above 20, which also has a reactant power of 1 to 30 mol% and a key compound represented by the formula (24) of 1 to 20 mol%. 23. including a step of forming a cured film layer obtained by curing the composition by applying the liquid curable composition according to any one of the above 1 to 4 on a substrate and irradiating the composition with radiation. The manufacturing method of a laminated body.

[0018] According to the present invention, liquid curing that can form a coating film (coating) having excellent curability and excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. Composition and a cured film thereof can be provided.

According to the liquid curable composition of the present invention, a cured film having both antistatic properties and transparency requirements can be obtained.

According to the present invention, it is possible to provide an antistatic laminate having a cured film obtained by curing the liquid curable composition.

Conventionally, in order to obtain sufficient conductivity using tin-containing indium oxide (ITO), expensive tin-containing indium oxide (ITO) particles had to be blended at a high content (usually about 60% by weight). According to the present invention, even when the content of tin-containing indium oxide (ITO) particles is low, sufficient conductivity can be exhibited, and an antistatic laminate having a cured film having excellent antistatic performance. You can get a body.

Further, according to the present invention, by using fine tin-containing indium oxide (ITO) particles,

Even if the content is kept low, it is possible to achieve both a sufficient surface resistance value and transparency of the cured film, and the laminate of the present invention is an optical component having an antistatic function, particularly an antistatic device. It is useful as an antireflection film having a function.

Furthermore, by forming 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 a basic configuration of a laminate according to 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. 2C is a schematic view showing a second embodiment of the antireflection film with an antistatic function of the present invention.

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

FIG. 2E is a schematic view showing a third embodiment of the antireflection film with an antistatic function of the present invention.

FIG. 2F is a schematic view showing another form of the third form of the antireflection film with an antistatic function of the present invention.

FIG. 3 is an electron micrograph of a cross section of the cured film of the present invention showing a typical state in which ITO particles of component (A) are unevenly distributed on the substrate side.

BEST MODE FOR CARRYING OUT THE INVENTION

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

The laminate of the present invention has at least a substrate and a cured film layer obtained by curing a liquid curable composition containing the following components (A) to (D).

[Liquid curable composition]

(C) Photopolymerization initiator

(D) Solvent

[0022] In addition, the antireflection film, which is a preferred embodiment of the laminate of the present invention, is such that the antistatic layer and the low refractive index layer comprising at least the cured film layer are close to the base material on the base material. The side force is also an antireflection film laminated in this order, and the low refractive index layer is a cured product of a curable resin composition containing the following components (G) and (H).

(G) Ethylenically unsaturated group-containing fluorine-containing weight obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer Coalescence

(H) Silica particles

[0023] I. Laminate

The most basic structure of the laminate of the present invention is shown in FIG. The laminate 1 of the present invention has a base film 10 and a cured film layer 12 formed by curing the liquid curable composition.

The laminate of the present invention only needs to have at least the substrate 10 and the cured film layer 12. Depending on the, various layers may be provided. The layer provided according to the purpose will be described later.

[0024] Since the laminate 1 of the present invention has the cured film layer 12 having excellent scratch resistance and adhesion, it is particularly useful as a hard coat.

In addition, the laminate 1 of the present invention has an antistatic laminate by disposing a cured film layer 12 having an excellent antistatic function on a substrate of various shapes such as a film, a plate, or a lens. Useful as a 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.

[0026] (1) Cured film layer

The cured film layer provided on the substrate of the laminate of the present invention comprises the following liquid curable composition (hereinafter, simply “composition” or “antistatic layer forming composition”). It is obtained by curing, and the laminate can be given a function as a conductive film and a function as Z or a hard coat.

Hereinafter, the liquid curable composition (antistatic layer forming composition) used in the present invention will be specifically described.

1.Component (A)

Component (A) used in the present invention is tin-containing indium oxide (hereinafter, also simply referred to as “ITO”) particles. The component (Α) is an essential component for imparting conductivity (antistatic property) to the cured film obtained by curing the composition of the present invention. The primary particle size of the soot particles is 20 nm or less, and the secondary particle size is 50 nm or less. By setting the particle size of the ITO particles as described above, it is possible to ensure the conductivity (antistatic property) and at the same time maintain the transparency of the cured film. If the primary particle size and the secondary particle size of ITO particles exceed 20 nm and 50 nm, respectively, the transparency of the resulting cured film may be impaired.

The primary particle size of the ITO particles is preferably 15 nm or less, and the secondary particle size is preferably 40η. m or less.

[0027] The primary particle size of the ITO particles of component (A) is a value measured with a transmission electron microscope when the shape is spherical, regardless of the presence or absence of the surface treatment described later, and the shape is needle-like. Thus, in the case of a long and narrow plate, the value obtained as the number average particle size by observing the short axis with a transmission electron microscope.

The secondary particle size of the soot particles of the component (Α) is a value obtained by a dynamic light scattering type particle size distribution measuring device regardless of the presence or absence of surface treatment described later.

[0028] Examples of such commercially available powders of soot particles include a trade name: soot powder manufactured by Fuji Chemical Co., Ltd.

[0029] The soot particles used as the component (Α) can be used in a state of being dispersed in a powder or a solvent. However, since uniform dispersibility is easily obtained, it is preferable to use in a state of being dispersed in a solvent. Yes.

[0030] Examples of commercially available products in which the soot particles used as the component (soot) are dispersed in a solvent include trade name: Houtform NID-20 manufactured by Fuji Chemical Co., Ltd.

[0031] The soot particles used as the component (soot) may be soot particles surface-treated with a surface treatment agent or the like in order to improve dispersibility in a solvent.

Here, examples of the surface treatment agent include alkoxysilane compounds, tetrabutoxysilane, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.

[0032] Specific examples of the alkoxysilane compound include a group of compounds having an unsaturated double bond in the molecule, such as γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, and burtrimethoxysilane. γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and other compounds having an epoxy group in the molecule, γ-aminopropyltriethoxysilane, y-amaminopropyltrimethoxysilane, etc. Compound group having an amino group in the molecule, compound group having a mercapto group in the molecule such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Alkyl silanes such as phenyltrimethoxysilane Etc. can be mentioned. Among these surface treatment agents, γ-mercaptopro Pyrtrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenoltrimethoxysilane, etc. Surface treatment 好 Preferable in terms of dispersion stability of particles.

[0033] Further, as the surface treatment agent, a reactive surface treatment agent having a functional group that is copolymerized or cross-linked with an organic resin (reactive surface treatment agent) is also preferable. Examples of such a surface treatment agent include a compound group having an unsaturated double bond in the molecule, two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or hydrolysis. A compound having a group that forms a silanol group is preferred.

X— C (= Y) — ΝΗ— (1)

[0034] The group represented by the formula (1) is preferably a urethane bond [OC (= 0) —NH, one O—C (═S) —NH and thiourethane bond [—S—C (= 0) — At least one group selected from the group consisting of NH].

[0035] Examples of such a surface treatment agent include urethane bonds [0—C (= 0) NH] and Z or thiourethane bonds [S—C (═O) NH] in the molecule, and two or more polymerizable properties. Examples thereof include alkoxysilane compounds having an unsaturated group. Specifically, a compound represented by the following formula (2) can be exemplified.

[Chemical 5]

Ri

(2)

In the formula, R ¹ is a methyl group, R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, m is 1 or 2, n is an integer of 1 to 5, and X is 1 to 5 carbon atoms 6 divalent alkylene group, Y is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms, Z is an (n + 1) valent chain, cyclic or branched Is a divalent hydrocarbon group having 2 to 14 carbon atoms. In Z, It may contain a single bond.

[0036] The compound represented by the formula (2) can be produced by reacting mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates.

As a preferable production method, for example, an intermediate bonded with a thiourethane bond by reaction of mercaptoalkoxysilanes and diisocyanates is prepared, and then the remaining isocyanate is reacted with a hydroxyl group-containing polyfunctional (meth) acrylate. A method for producing a product bonded with a urethane bond can be mentioned.

[0037] It is to be noted that an intermediate bonded with a urethane bond is first produced by a reaction between a diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate, and then the remaining isocyanate is reacted with a mercaptoalkoxysilane. Even if the same product is obtained, the addition reaction between the mercaptoalkoxysilanes and the (meth) acrylic group occurs simultaneously, so that the purity is lowered and a gel-like product may be formed.

[0038] Examples of mercaptoalkoxysilanes used in the production of the compound represented by formula (2) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltributoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropylmethyldimethoxysilane and the like can be mentioned. Of these, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferable.

[0039] Examples of commercially available mercaptoalkoxysilanes include trade name: SH6062 manufactured by Toray Dow Co., Ltd.

[0040] The diisocyanates include, for example, 1,4-butylene diisocyanate, 1,6 monohexylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated bisphenolate. Α diisocyanate, 2,4-tonylene diisocyanate, 2,6-toluene diisocyanate, and the like. Of these, 2,4-toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylylene diisocyanate are preferable.

[0041] Commercially available products of polyisocyanate compounds include, for example, product names manufactured by Mitsui Nisso Urethane Co., Ltd .: TDI—80Z20, TDI—100, MDI—CR100, MDI—CR300, MDI—PH, NDI, manufactured by Nippon Polyurethane Industry Co., Ltd. Trade name: Coronate T, Millionate ΜΤ, Millionone MR, HDI, Takeda Pharmaceutical Co., Ltd. Product name: Takenate 600, etc.

[0042] Examples of the hydroxyl group-containing polyfunctional (meth) atalylates include, for example, trimethylolpropandi (meth) atalylate, tris (2-hydroxyethyl) isocyanurate di (meth) atalylate, pentaerythritol. Examples thereof include tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. Of these, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred. These form two or more polymerizable unsaturated groups in the compound represented by the formula (2).

[0043] These mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates may be used alone or in combination of two or more.

[0044] Preference is given to the production of the compound represented by formula (2)! /, The compounding ratio of mercaptoalkoxysilanes, di-socyanates, and hydroxyl group-containing polyfunctional (meth) acrylates is mercaptoalkoxysilanes. The molar specific force S of the diisocyanates with respect to is preferably 0.8 to 1.5, more preferably 1.0 to 1.2. When this molar ratio is less than 0.8, the storage stability of the composition may be lowered, and when it exceeds 1.5, the dispersibility may be lowered.

Further, the molar ratio of the hydroxyl group-containing (meth) acrylates to the diisocyanates is preferably from 1.0 to 1.5, more preferably from 1.0 to 1.2. If this mono ktt force is less than S1.0, gelation may occur, and if it exceeds 1.5, the antistatic property may deteriorate.

[0045] The compound represented by formula (2) is usually preferably produced in dry air in order to prevent anaerobic polymerization of acrylic groups and to prevent hydrolysis of alkoxysilanes. The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.

[0046] During the production of the compound represented by the formula (2), a known catalyst may be added in the urethane reaction for the purpose of shortening the production time. Examples of the catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin di (2-ethylhexanoate), and octyltin triacetate. The amount of the catalyst added is from 0.01 to 1% by weight based on the total amount with the diisocyanates.

[0047] Further, for the purpose of preventing thermal polymerization of the compound represented by the formula (2), a thermal polymerization inhibitor is added during the production. It may be added. Examples of the thermal polymerization inhibitor include P-methoxyphenol and hydrated quinone. The addition amount of the thermal polymerization inhibitor is preferably 0.01% by weight to 1% by weight with respect to the total of the hydroxyl group-containing polyfunctional (meth) acrylates.

[0048] The compound represented by formula (2) can also be produced in a solvent. As the solvent, for example, a solvent having a boiling point of 200 ° C. or lower that does not react with mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates can be appropriately selected. Specific examples of such solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, and hydrocarbons such as toluene and xylene. Can be mentioned.

In the present invention, (A) the surface-treated ITO particles can be produced by hydrolyzing the surface treatment agent in the presence of the ITO particles. The preferred manufacturing method is (A) IT

In this method, water is added to a mixture of O particles, a surface treatment agent, and an organic solvent, followed by hydrolysis.

In this production method, the alkoxy group is temporarily converted into a silanol group (Si—OH) by hydrolysis of the surface treatment agent, and this silanol group reacts with the metal hydroxide (M—OH) on the ITO particles. Then, it is presumed that the surface treatment agent is fixed on the ITO particles by forming a metalloxane bond (M—O—Si).

[0050] The compounding amount of the surface treatment agent is preferably 0.1 to 50 parts by weight, more preferably 1 to 35 parts by weight with respect to 100 parts by weight of the (A) ITO particles. If the surface treatment agent is less than 0.1 part by weight, the cured film may have insufficient wear resistance, and if it exceeds 50 parts by weight, the antistatic performance may be insufficient.

[0051] The amount of water is preferably 0.5 to 1.5 equivalents relative to the total alkoxy equivalent in the surface treatment agent, and 0.5 to 5 with respect to 100 parts by weight of the surface treatment agent. It is preferable to add 0 part by weight. The water used is preferably ion exchange water or distilled water.

[0052] The hydrolysis reaction can be carried out in the presence of an organic solvent by heating and stirring at a temperature of 0 ° C to the boiling point of the component, usually 30 to 100 ° C, for 1 to 24 hours. As the organic solvent, when (A) ITO particles dispersed in an organic solvent in advance are used, it can be carried out as they are, but an organic solvent may be added separately. [0053] It should be noted that an acid or a base may be added as a catalyst in order to promote the reaction during the hydrolysis.

Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, toluene sulfonic acid, phthalic acid, malic acid, tartaric acid, malonic acid, formic acid, oxalic acid, methacrylic acid, acrylic acid, Examples thereof include organic acids such as itaconic acid, and ammonium salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride.

Examples of the base include amines such as aqueous ammonia, triethylamine, tributylamine, and triethanolamine. A preferable catalyst is an acid, and an organic acid is more preferable. The amount of these catalysts added is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound.

[0054] By adding a dehydrating agent at the end of the hydrolysis reaction, (A) the hydrolyzate of the surface treatment agent can be more effectively fixed on the ITO particles.

Examples of the dehydrating agent are organic carboxylic acid orthoesters and ketals. Specifically, for example, orthoformate methyl ester, orthoformate ethyl ester, orthoacetic acid methyl ester, orthoacetic acid ethyl ester, etc., acetone dimethyl ketal, jetyl ketone dimethyl ketal, Examples include cetophenone dimethyl ketal, cyclohexanone dimethyl ketal, cyclohexanone jetyl ketal, and benzophenone dimethyl ketal. Among them, preferred are organic carboxylic acid orthoesters, and more preferred are orthoformate methyl ester and orthoformate ethyl ester.

[0055] These dehydrating agents can be added in an amount of not less than 10 moles and not more than 10 moles, preferably not less than 3 moles and not more than the amount of water contained in the composition. If it is less than the equivalent mole, the storage stability may not be sufficiently improved. These dehydrating agents are preferably added after the preparation of the composition. This promotes the storage stability of the composition and the formation of chemical bonds between the silanol groups in the hydrolyzate of the surface treatment agent and (A) ITO particles.

[0056] Since the (A) ITO particles surface-treated with such a surface treatment agent have extremely good dispersibility in the solvent, the surface treatment agent is mediated by a siloxy group (Si—O—). It is presumed that (A) it is fixed on the surface of ITO particles by chemical bonding. In the present invention, the (A) ITO particles surface-treated with a reactive surface treatment agent are particularly referred to as reactive particles (RA).

The blending amount of component (A) is not particularly limited, but is preferably 5 to 40% by weight, more preferably 7 to 35% by weight in 100% by weight of the total solid content of the composition of the present invention. The same applies when component (A) is surface treated. If the blending amount is less than 5% by weight, the antistatic property may be inferior, and if it exceeds 40 parts by weight, the film forming property of the coating film may be inferior. Here, the blending amount of component (A) refers to the blending amount as a solid content, and does not include a dispersion medium.

[0058] 2. Component (B)

Component (B) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule. The cured film obtained by curing the composition of the present invention has film-forming properties and transparency. It is an ingredient to be given. By using such a component (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

[0059] 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, tricyclodecane Dirudimethanol di (meth) acrylate and the starting alcohols in the production of these compounds Poly (meth) acrylates of ethylene oxide or propylene oxide with two or more in the molecule Oligoesters having (meth) atallyloyl groups (Meth) acrylates, Oligoethers (Meth) acrylates, Oligourethanes (Meth) acrylates, and Examples include oligoepoxy (meth) acrylates.

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 Rate, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclo Decandyl dimethanol di (meth) acrylate is preferred! These (B) components may be used individually by 1 type, and may use 2 or more types together.

[0060] The amount of component) is preferably 55 to 94% by weight, more preferably 60 to 92% by weight, based on 100% by weight of the total solid content of the composition of the present invention. If the blending amount of component (B) is less than 55% by weight, the resulting cured product may have poor transparency, and if it exceeds 94% by weight, the antistatic property may be inferior.

[0061] 3. Component (C)

Component) is a photopolymerization initiator and is added to increase the curing rate when the composition of the present invention is cured by irradiation with radiation.

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

[0062] The blending amount of component (C) is preferably 0.1 to 15% by weight, more preferably 0.5 to LO weight, based on 100% by weight of the total solid content of the composition of the present invention. %. Component (C) can be used alone or in combination of two or more.

[0063] Examples of the component (C) include 1-hydroxycyclohexyl phenol ketone, 2,2 dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole , 3-methylacetophenone, 4-clobenbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ether, benzil dimethyl ketal, 1 Mono (4 isopropyl phenol) 2 hydroxy 2 methyl Propane 1-one, 2-Hydroxy-1-2-Methyl-1-Fane Propane 1-one, Thioxanthone, Jetylthioxanthone, 2-Isopropylthixanthone, 2-Chlorothioxanthone, 2-Methyl-11 ) Fuel] 2 Morpholino-propane 1-one, 2, 4, 6 Trimethylbenzoyl diphenylphosphine oxide, bis (2,6 dimethoxybenzoyl) -1,2,4,4 trimethylpentylphosphine oxide, etc. Can be mentioned.

[0064] 4. Component (D)

Component (D) used in the present invention is a solvent, and is a component for adjusting the fluidity of the composition of the present invention.

[0065] The solvent as the component (D) in the composition of the present invention has a concentration of the total solid content of the composition of 0.

It is preferable to add so that it may become 5 to 75 weight%. That is, (D) the amount of the solvent added is preferably within the range of 33.3 to 19,900 parts by weight when the total solid content of the composition of the present invention is 100 parts by weight. The reason for this is that (D) when the amount of the solvent added is less than 33.3 parts by weight, the viscosity of the composition may increase and the coatability may decrease, whereas when the amount exceeds 19,900 parts by weight. In other words, the resulting cured product is too thin and may not exhibit sufficient hardness.

[0066] The type of the solvent is not particularly limited, but usually a solvent having a boiling point of 200 ° C or lower 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.

[0067] Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxhetano monoole, diethyleneglycolenomonoethinoreethenole, 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, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), and the like. Esters include, for example, ethyl acetate, butyl acetate, ethyl lactate, methyl acetate And ethyl acetate. Examples of hydrocarbons include toluene and xylene. Examples of amides include N, N dimethylformamide, N, N dimethylacetamide, N-methylpyrrolidone and the like.

[0068] In the case of a dispersion in which the ITO particles of component (A) are dispersed in a dispersion medium, the dispersion medium is different from the dispersion medium that may be used as the solvent of component (D) as it is. It is possible to use only a solvent, or a combination of a dispersion medium and another solvent can be used as a solvent for component (D)!

[0069] 5. Other compounds having a polymerizable unsaturated group

In the composition of the present invention, as a component other than components (A) to (D), other compounds having a polymerizable unsaturated group (component (E)) can be blended as necessary. Here, the component is a compound having one polymerizable unsaturated group in the molecule.

Specific examples of the component (E) include, for example, N-bulupyrrolidone, N-vinylcaprolactam-containing burata-containing ratata, isobornyl (meth) acrylate, boryl (meth) acrylate, tricyclodehydrate. Containing alicyclic structures such as force (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 (3).

^{CH -C (R 4) -COO (} R 5 0) -Ph-R 6 Formula (3)

2 P

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 to 9 alkyl group, Ph represents a fullerene group, and p represents a number of 0 to 12, preferably 1 to 8.)

[0070] Commercially available components (E) 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.).

[0071] 6. Non-conductive particles

In the present invention, the liquid curable composition is obtained by reacting non-conductive particles or non-conductive particles with an alkoxysilane compound in an organic solvent within a range that does not cause problems such as separation and gelling. You can use the resulting particles together!

[0072] By using non-conductive particles in combination with ITO particles as component (A), the antistatic function, that is, the surface resistance when a cured film is maintained while maintaining a value of 10 ¹³ Ω or lower, Abrasion resistance can be improved.

[0073] As such non-conductive particles, specifically, silicon oxide, acid aluminum, acid Oxide particles such as zirconium oxide, titanium oxide, cerium oxide, etc., or oxides containing two or more elements selected from group forces consisting of silicon, aluminum, zirconium, titanium, and cerium Particles can be mentioned.

[0074] The primary particle diameter of the non-conductive particles is preferably 0.1 m or less, more preferably 0.001 to 0.05 μm, as a value obtained by observation with a transmission electron microscope. It is. If it exceeds 0.1 m, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.

[0075] When blending non-conductive particles in the composition of the present invention, 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 nonconductive particles. The hydrolysis treatment of the non-conductive particles and the alkoxysilane compound in an organic solvent can be performed in the same manner as the method for treating the oxide particles as the component (A) described above.

[0076] Commercially available non-conductive particles include, for example, acid silica particles (for example, 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 can be listed. In addition, powder silica is manufactured by 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 Industry 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. Can be mentioned.

In addition, as the water dispersion of acid aluminum (alumina), trade names of 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.

[0077] The blending ratio of the non-conductive particles is preferably 0.1 to 35% by weight, more preferably 1 to 30% by weight in 100% by weight of the total solid content of the composition of the present invention. [0078] 7. Additives

In the composition of the present invention, as other additives, an antioxidant, an ultraviolet absorber, a photostabilizer, a thermal polymerization inhibitor, a leveling agent, a surfactant, a lubricant and the like are blended as necessary. can do. Anti-oxidation agent manufactured by Chino Specialty Chemicals Co., Ltd. Trade name: Ilganox 1010, 1035, 1076, 1222, etc. Ultraviolet absorbers manufactured by Ciba Specialty Chemicals Co., Ltd. Product name: Tinuvin P234, 320 , 326, 327, 328, 213, 329, manufactured by Sipro Kasei Co., Ltd. Product name: Seasorb 102, 103, 501, 202, 712, etc. As a light stabilizer, manufactured by Ciba Specialty Chemicals Co., Ltd. Product name: Tinuvin 292 144, 622L D, Sankyo Co., Ltd. trade name: Sanol LS770, LS440, Sumitomo Chemical Co., Ltd. trade name: Sumisorp TM-061.

[0079] The viscosity of the composition of the present invention thus obtained is usually 1 to 20, 0 OOmPa's, preferably 1 to 1, OOOmPa's at 25 ° C.

[0080] As described above, the solid content excluding the solvent (D) of the composition of the present invention is preferably in the range of 0.5 to 75% by weight. If the solid content is less than 0.5% by weight, the resulting cured product may be too thin and may not exhibit sufficient hardness. If it exceeds 75% by weight, the viscosity of the composition will increase. As a result, applicability may decrease.

[0081] 8. Method for preparing composition for forming antistatic layer

The liquid curable composition of the present invention comprises the above components (A) to (D) and, if necessary, the above-mentioned compounds having other polymerizable unsaturated groups, non-conductive particles, and other additives. In addition, it is obtained by mixing.

[0082] 9. Method for forming cured film layer

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

If the surface resistance of the obtained cured film layer is 1 X 10 ¹³ Ω or less, sufficient antistatic performance can be exhibited, usually 1 to 10 ¹² Ω or less, preferably 1 to 10 ^{1 ()} Ω In the following, it is more preferably 1 to 10 ⁸ Ω. If the surface resistance exceeds 1 Χ 10 ¹² Ω well, the antistatic performance is sufficient and the dust is not easily attached or the attached dust cannot be removed easily. There is a case.

The surface resistance of the laminate (antireflection film with an antistatic function) of the present invention when a low refractive index layer or the like described later is formed on a cured film layer having a surface resistance value in the above range is usually normal. 1 Χ 10 ¹³ Ω / mouth or less, preferably Ι Χ ΙΟ ^ Ω / mouth or less, more preferably 1 Χ 10 ⁸ Ω / mouth or less.

[0083] The method for applying the composition for forming an antistatic layer is not particularly limited! /, But for example, a known method such as roll coating, spray coating, flow coating, diving, screen printing, ink jet printing or the like is applied. be able to.

[0084] 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.

[0085] The thickness of the cured film layer is preferably 0.05-30 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 m. On the other hand, when used as an antistatic film for an optical film, 0.05 to L0 m is preferable.

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

[0086] (2) Substrate

Base materials used in the laminate of the present invention are metal, ceramics, glass, plastic, wood The material, slate, etc. are not particularly limited and may be appropriately selected depending on the purpose of use.However, as a material capable of exhibiting high productivity and industrial utility such as radiation curability, for example, a film or a fiber-like substrate. Preferably applied. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene Z polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, and diethylene glycol diaryl. Examples include carbonate (CR-39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene-based resin).

[0087] It should be noted that since the tin-containing indium oxide (ITO) particles of component (A) are unevenly distributed on the substrate side and higher conductivity (antistatic property) is obtained, the antistatic layer forming composition is applied. The base material to be used is preferably a base material such as polyester or polyethylene terephthalate (PET) in which the surface to which the composition for forming an antistatic layer is applied is subjected to an easy adhesion treatment.

Examples of such easy adhesion treatment include corona discharge treatment and easy adhesion layer coating treatment.

A preferred example of a commercially available base material subjected to easy adhesion treatment is polyester film A4300 (manufactured by Toyobo Co., Ltd.).

[0088] The thickness of the substrate should be appropriately set according to the purpose and is not particularly limited.

~ 5000 μm, preferred <ί or 50-2000 μm.

[0089] II. Antireflection film with antistatic function

Next, the structure 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 FIGS. 2A to 21.

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.

FIG. 2A shows a first embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function. The antireflection film 2 with an antistatic function is formed by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a base material 10, and further thereon. A low refractive index layer 18 is formed. In the first embodiment, the antistatic layer 12 has both an antistatic function and a function as a hard coat layer. In the first embodiment, the refractive index of the antistatic layer 12 needs to be higher than the refractive index of the low refractive index layer 18.

[0090] 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 also be provided separately. In this case, the hard coat layer _n is provided between the antistatic layer 12 and the low refractive index layer 18. In this case, 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 FIG. 2C.

FIG. 2D 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 base material 10, and further thereon. The high refractive index layer 16 and the low refractive index layer 18 are formed in this order. In the second 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 refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16. It must be higher than the refractive index.

[0092] In the second mode, a mode in which a hard coat layer is separately provided is also possible as in the first mode. The hard coat layer 11 can be provided between the antistatic layer 12 and the high refractive index layer 16. These configurations are shown in Figure 2F.

[0093] FIG. 2G 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 obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the liquid curable composition on a base material 10, and further thereon. The middle refractive index layer 14, the high refractive index layer 16, and the low refractive index layer 18 are formed in this order. In the third form, the antistatic layer 12 has both an antistatic function and a function as a hard coat.

[0094] In the third embodiment, it is also possible to provide a hard coat layer separately as in the first embodiment. The hard coat layer 11 can be provided between the antistatic layer 12 and the medium refractive index layer 14. These forms are shown in FIG. The layers other than the antistatic layer and the substrate provided in the first to third embodiments of the antireflection film with an antistatic function will be described.

(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 a preferred embodiment in which the laminate of the present invention is used as an antireflection film, a low refractive index layer is formed using a curable resin composition containing components (E) and (F) described later.

[0096] (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.

[0097] Specific examples of metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, oxide-zinc (ZnO) particles, antimony-containing ZnO, and Al-containing Z ηθ. Particles ZrO particles, TiO particles, silica-coated TiO particles, Al 2 O 3 / 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.

[0098] (4) Medium refractive index layer

When combining layers with three or more refractive indexes, the refractive index is 1.50 ~: L 90 Therefore, a layer having a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer is referred to as a middle refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to L80, more preferably 1.50 to L75. The middle refractive index layer has a thickness in the range of 0.05 to 0.20 / zm.

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

[0099] Specific examples of metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, A1-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.

[0100] 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 middle refractive index layer. Can be reduced and the glare can be reduced.

[0101] (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. Alternatively, the refractive index of the coated layer is usually in the range of 1.45 to 1.70, preferably 1.45 to L60.

[0102] (6) Substrate for use as antireflection film

The material of the substrate when the laminate of the present invention is used as an antireflection film must be transparent. For example, polycarbonate, polymethylol methacrylate, polystyrene Z polymethyl methacrylate copolymer, polystyrene , Polyester, polyolefin, triacetyl cellulose resin, diethylene glycol diaryl carbonate (CR-39), ABS Examples thereof include resin, AS resin, polyamide, epoxy resin, melamine resin and cyclized polyolefin resin (for example, norbornene-based resin).

As described above, since the tin-containing indium oxide (ITO) particles of the component (A) are unevenly distributed on the substrate side and higher conductivity (anti-static property) is obtained, the base subjected to the easy adhesion treatment is used. Material is preferred. Examples of such easy adhesion treatment include corona discharge treatment and easy adhesion layer coating treatment.

[0103] Polyester film A4300 (manufactured by Toyobo Co., Ltd.) subjected to easy adhesion treatment is coated with the liquid curable composition of the present invention and cured to form the ITO particles of component (A). Fig. 3 shows an electron micrograph of a cured film cross section showing a typical state of uneven distribution on the material side. In FIG. 3, the lower part is the substrate side, the upper part is the air side, and it can be seen that the ITO particles are unevenly distributed on the substrate side.

[0104] 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.

[0105] (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.

[0106] The laminate of the present invention has scratches on, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic casings, plastic containers, flooring materials for building interior materials, wall materials, artificial stones, etc. It can be suitably used as a hard coating material for preventing (scratching) and preventing contamination; an adhesive for various base materials, a sealing material; a binder material for printing ink, and the like.

[0107] 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.

[0108] 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 cured film layer. The low refractive index layer formed in the laminate of the present invention comprises (G) a curable polymer containing an ethylenically unsaturated group and (i) a curable resin composition containing silica particles (hereinafter referred to as “low refractive index”). The cured product is preferably composed of a composition for forming a rate layer “t”.

Hereinafter, components (G) and (H) will be described.

[0109] 1. Component (G)

The ethylenically unsaturated group-containing fluoropolymer (G) used for the composition for forming a low refractive index layer is composed of a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It can be obtained by reacting with a fluoropolymer.

[0110] (1) Compound containing one isocyanate group and at least one ethylenically unsaturated group

The compound containing one isocyanate group and at least one ethylenically unsaturated group contains one isocyanate group and at least one ethylenically unsaturated group in the molecule. If it is a compound, it is not 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.

[0111] Such a compound reacts with diisocyanate and a hydroxyl group-containing (meth) acrylate. Let me synthesize it.

Examples of diisocyanates include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexenoylisocyanate), 1,3-bis (isocyanate) Methyl) cyclohexane is preferred.

[0112] As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.

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. can be obtained.

[0113] (2) Hydroxyl-containing fluoropolymer

The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).

(a) A structural unit represented by the following formula (11).

(b) A structural unit represented by the following formula (12).

(c) A structural unit represented by the following formula (13).

[0114] [Chemical 6]

F R

C— — C

F F

[0115] [Chemical 7]

HR ¹³ —— C, — C—— (12) HR ⁴

2 Is a group represented by OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group]

[Chemical 8]

HR ¹⁶

H (CH ₂ ) _v OR ¹⁷

[0117] (i) Structural unit (a)

In the above formula (11), the fluoroalkyl group of R ¹¹ and R ¹² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a no-fluorine hexyl group. And a fluoroalkyl group having 1 to 6 carbon atoms such as perfluorocyclohexyl group. Examples of the alkyl group for R ¹² 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.

[0118] 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 butyl ether) s such as propoxypropyl butyl ether) may be used alone or in combination of two or more.

Among these, hexafluoropropylene and perfluoro (alkyl buulete) ) Or perfluoro (alkoxyalkyl butyl ether) is more preferred, and it is further preferred to use a combination of these! /.

[0119] The content of the structural unit (a), the sum of the structural units (a) ~ (c) is 100 mol%, 20 to 70 mole ^_0/0. This is because if the content is less than 20 mole ^_0/0, which is characteristic of the optically fluorine-containing material where the application is intended, it may be a case where the expression of the low refractive index becomes difficult, whereas This is because if the content exceeds 70 mol%, the solubility of the hydroxyl group-containing fluorine-containing polymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.

For these reasons, the content of the structural unit (a) is more preferably 25 to 65 mol%, and further preferably 30 to 60 mol%! /.

[0120] (ii) Structural unit (b)

In the formula (12), examples of the alkyl group of R ¹³ or R ¹⁴ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group. Examples of the alkoxycarbonyl group represented by R ¹⁵ include a methoxycarbonyl group and an ethoxycarbonyl group.

[0121] 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 ethereol, ethino levinino le ethere, _n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert -Butyl vinyl etherenole, n-pentinolevinoreethenole, n-hexenolevinoreethenore, n-year-old cubinorebi-noreethenore, n-dodecinolevinorethenore, 2-ethinorehexinolevinoreteol, cyclohexyl vinyl ether Alkyl butyl ethers or cycloalkyl alkyl ethers such as: ethyl ether such as ethyl allyl ether and butyl allyl ether; butyl acetate, butyl propionate, butyl butyrate, pivalate butyl, strength benzoate, versatic Acid bull, Carboxylic acid butyl esters such as tea acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2- (ethoxy) ethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, etc. Rylic acid esters; single (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. may be used alone or in combination of two or more.

[0122] The content of the structural unit (b) is 10 to 70 mol% when the total of the structural units (a) to (c) is 100 mol%. The reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, the content exceeds 70 mol%. This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.

For these reasons, the content of the structural unit (b) is more preferably 20 to 60 mol%, and even more preferably 30 to 60 mol%! /.

[0123] (iii) Structural unit (c)

In the formula (13), as the hydroxyalkyl group of R ¹⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl Group, 6-hydroxyhexyl group and the like.

[0124] 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.

[0125] The content of the structural unit (c) is preferably 5 to 70 mol% when the total of the structural units (a) to (c) is 100 mol%. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in an organic solvent may decrease. On the other hand, if the content exceeds 70 mol%, the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.

For these reasons, the content of the structural unit (c) is more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol%.

[Iv] (iv) Structural unit (d) and structural unit (e)

The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

[0127] (d) A structural unit represented by the following formula (14).

[Chemical 9]

[0128] In the formula (14), the alkyl group represented by R ¹⁸ or R ^{19 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group. The halogenoalkyl group is a trifluoromethyl group, C1-C4 fluoroalkyl group, such as perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc. Examples of aryl groups include a phenyl group, a benzyl group, and a naphthyl group. It is done.

[0129] The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (14). Examples of such an azo group-containing polysiloxane compound include compounds represented by the following formula (15).

[0130] [Chemical 10]

(15)

Is the same or different hydrogen atom, alkyl group or cyan R ^{24 to} R ²⁷ represent a hydrogen atom or an alkyl group which may be the same or different, d and e are numbers 1 to 6, s and t are numbers 0 to 6, and y is A number from 1 to 200, z represents a number from 1 to 20. [0131] When the compound represented by the formula (15) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

[0132] (e) A structural unit represented by the following formula (16).

[Chemical 11]

_R 21 _R 24 _R 25 R20

― CI— (CH ₂ ) _e CONH (CH ₂ ) _s ― S Ii— (OS Ii) _y (CH2) t NHCO (CH ₂ ) _d — CI ( _{1 6} )

Ft ²³ R ^2e R ²⁷ R ²²

[Wherein, R ^{2 to} R ²³ , R ^{24 to} R ²⁷ , d, e, s, t, and y are the same as those in the above formula (15). [0133] In the formulas (15) and (16), the alkyl group represented by R ^{2 to} R ²³ is a C ^{1 to} C group such as a methyl group, an ethyl group, a propyl group, a hexyl group, or a cyclohexyl group. 12 alkyl groups, and R ^{24 to} R ²⁷ alkyl groups include methyl groups, ethyl groups, propyl groups, etc.

3 alkyl groups are mentioned.

[0134] In the present invention, the azo group-containing polysiloxane compound represented by the above formula (15) is

A compound represented by the following formula (17) is particularly preferable.

[0135] [Chemical 12]

0 † H ₃ CH ₃ CH ₃ CH ₃

HO-t— C (CH ₂ ) ₂ C— N = N— C— (CH ₂ ) ₂ CONH (CH ₂ ) ₃ ― Si— (OSi) _y (CH ₂ ) ₃ NH ~ I ~ H _{(1 7)}

C IHg C IH3 C IH3 C IH3

[Wherein y and z are the same as in the above formula (15). ]

[0136] 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) to (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. When the ratio exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and 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.

[0137] (V) Structural unit (f)

The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f).

[0138] (f) A structural unit represented by the following formula (18).

[Chemical 13]

HR ²⁵

'C' (18)

H H

[Wherein represents a group having an emulsifying action]

[0139] In the formula (18), the group having an emulsifying action of R ²⁵ has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. Some groups are preferred.

[0140] Examples of such an emulsifying group include a group represented by the following formula (19).

[Chemical 14]

^H 2g + lCg

9)

[Where g is a number from 1 to 20, f is a number from 0 to 4, and u is a number from 3 to 50]

[0141] 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 formula (20). [0142] [Chemical 15]

[Wherein g, f and u are the same as in the above formula (19)]

[0143] The content of the structural unit (f) is preferably 0.1 to 5 mol parts with respect to a total of 100 mol parts of the structural units (a) to (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. This is because the tackiness of the resin composition does not increase excessively, handling becomes easy, and 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 mol parts, and even more preferably 0.2 to 3 mol parts.

[0144] (vi) Molecular weight

The hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent. 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.

[0145] (3) Reaction molar ratio

The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer. Obtained. A compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing fluoropolymer are an isocyanate group Z It is preferable to carry out the reaction at a hydroxyl group molar ratio of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be reduced. 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 aqueous alkali solution may be reduced.

For this reason, the molar ratio of the isocyanate group Z hydroxyl group is preferably 1.1 to 1.5, more preferably 1.2 to 1.5.

[0146] The addition amount of the component (G) in the curable resin composition is not particularly limited, but is usually 1 to 95% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 1% by weight, the refractive index of the cured coating film of the curable resin composition increases, and a sufficient antireflection effect may not be obtained. If the added amount exceeds 95% by weight, the scratch resistance of the cured coating film of the curable resin composition cannot be obtained! This is because there are cases.

For such reasons, the addition amount of the component (G) is more preferably 2 to 90% by weight, and further preferably 3 to 85% by weight.

[0147] 2. Ingredient (H)

(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 (H) 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. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

[0148] Further, 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; methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and γ-butalate ratatones; Tetrahydrofuran, 1,4 dioxane, etc. In particular, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

[0149] Examples of commercially available silica-based particles include colloidal silica manufactured by Nissan Chemical Industries, Ltd. Product names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ΜΕΚ— ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ゝ ST— OUP ゝ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST-50, ST-OL, etc. can be mentioned.

[0150] Further, the surface of the colloidal silica subjected to surface treatment such as chemical modification can be used. For example, it contains a hydrolyzable silicon 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, etc. that has a thiocyanate group, such as 3-thiocyanatepropyltrimethoxysilane, which has an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxyhexoxyl) ethyltrimethoxysilane, and the like having a thiol group such as 3-mercaptopropyltrimethoxysilane Can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane.

[0151] (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. .

[0152] Here, examples of the surface treating agent include alkoxysilane compounds, tetrabutoxysilane, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.

[0153] 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 (21).

[Chemical 16]

Where R. Is a methyl group, R is an alkyl group having 1 to 6 carbon atoms, is a hydrogen atom or a methyl group, a is 1 or 2, b is an integer of 1 to 5, and A is a divalent alkylene group having 1 to 6 carbon atoms , B is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms, Z is a (b + 1) valent chain number, cyclic or branched carbon number 2 to 14 This is a divalent hydrocarbon group. Z 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. [0154] (3) Preferred embodiment (porous silica particles)

As silica particles used in the composition for forming a low refractive index layer, porous silica particles are preferred.

It is more preferable to use the first porous silica particles (HI) or the second porous silica particles (H2) as the porous silica particles. The first porous silica particles (HI) are obtained by hydrolysis and Z or hydrolysis condensation of a key compound represented by the following formula (22) and a key compound represented by the following formula (23). . That is, it is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (22), and subjecting the keen compound represented by the formula (23) to hydrohydrolysis and Z or hydrolytic condensation. It is done. The key compound represented by the formula (22) and the key compound represented by the formula (23) may be mixed and subjected to hydrolysis and Z or hydrolytic condensation at the same time. It is also possible to hydrolyze and Z or hydrolyze and condense the key compound represented by the formula (2), and then add the key compound represented by the formula (23) to perform further hydrolysis and Z or hydrolytic condensation. The second porous silica particles (H2) are a key compound represented by the following formula (22), a key compound represented by the following formula (23), and a key compound represented by the following formula (24). Obtained by hydrolysis of Z and Z or hydrolytic condensation. That is, hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (22), and hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (23), and It is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (24). The key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) are mixed and simultaneously hydrolyzed and Z or hydrolyzed. However, the key compound represented by formula (22) is hydrolyzed and Z or hydrolyzed, and then the key compound represented by formula (23) and formula (24) are used. Further, hydrolysis and Z or hydrolysis condensation may be carried out by adding the above-mentioned key compound.

SiX (22)

Four

R ²⁹ SiX (23)

j 4-j

R ³⁰ SiX (24)

k 4-k

[0155] In the formulas (22), (23) and (24), each X independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, a carboxyl group, or an alkyloxy group having 2 to 4 carbon atoms. Carbo Or an alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, and more preferably an alkoxy group. In the formulas (22), (23) and (24), Xs may be the same or different.

Examples of the compound represented by the formula (22) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane.

In formula (23), R ²⁹ 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 formula (23), j is an integer of 1-3, Preferably it is 1-2.

Examples of the compound represented by the formula (23) include vinyltrimethoxysilane, butyltrioxysilane, vinyltrichlorosilane, talyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.

By using the compound represented by the formula (23), 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.

In the formula (24), R ³ 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 fluorine having 3 to 10 carbon atoms. Substituted alkyl group.

In the formula (24), k is an integer of 1 to 3, preferably 1 to 2.

Examples of the compound represented by the formula (24) include 3, 3, 3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, and 2-perfluorohexoxysilyltrimethoxy. Silane, 2-perfluorooctyltrimethylsilane, 2-perfluorooctyltriethoxysilane, 3,3-di (trifluoromethyl) -3-fluoropropyltriethoxysilane, etc. Can be mentioned.

By using the compound represented by the formula (24), the porous silica particles can contain a fluorine-containing alkyl group. 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 (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) may be used.

[0158] In the first porous silica particles (HI), when the total of the key compound represented by the formula (22) and the key compound represented by the formula (23) is 100 mol%, the formula ( Kei-containing compound represented by Kei-containing compound Z formula represented by 22) (23), 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 (H2), the total of the key compound represented by the formula (22), the key compound represented by the formula (23) and the key compound represented by (24) is 100. When the mol% is used, the key compound represented by the formula (22), the key compound represented by the formula Z (23), and the key compound represented by the formula Z (2 4) are preferably 60 to 9871. It is hydrolyzed and / or hydrolyzed and condensed at a ratio of ˜301 to 20 (mol%), preferably 65 to 962 to 202 to 15 (mol%).

[0159] The first and second porous silica particles (HI) and (H2) 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.

[0160] The porous silica particles (H) are obtained by the production method described below.

The first or second porous silica particles (HI) and (H2) 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 above formula (22) and the key compound represented by the formula (23), or the key compound represented by the above formula (22), the formula (23 ) And the compound represented by formula (24) are hydrolyzed and Z Or it can manufacture by hydrolytic condensation.

[0161] As the basic compound, for example, amine compounds are 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, tetraptylammo-umhydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-jetylamine, N, N-dipropylamine, N, N-dibutylamine , It may be mentioned Torimechiruamin, Toryechiruamin, tripropylamine § Min, the Toribuchiruamin like. Preferably, ammonia, ethanolamine, hydroxy-tetramethylamine or the like is used.

There is one kind of these basic compounds, or two or more kinds may be used at the same time.

[0162] The acid amide, diol or diol half-ether is preferably compatible with water and 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. .

[0163] 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.

[0164] The total concentration of the key compound of formula (22) and the key compound of formula (23) or the key compound of formulas (22) to (24) in the reaction solution is usually 0 in terms of complete hydrolysis condensate. 5 to 10% by weight, preferably 1 to 8% by weight. Here, “in terms of complete hydrolyzed condensate” is a theoretical value calculated assuming that the key compound was completely hydrolyzed and condensed. This corresponds to the weight of X in the compound and the compound of (23) or the compounds of formulas (22) to (24) when X is substituted with 2 moles of oxygen atoms. 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 (22) and the compound of formula (23), or the compound of formula (22), the compound of formula (23) and the compound of formula (24) 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 (22) is hydrolyzed and subjected to Z or hydrolytic condensation, and then the key compound represented by the formula (23) or the formula (23), respectively. Further, hydrolysis and Z or hydrolysis condensation may be carried out by adding a key compound and a key compound represented by the formula (24).

[0165] The reaction temperature for 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. The reaction time is defined by the formula (22), the compound represented by formula (23), the type of formula (24), the reaction rate, the 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.

[0166] The dispersion medium is water! /, And organic solvents are preferred. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycolol, 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, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and γ-butalate Rataton; 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 combination as a dispersion medium. The

[0167] The compounding amount of the porous silica particles (H) in the resin composition is usually 5 to 99% by weight, preferably 10 to 98% by weight, based on the total amount of the composition other than the organic solvent. More preferred is -97% by weight. If it is less than 5% by weight, the hardness of the cured film may be insufficient. If it exceeds 99% by weight, 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 particles does not include the amount of solvent.

[0168] (4) Optional additives

The following components can be added to the composition for a low refractive index layer used in the present invention, if necessary.

[0169] (I) A polyfunctional (meth) ataritoy compound containing at least two or more (meth) atalyloyl groups and Z or a fluorine-containing (meta) containing at least one or more (meth) atalyloyl groups ) A create ich compound

In the curable resin composition, if necessary, the polyfunctional (meth) attareito toy compound containing at least two or more (meth) attaroyl groups and Z or at least one or more (meth) alkyls. It is also possible to add a fluorine-containing (meth) attareito toy compound containing a acryloyl group.

[0170] (1) A polyfunctional (meth) atareto toy 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) , Made by Shin Nakamura Co., Ltd.) or a combination of two or more Is mentioned.

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.

[0171] (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 can be used alone or in combination of two or more.

[0172] The amount of component (I) to be added is not particularly limited, but is usually 0 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount exceeds 90% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained.

For such reasons, the amount of component (I) added is more preferably 80% by weight or less, and further preferably 60% by weight or less.

[0173] Compounds that generate active species by irradiation of ω-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.

[0174] (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. As such an active energy ray, Light energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, j8 rays, γ rays and the like can be mentioned. 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.

[0175] (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-1-one [4- (methylthio) phenol] 1-2 morpholinopropane 11-one, triphenyl -Luamine, 2, 4, 6 Trimethylbenzoyl diphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydro 2-Methyl-1-phenylpropanone 1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3, 3 ', 4, 4'-tetra Xylcarbole) benzophenone (BTTB), 2- (dimethylamino) — 1— [4— (morpholol) phenol] —2-phenol methyl) 1-butanone, 4 benzoyl 4′-methyldiphenyl Examples include sulfide, benzil, or a combination of BTTB and xanthene, thixanthene, coumarin, ketocoumarin, and other dye sensitizers.

[0176] Among these photopolymerization initiators, 2, 2 dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 Trimethyl benzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 1 (methylthio) phenol] 1 2 Morpholinopropane 1 1-one, 2 (dimethylamino) 1 1 [4 (morpholol) phenol 1] -butanone and the like are more preferable, 1-hydroxycyclohexylphenylketone, 2-methyl-1-one [4 (methylthio) phenol] 2 morpholinopropane 1-o 2— (Dimethylamino) — 1— [4- (Morpholol) phenol] —2 Phenylmethyl )-1-butanone and the like.

[0177] (ii) Amount added

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

For these reasons, it is more preferable to add the photopolymerization initiator to 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent. It is more preferable to do this.

[0178] (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.

[0179] (i) Kind

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.

[0180] (ii) Addition amount

The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the amount of added calories is less than 0.01% by weight, 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% by weight, the refractive index of the cured film increases and the antireflection effect may decrease. For this reason, it is more preferable to add the thermal polymerization initiator to 0.05 to 15% by weight 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.

[0181] (K) Organic solvent

It is preferable to add an organic solvent to the curable resin composition. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. As such an organic solvent, an alcohol solvent having 1 to 8 carbon atoms, a ketone system having 3 to 10 carbon atoms, or an ester solvent having 3 to carbon atoms: L0 can be preferably used. Ethyl ketone, methyl amyl ketone, methanol, ethanol, tert-butanol, isopropanol, propylene glycolanol monomethylol ether, propylene glycol norethyl ether, propylene glycol monopropyl ether, etc. are particularly preferred and can be mentioned as examples. . These organic solvents can be used alone or in combination of two or more.

[0182] The addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by weight with respect to 100 parts by weight of the composition other than the organic solvent. The reason for this is that when the addition amount is less than 100 parts by weight, 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 weight, the curable resin composition is difficult to adjust. This is because the storage stability of the composition may be decreased, or the viscosity may be excessively decreased to make handling difficult.

[0183] Additives

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. Additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (H), pigments, dyes and the like can also be contained.

[0184] (5) Method for preparing composition for forming low refractive index layer

The curable resin composition used in the present invention comprises the (G) ethylenically unsaturated group-containing fluoropolymer and the (H) component, or, if necessary, the (I) component, the ω component, ( Ii) It can be prepared by adding an organic solvent and an additive, respectively, and mixing at room temperature or under heating conditions. Specifically, mixers, aders, ball mills, triple rolls, etc. It can be prepared using a mixer. However, when mixing under heating conditions

It is preferable that the temperature is not higher than the decomposition start temperature of the thermal polymerization initiator.

(6) 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 to a value in the range of 0.1 to 5 jZcm ² , and it is more preferable to set the exposure value to a value in the range of 0.3 to ³ jZcm ² .

[0186] 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]

[0187] 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.

[0188] Example 1

(1) Production of liquid curable composition

In a container shielded from ultraviolet rays, tin-containing indium oxide dispersion (Fuji Chemical Co., Ltd. Houtform NID-20, dispersion solvent isopropyl alcohol, tin-containing indium oxide 20% by weight, average primary particle size 13nm Hereinafter, it may be referred to as ITO particles—1) 50 parts, dipentaerythritol hexaatalylate (trade name KAYA, manufactured by Nippon Gyaku Co., Ltd.) RAD DPHA Hereinafter, it may be referred to as B-l. ) 86 parts, 1-hydroxycyclohexyl phenol ketone 2.5 parts, 2-methyl-1-one (4- (methylthio) phenol) -2-morpholinopropane-1-one 1.5 parts, isopropyl alcohol 141.8 parts Then, 51.3 parts of propylene glycol monomethyl ether was stirred at 50 ° C. for 2 hours to obtain a uniform solution composition. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 170 ° C. for 1 hour and weighed to determine the solid content, which was 30% by weight. Also, after weighing 2g of this composition in a magnetic crucible, it was pre-dried on a hot plate at 80 ° C for 30 minutes and baked in a 750 ° C pine furnace for 1 hour. The inorganic content was determined to be 10% by weight.

[0189] Examples 2 to 3, Comparative Examples 1 to 3

By the same operation method, each composition of Examples 2-3 and Comparative Examples 1-3 shown in Table 1 was obtained. In Table 1, the blending amount of ITO particles and dispersant represents only the solid content in the added dispersion, and the dispersion medium is included in the blending amount of the solvent.

[0190] <Preparation of cured film>

Obtained in Examples 1-3 and Comparative Examples 1-3 on a polyester film A4 300 (made by Toyobo Co., Ltd., film thickness 188 111) subjected to surface easy adhesion treatment using a wire bar coater Each of the compositions was applied and dried in an oven at 80 ° C. for 3 minutes to form a coating film. Next, the coating film was cured with ultraviolet light under a light irradiation condition of UZcm ² using a metal nitride lamp in the atmosphere to form a cured film (hard coat layer) having a thickness of 3 μm.

[0191] <Evaluation of cured film>

The total cured light transmittance, haze, and surface resistance of the obtained cured film were evaluated according to the following criteria. The results obtained are shown in Table 1.

(1) Total light transmittance, haze

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

(2) Pencil hardness

The pencil hardness of the cured film was evaluated according to JIS K5600-5-4, and the film cured on a glass substrate was evaluated. (3) Surface resistance

Apply the surface resistance (Ω Z port) of the cured film using a high resistance meter (Agilent Technologies, Inc., Agilent 4339B) and Resistivity Cell 16008B (Agilent, Technologies, Inc.) Measurements were made at a voltage of 100V.

[table 1]

The contents of the abbreviations in Table 1 are shown below.

ITO particles—1: Fuji Chemical Co., Ltd., Nutform NID-20 (—Next particle size: 13 nm, Secondary particle size: 25 nm IPA dispersion)

Dispersant 1: Dispersant contained in Fuji Chemical Co., Ltd., Utoform NID-20 ITO particles 2: Pastoran made by Mitsui Mining Co., Ltd. (Primary particle size: 30nm, Secondary particle size: 15Onm water dispersion)

Dispersant 2: Dispersant contained in Pastoran (ITO particle-2) manufactured by Mitsui Mining & Smelting Co., Ltd.

ITO particles-3: Nanotec (primary particle size: 25nm, secondary particle size: 80ηm EtOH dispersion) manufactured by Shi Kasei Co., Ltd.

Dispersant 3: Dispersant included in Nanotech manufactured by Shi Kasei Co., Ltd.

ITO particle-4: Pastoran manufactured by Mitsui Mining Co., Ltd. (Primary particle size: 30nm, Secondary particle size: 30Onm MeOH dispersion)

Dispersant 4: Dispersant contained in Pastoran (ITO particles—4) manufactured by Mitsui Mining Co., Ltd.

PGME: Propylene glycol monomethyl ether

IPA: Isopropanol

MeOH: Methanol

EtOH: ethanol

[0194] From the results in Table 1, Comparative Examples 1 and 3 are of the order of 10 ⁷ Ω, and the surface resistance is very small, but the haze is large and the transparency is poor. In Comparative Example 2, on the contrary, the haze is relatively low, but the surface resistance is as large as 10 ¹⁴ Ω, and the antistatic property is inferior. On the other hand, in Examples 1 to 3, the surface resistance is Both are in the order of ^ Ω, and the haze is 0.1% or 0.2%, which satisfies the requirements of both antistatic properties and transparency. Power.

[0195] Production Example 1: Preparation of specific organic compound (Aa)

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 Compound (Specific organic compound (Aa)) was obtained. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 cm ^{_ 1} characteristic of the mercapto group in the raw material and the absorption peak of 2260 cm ^_1 characteristic of the raw material isocyanate compound disappeared, and new urea bonds and S ( A peak of 1660 cm ^_1 characteristic for the C—O) NH— group and a peak of 1720 cm ^{_ 1} characteristic for the attaxy oxy group are observed, and one S (C = O) It was shown that oxy-oxyl-modified alkoxysilane having both NH- and urethane bonds was formed. As described above, this yarn composition contains a total of 773 parts of the compounds represented by the following formula (25) and the following formula (26), and 220 parts of pentaerythritol tetraatalylate which has not participated in the reaction. Are mixed.

[0196] [Chemical 17]

(In the formula, Acryl represents an allyloyl group.)

[0198] Production Example 2: Preparation of polyfunctional attalylate

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 the 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. It was. For the product in this reaction solution, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 1. As a result, it was 0.1% by weight or less, and it was confirmed that the reaction was performed almost quantitatively. . Further, it was confirmed that the molecule contained a urethane bond and an taliloyl group (polymerizable unsaturated group).

As described above, this composition contains 75 parts of the compound (B-1) represented by the following formula (27) and 37 parts of pentaerythritol tetraatalylate which is not involved in the reaction.

[0199] [Chemical 19]

(In the formula, Acryl represents an allyloyl group.)

[0200] Production Example 3: 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%) 143 g (43 g as silica particles), Production Example 1 2.8 g of the solution containing the specific organic compound (Aa) produced in 1), 0 lg of distilled water and 0. Olg of p-hydroquinone monomethyl ether were mixed and heated and stirred at 65 ° C. Four hours later, orthoformate methyl ester 1.Og was added, and the mixture was further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%.

[0201] Production Example 4: Production of hydroxyl-containing fluoropolymer

After replacing the stainless steel autoclave with a 1.5 L magnetic stirrer with nitrogen gas, 465 g of ethyl acetate, 138.5 g of perfluoro (propyl butyl ether), 37.5 g of ethyl vinyl ether, hydroxy ethyl vinyl 40.0 g of Ruether, “Adekalia Soap ER-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as a non-ionic reactive emulsifier 180.0 g, “VPS-1001” as a polydimethylsiloxane containing azo group (Wako Pure Chemical Industries Manufactured by Kogyo Co., Ltd.) 9 Og and lauroyl peroxide 1.5g was added, and after cooling to 50 ° C with dry ice methanol, oxygen in the system was removed again with nitrogen gas.

Hexafluoropropylene 86. Og was then added and heating was started. The pressure when the temperature in the autoclave reached 60 ° C was 2.9 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 2. OX 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was released to obtain a polymer solution having a solid content concentration of 30.0%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer.

[0202] Production Example 5: Production of fluoropolymer containing ethylenically unsaturated groups

A 1-liter separable flask equipped with a magnetic stirrer, a glass cooling tube, and a thermometer was charged with 70.0 g of the hydroxyl group-containing fluoropolymer obtained in Production Example 4, and 2, 6-di-t as a polymerization inhibitor. —Butylmethylphenol 0. Olg and MIBK520g were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer dissolved in MIBK and the solution became clear and uniform. Next, 22 g of 2-methacryloyloxychetyl isocyanate is added to this system and stirred until the solution is homogeneous, and then 0.2 g of dibutinoretin dilaurate is added to start the reaction, and the temperature of the system is increased. Was maintained at 55 to 65 ° C and stirring was continued for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to obtain a solid content of 15.0%.

[0203] Production Example 6: Preparation of composition 1 for forming a low refractive index layer

20 g of reactive silica particle sol obtained in Production Example 3 (6.2 g as reactive particles), fluoropolymer containing ethylenically unsaturated groups obtained in Production Example 5 101. Og (containing ethylenically unsaturated groups) 15.2 g) as a fluoropolymer, 1.7 g of dipentaerythritol pentaacrylate, 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1 on (C 2) 1.2 g, production example 2 0.4 g of the compound represented by the formula (27) obtained by the above, organic copolymer-containing special silicon (Floren AC-901, Kyoeisha Chemical Co., Ltd.) 0.lg, methyl isobutyl ketone 505.6 g, and 1 at room temperature Stir for hours to obtain composition 1 for forming a low refractive index layer It was. The solid content was determined in the same manner as in Production Example 1 and found to be 4% by weight.

[0204] Production Example 7: Synthesis of porous silica particles

In a quartz separable flask, 22.24 g of tetraethoxysilane, 841.97 g of methanol and 30.OOg of propylene glycol were added and mixed uniformly, and then 101.OOg of 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. When 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.

[0205] Production Example 8: Preparation of composition 2 for forming a low refractive index layer

56 g of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 5 (8.5 g as an ethylenically unsaturated group-containing fluoropolymer) and the porous silica obtained in Production Example 7 1750 g of the particle dispersion (87.5 g as porous silica particles), 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1-on 4 g, MIBK 700 g as a photopolymerization initiator were attached with a 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. When the solid content was determined in the same manner as in Example 1, it was 4% by weight. [0206] Example 4

Manufacture of antireflection laminate 1

The liquid curable composition obtained in Example 1 was applied to a polyester film A4300 (made by Toyobo Co., Ltd., film thickness 188 μm) subjected to surface easy adhesion treatment using a wire bar coater # 20. And dried in an oven at 80 ° C for 3 minutes. Subsequently, the coating film was UV-cured under a light irradiation condition of UZcm ² using a methanolide lamp in the atmosphere to produce a film having an antistatic hard coat layer. When the film thickness of the antistatic hard coat layer was measured with a stylus type surface shape measuring instrument, it was 3 m. On this film with an antistatic hard coat, the composition 1 for forming a low refractive index layer obtained in Production Example 6 was applied using a wire bar coater # 3, and the conditions of 80 ° C for 1 minute in an oven were applied. And dried. Next, using a metal nitride lamp under a nitrogen atmosphere, the coating film was UV-cured under the light irradiation conditions of UZcm ² to form a low refractive index layer, thereby producing an antireflection laminate 1. Reflectance power of the obtained antireflection laminate 1 The film thickness of the low refractive index layer was calculated.

[0207] Example 5

Manufacture of antireflection laminate 2

An antireflection laminate 2 was prepared in the same manner as in Example 4 except that the low refractive index layer forming composition 2 obtained in Production Example 8 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.

[0208] Example 6

Manufacture of antireflection laminate 3

An antireflection laminate 3 was produced in the same manner as in Example 4 except that the liquid curable composition obtained in Example 3 was used instead of the liquid curable composition obtained in Example 1. When the film thickness of the low refractive index layer was calculated in the same manner as in Example 4, it was 0 .: Lm.

[0209] Example 7

Manufacture of antireflection laminate 4

An antireflection laminate 4 was prepared in the same manner as in Example 6 except that the low refractive index layer forming composition 2 obtained in Production Example 8 was used instead of the low refractive index layer forming composition 1. [0210] Comparative Example 4

Manufacture of antireflection laminate 5

Example except that the liquid curable composition obtained in Comparative Example 2 was applied on the base material using a wire bar coater # 40 instead of the liquid resin composition obtained in Example 1. In the same manner as in Example 4, 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 4, it was 0.1 m.

[0211] Comparative Example 5

Manufacture of antireflection laminate 6

An antireflection laminate 6 was prepared in the same manner as in Comparative Example 4 except that the low refractive index layer forming composition 2 obtained in Production Example 8 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 4, it was 0 .: Lm.

[0212] Evaluation example

The following properties were evaluated for the antireflection laminates 1 to 6 obtained in Examples 4 to 7 and Comparative Examples 4 to 5.

[0213] (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 2 shows the results obtained.

[0214] (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 2.

[0215] (d) Reflectance

The reflectance of the resulting anti-reflection laminate was measured with a spectral reflectance measuring device (instant multi-photometering system, MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). The absolute reflectance was measured in the wavelength range of 400 to 800 nm. And evaluated. Table 2 shows the reflectance at a wavelength of 550 nm.

[0216] (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 the Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with 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. Table 2 shows the results obtained.

◯: 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.

[0217] (f) Scratch resistance test 2 (cloth abrasion resistance)

The cloth rubbing resistance test of the antireflection laminate was carried out by the following method. In other words, a non-woven fabric (B EMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) was attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was subjected to a load of 1000 g 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. Table 2 shows the results obtained.

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

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

[0218] (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.), and the surface of the cured film 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. Table 2 shows the results obtained.

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

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

[0219] [Table 2] 0220

Table 2

Examples 4 to 7 using particles (ITO particles 1) containing tin-containing indium oxide (ITO) as a main component are high in total light transmittance, low in haze, low in surface resistance, scratch resistance, and chemical resistance. It can be seen that it is excellent in quality.

Industrial applicability

[0221] According to the present invention, a liquid curing that is excellent in curability and can form a coating film (film) excellent in antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. Composition, cured film and antistatic laminate can be provided.

[0222] Since the cured film of the present invention has excellent scratch resistance and adhesion, it is useful as a hard coat. Further, since it has an excellent antistatic function, it is useful as an antistatic film by being disposed on a substrate of various shapes such as a film, a plate, or a lens.

[0223] Examples of the application of the cured film of the present invention include, for example, touch panel protective films, transfer foils, optical disk hard coats, automotive window films, antistatic protective films for lenses, cosmetic containers, and the like. Use as a hard coat mainly for the purpose of preventing surface scratches on product surfaces, etc., and preventing dust from adhering to static electricity, as well as CRT, liquid crystal display panels, plasma display panels, and electoric luminescence Examples thereof include use as an anti-reflection film for antistatics for various display panels and the like, and use as an anti-reflection film for anti-statics such as plastic lenses, polarizing films and solar battery panels.

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, electo-luminescence display panel, etc. as a hard coat for the purpose of preventing product surface scratches and electrostatic dust. 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 can prevent scratches (scratches) on, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic housings, 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] The following components (A), (B), (C) and (D):

(C) Photopolymerization initiator

(D) Solvent

A liquid curable composition containing

[2] The liquid curable composition according to claim 1, wherein the content of the component (A) is 5 to 40% by weight in the total solid components.

[3] The liquid curable composition according to claim 1 or 2, wherein the component (A) is a particle mainly composed of tin-containing indium oxide (ITO) surface-treated with a surface treatment agent.

[4] The surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. The liquid curable composition as described in 1.

X— C (= Y) — NH— (1)

[In the formula, X represents NH, 0 (oxygen atom) or S (ion atom), and Y represents O or S.

]

[5] A cured film obtained by curing the liquid curable composition according to any one of claims 1 to 4.

6. The cured film according to claim 5, having a surface resistance value of 1 × 10 ¹³ Ω or less.

[7] A method for producing a cured film, comprising the step of irradiating the liquid curable composition according to any one of claims 1 to 4 with radiation to cure the composition.

[8] at least a substrate;

A cured film layer obtained by curing the liquid curable composition according to any one of claims 1 to 4, and

A laminate having

9. The laminate according to claim 8, which is an optical component having an antistatic function.

10. The laminate according to claim 9, which is an antireflection film. [11] The laminate according to any one of claims 8 to: LO having a surface resistance value of IX 10 ¹³ Ω or less.

[12] The laminate is an antireflection film in which at least an antistatic layer and a low refractive index layer are laminated on a base material in this order from the side close to the base material,

12. The laminate according to claim 10, wherein the cured film layer is an antistatic layer.

13. The laminate according to claim 12, wherein a refractive index of the antistatic layer is higher than a refractive index of the low refractive index layer.

[14] The laminate according to any one of [8] to [13], wherein a hard coat layer is formed on the substrate.

[15] The low refractive index layer is

The following ingredients (G) and (H):

(G) a compound containing l isocyanate groups and at least one ethylenically unsaturated group, and

A hydroxyl group-containing fluoropolymer,

(H) particles based on silica,

The laminate according to claim 12, which is a cured product of a curable resin composition containing

[16] When the total of the following structural units (a) to (c) is 100 mol%, the hydroxyl group-containing fluoropolymer is (&) 20 to 70 mol%, (1)) 10 to 70 mol % And (.) 5 to 70 mol%, and

The laminate according to claim 15, 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 (11)

(b) Structural unit represented by the following formula (12)

(c) Structural unit represented by the following formula (13)

[Chemical 20] R 11

• C c-

(1 1)

[Chemical 21]

HR ¹³

-C—— C- (12)

H R 14

[Wherein R "represents a hydrogen atom or a methyl group, R ¹⁴ represents an alkyl group,-(CH) -OR ¹⁵

2 c

Is a group represented by OCOR ¹⁵ (R ¹⁵ represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group]

[Chemical 22]

The hydroxyl group-containing fluoropolymer further comprises the following structural unit (d) 0 derived from an azo group-containing polysiloxane compound with respect to a total of 100 mole parts of the structural units (a) to (c). The layered product according to claim 15 or 16, comprising 1 to: L0 mole part.

(d) Structural unit represented by the following general formula (14)

[Chemical 23] R ¹⁸

Si― O (14)

1 ⁹

18. The component (H) is a silica particle having an ethylenically unsaturated group on the surface.

The laminate according to any one of to 17.

[19] The component (H) is

SiX (22)

Four

R ²⁹ SiX (23)

j 4-j

(X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ Is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, and j is an integer of 1 to 3. Formula (22) X in formula (23) and X in formula (23) may be the same or different.)

The laminate according to any one of claims 15 to 18.

[20] The component (H) is

SiX (22)

Four

R ²⁹ SiX (23)

j 4-j

R ³⁰ SiX (24)

k 4-k

(X is each independently an alkoxy group having 1 to 4 carbon atoms, halogeno group, isocyanate group, carbon It represents an alkyloxycarbo group having 2 to 4 prime numbers or an alkylamino group having 1 to 4 carbon atoms. R ²⁹ represents an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, and j represents an integer of 1 to 3. R ³ represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and k represents an integer of 1 to 3. X in formula (22), X in formula (23), and X in formula (24) may be the same or different. )

The laminate according to any one of claims 15 to 18.

[21] The porous silica particle (HI) is a silicon compound represented by the formula (22) and the formula

When the total amount of the key compound represented by (23) is 100 mol%, the hydrolyzate and Z or the hydrolyzed condensate are 67 to 99 mol% of the key compound represented by the formula (22) and The laminated body according to claim 19, which also has a reactant power of 33 to 1 mol% of the silicon compound represented by the formula (23).

[22] Force of the porous silica particles (H2) The key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) Assuming that the total amount is 100 mol%, the hydrolyzate and Z or hydrolysis condensate are 60 to 98 mol% of the key compound represented by the formula (22) and the key represented by the formula (23). Elementary compound 1-30 mol% and formula

21. The laminate according to claim 20, which also has a reactant power of 1 to 20 mol% of the silicon compound represented by (24).

[23] A cured film layer obtained by curing the composition by applying the liquid curable composition according to any one of claims 1 to 4 on the substrate and irradiating with radiation. The manufacturing method of the laminated body including the process of forming.