KR101268700B1 - Liquid curable composition, cured film, and antistatic layered product - Google Patents

Abstract

The present invention provides (A) phosphorus-containing tin oxide particles, (B) a compound having two or more polymerizable unsaturated groups in the molecule, (C) a photopolymerization initiator having a molar extinction coefficient of 5,000 L / mol · cm or less at 313 nm, and ( D) liquid curable composition containing a solvent; And at least, the laminated body which has a base material and the cured film layer which hardens the said liquid curable composition is provided.

Laminate, liquid curable composition, cured film, antireflective film having antistatic function

Description

Liquid curable composition, cured film, and antistatic laminate {LIQUID CURABLE COMPOSITION, CURED FILM, AND ANTISTATIC LAYERED PRODUCT}

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

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

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

Recently, the development and generalization of information and communication devices are remarkable, and further improvement of productivity and productivity of hard coating, antistatic film, antireflection film, etc. have been required.

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

With respect to these demands, various radiation curable materials have been proposed in view of high productivity and the ability to cure at room temperature.

As such a technique, for example, a composition containing sulfonic acid and a phosphoric acid monomer as an ion conductive component (following patent document 1), a composition containing a chain metal powder (following patent document 2), tin oxide particles, and a polyfunctional acrylate , And a composition containing a copolymer of methyl methacrylate and polyether acrylate as a main component (Patent Document 3), a conductive coating composition containing a pigment coated with a conductive polymer (Patent Document 4), a trifunctional acrylate ester, Optical disk material containing monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator and conductive powder (Patent Document 5), hydrolyzate of antimony doped tin oxide particles and tetraalkoxysilane dispersed with silane coupler, light Conductive paint containing a sensitizer and an organic solvent (Patent Document 6), containing a polymerizable unsaturated group in the molecule A 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), a conductive oxide fine powder having a primary particle size of 100 nm or less, and the conductive oxide fine powder The coating material for transparent conductive film formation (the following patent document 8) containing an easily dispersible low boiling point solvent, the poorly dispersible low boiling point solvent of the said conductive oxide fine powder, and binder resin is mentioned.

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

In these display panels, the surface is often wiped off with a gauze impregnated with ethanol to remove fingerprints, dust, and the like, and thus scratch resistance is required. In addition, there is a need for stain resistance that can easily wipe off fingerprints, dust and the like.

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

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

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

However, in such a fluororesin paint, in order to cure the coating film, it is necessary to crosslink by heating a hydroxyl group-containing fluorine-containing polymer and a curing agent such as melamine resin under an acid catalyst, and the curing time is excessively long depending on the heating conditions. There was a problem that the type of substrate that can be used is limited.

Moreover, also about the obtained coating film, although it was excellent in weather resistance, there existed a problem of being scratch-resistant and lacking in durability.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

This invention is made | formed in view of the above-mentioned problem, Even if there is little compounding quantity of electroconductive particle, sufficient antistatic performance can be expressed, excellent in sclerosis | hardenability, and excellent in antistatic property, hardness, and abrasion resistance on the surface of various base materials. It is an object of the present invention to provide a liquid curable composition and a cured film capable of forming a coating film (film) having both transparency and surface resistance.

The present invention can exhibit sufficient antistatic performance even when the amount of the conductive particles is small, excellent in curability, and excellent in antistatic property, hardness and scratch resistance, and a coating film having both transparency and surface resistance. It aims at providing the antistatic laminated body which has a cured film layer which hardens the liquid curable composition which can form a (film), especially the antireflective film laminated body which has an antistatic function.

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the problem mentioned above, this inventor hardens the composition containing the electroconductive particle which has a specific primary particle diameter, the compound which has a specific polymerizable unsaturated group, the photoinitiator which has a specific light absorption characteristic, and a solvent. The present invention was completed by discovering that the above object can be achieved by a laminate having a cured film layer.

In addition, by combining a low-refractive-index film obtained by curing a curable resin composition containing a specific ethylenically unsaturated group-containing fluorine-containing polymer and silica particles, the inventors have found that scratch resistance and fouling resistance of the antireflective laminate are improved, thereby completing the present invention. .

That is, this invention provides the following liquid curable compositions, the cured film, the manufacturing method of a cured film, a laminated body, and the manufacturing method of a laminated body.

1. Liquid curable composition containing following component (A)-(D).

(A) Phosphorus-containing tin oxide particles

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

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

(D) Solvent

2. Liquid curable composition as described in said 1 whose primary particle diameter of said (A) phosphorus containing tin oxide particle is 10 nm-100 nm.

3. The photoinitiator of the above (C) is 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one Liquid curable composition as described in said 1 or 2 which is 1 or more types selected.

4. Cured film formed by hardening | curing the liquid curable composition in any one of said 1-3, and whose surface resistance value is 1 * 10 <^{12> (} ohm) / square or less.

5. The manufacturing method of the cured film which has a process of irradiating a liquid curable composition in any one of said 1-3 and hardening the said composition.

6. At least with the substrate,

The laminated body which has a cured film layer formed by hardening | curing the liquid curable composition containing following component (A)-(D).

[Liquid curable composition]

(A) Phosphorus-containing tin oxide particles

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

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

(D) Solvent

7. The said laminated body of 6 whose primary particle diameters of the said phosphorus containing tin oxide particle (A) are 10 nm-100 nm.

8. Antistatic laminated body of said 6 or 7 whose thickness of said cured film layer is 0.05-20 micrometers.

9. The laminated body in any one of said 6-8 which is an optical component which has an antistatic function.

10. The laminated body of said 9 which is an antireflection film.

11. Laminated body in any one of said 6-10 whose surface resistance value is 1 * 10 <^{12> (} ohm) / square or less.

12. The laminate is an antireflection film having at least an antistatic layer and a low refractive index layer laminated on the substrate in this order from the side close to the substrate,

The laminated body of said 10 or 11 whose said cured film layer is an antistatic layer.

13. The said laminated body of 12 which is higher in refractive index of the said antistatic layer than the refractive index of the said low refractive index layer.

14. Furthermore, the laminated body in any one of said 6-13 in which the hard coat layer is formed on the base material.

15. The low refractive index layer

The laminated body in any one of said 12-14 which is hardened | cured material of curable resin composition containing following component (E) and (F).

(E) a compound containing one isocyanate group and at least one ethylenically unsaturated group, and

Hydroxyl-containing fluorine-containing polymer

Ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting

(F) Particles based on silica

16. Structure wherein the hydroxyl group-containing fluorine-containing polymer is represented by the structural unit (a) represented by the following formula (2): 20 to 70 mol%, the structural unit (b) represented by the following formula (3) by the following formula (4) 5 to 70 mol% of unit (c);

The laminated body of said 15 whose polystyrene conversion number average molecular weight measured by the gel permeation chromatography is 5,000-500,000.

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

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

In formula (4), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

17. The laminate according to 15 or 16, wherein the hydroxyl group-containing fluorine-containing polymer further comprises 0.1 to 10 mol% of the structural unit (d) represented by the following general formula (5) derived from an azo group-containing polysiloxane compound.

[In Formula 5, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

18. The laminate according to any one of 15 to 17, wherein the component (F) is a silica particle having an ethylenically unsaturated group on its surface.

19. The component (F) is

15 to 18, which are porous silica particles (F1) containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following Chemical Formula 6 and a silicon compound represented by the following Chemical Formula 7, and having an average particle diameter of 5 to 50 nm. The laminate according to any one of the above.

SiX ₄

R ¹⁰ _j SiX _{4 -j}

(X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, and R ¹⁰ is an alkenyl group having 2 to 8 carbon atoms) , An acryloxyalkyl group having 4 to 8 carbon atoms or a methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3, X in Formula 6 and X in Formula 7 may be the same or different)

20. Component (F) is

A porous silica having a silicon compound represented by the following formula (6), a silicon compound represented by the following formula (7) and a silicon compound represented by the following formula (8), and a hydrolyzate and / or a hydrolysis condensate, having an average particle diameter of 5 to 50 nm. The laminated body in any one of said 15-18 which is particle | grain (F2).

(6)

SiX ₄

&Lt; Formula 7 >

R ¹⁰ _j SiX _{4 -j}

R ¹¹ _k SiX _{4 -k}

(X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, and R ¹⁰ is an alkenyl group having 2 to 8 carbon atoms) , represents a methacryloxy alkyl group having acryloxy group or a carbon number of 5 to 8 having a carbon number of 4 to 8, j is an integer of 1 to 3, R ¹¹ represents a fluorine-substituted alkyl group having 1 to 12, k is 1 to An integer of 3, wherein X in Formula 6, X in Formula 7, and X in Formula 8 may be the same or different)

21. When the porous silica particles (F1) have a total sum of the silicon compound represented by the formula (6) and the silicon compound represented by the formula (7) at 100 mol%, the hydrolyzate and / or the hydrolyzed condensate are represented by the formula (6). The laminated body as described in said 19 containing 67-99 mol% of silicon compounds represented by the above, and 33-1 mol% of the silicon compounds represented by General formula (7).

22. When said porous silica particle (F2) makes the sum total of the silicon compound represented by the said Formula (6), the silicon compound represented by the said Formula (7), and the silicon compound represented by the said Formula (8) to 100 mol%, the said hydrolyzate and And / or the hydrolyzed condensate comprises a reactant of 60 to 98 mol% of the silicon compound represented by the formula (6), 1 to 30 mol% of the silicon compound represented by the formula (7) and 1 to 20 mol% of the silicon compound represented by the formula (8). The laminated body of said 20 to perform.

23. The manufacturing method of the laminated body including the process of forming the cured film layer obtained by apply | coating the liquid curable composition containing the following components (A)-(D) on a base material, and irradiating a radiation, and hardening the said composition. .

[Liquid curable composition]

(A) Phosphorus-containing tin oxide particles having a primary particle diameter of 10 nm to 100 nm

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

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

(D) Solvent

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

Conventionally, in order to obtain sufficient electroconductivity, it was necessary to mix | blend electroconductive particle with high content, but according to this invention, even if content of electroconductive particle is low, sufficient electroconductivity can be expressed and the antistatic lamination which has a cured film excellent in antistatic performance is carried out. You can get a sieve.

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

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the basic structure of the laminated body of this invention.

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

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

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

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

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

It is a schematic diagram which shows another form of the 2nd form of the antireflection film which has an antistatic function of this invention.

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

It is a schematic diagram which shows another form of the 3rd form of the antireflection film which has an antistatic function of this invention.

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

BEST MODE FOR CARRYING OUT THE INVENTION [

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

The laminated body of this invention has a cured film layer which hardens at least a base material and the liquid curable composition containing following components (A)-(D), It is characterized by the above-mentioned.

[Liquid curable composition]

(A) Phosphorus-containing tin oxide particles

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

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

(D) Solvent

Moreover, the antireflective film which is a preferable aspect and use of the laminated body of this invention is an antireflective film laminated | stacked in this order from the side which the antistatic layer and low refractive index layer which contain the said cured film layer at least to the base material on the base material, The low refractive index layer is a cured product of the curable resin composition containing the following components (E) and (F).

(E) An ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer at a ratio of molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9.

(F) silica particles

I. Laminates

The most basic structure of the laminated body of this invention is shown in FIG. The laminated body 1 of this invention has the cured film layer 12 formed by hardening | curing the base material 10 and the said liquid curable composition (henceforth a "composition for antistatic layer formation").

Since the laminated body 1 of this invention has the cured film layer 12 which has the outstanding scratch resistance and adhesiveness, it is especially useful as a hard coating, and when using the laminated body 1 of this invention as an antireflection film, it has a high refractive index. It is also useful as a high refractive index layer expressing sex.

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

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

Next, the structure of each layer at the time of using the laminated body of this invention as an antireflective film which has an antistatic function is demonstrated, referring FIGS. 2A-2C.

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

The 1st aspect at the time of using the laminated body of this invention as an antireflection film which has an antistatic function is shown to FIG. 2A. The anti-reflective film 2 which has an antistatic function forms the antistatic layer 12 which is a cured film layer which hardens the said liquid curable composition on the base material 10, and further forms the low refractive index layer 18 on it. It is done by In the first aspect, the antistatic layer 12 also has an antistatic function, a function as a hard coating layer, and also a function as a high refractive index layer. In the first aspect, it is necessary that the refractive index of the antistatic layer 12 is higher than the refractive index of the low refractive index layer 18.

As another form, although the antistatic layer 12 of the antireflection film 2 of this invention can also exhibit the function as a hard-coat layer, you may provide a hard-coat layer separately. In this case, the hard coat layer 11 is provided between the base material 10 and the antistatic layer 12 or between the antistatic layer 12 and the low refractive index layer 18. When the hard coating layer 11 is provided between the antistatic layer 12 and the low refractive index layer 18, the refractive index of the hard coating layer 11 should be higher than the refractive index of the low refractive index layer 18. These embodiments are shown in Figures 2B and 2C.

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

Also in a 2nd aspect, the form which provides a hard-coat layer separately as with 1st aspect is also possible. The hard coating layer 11 can be provided between any one of the base material 10 and the antistatic layer 12, or between the antistatic layer 12 and the high refractive index layer 16. FIG. These forms are shown in FIG. 2E and FIG. 2F.

The 3rd form at the time of using the laminated body of this invention as an antireflection film which has an antistatic function is shown to FIG. 2G. In the third aspect, the antireflection film 2 having an antistatic function forms an antistatic layer 12, which is a cured film layer formed by curing the liquid curable composition on the substrate 10, and further has a medium refractive index layer ( 14), the high refractive index layer 16 and the low refractive index layer 18 are formed in this order. In the third aspect, the antistatic layer 12 has a function as an antistatic function and a hard coating.

Also in a 3rd aspect, it is also possible to provide a hard-coat layer separately like a 1st aspect. The hard coat layer 11 can be provided between any one of the base material 10 and the antistatic layer 12, or between the antistatic layer 12 and the medium refractive index layer 14. These forms are shown in Figures 2H and 2I.

Layers and base materials other than the antistatic layer provided in the first to third aspects of the antireflection film having the antistatic function will be described.

(2) low refractive index layer

The low refractive index layer is a layer whose thickness is in the range of 0.05 to 0.20 mu m and the refractive index is 1.30 to 1.45.

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

In the preferable aspect which uses the laminated body of this invention as an antireflection film, a low refractive index layer is formed using curable resin composition containing component (E) and (F) mentioned later.

(3) high refractive index layer

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

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

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

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

(4) medium refractive index layer

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

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

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

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

(5) hard coating layer

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

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

(6) mention

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

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

(7) other layers

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

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

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

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

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

II. Cured film layer (Antistatic layer)

The cured film layer provided on the base material of the laminated body of this invention is obtained by hardening | curing the said liquid curable composition (Hereinafter, it may only be called "composition" or "antistatic layer forming composition."), It is conductive to a laminated body, A function as a high refractive index film and / or a function as a hard coating can be imparted.

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

1. Ingredient (A)

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

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

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

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

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

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

2. Ingredient (B)

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

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

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

Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth ) Acrylate and tricyclodecanediyldimethanol di (meth) acrylate are preferred. These (B) components may be used individually by 1 type, and may use 2 or more types together.

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

3. Ingredient (C)

Even if the component (C) used for this invention is mix | blended with small content of the electroconductive particle of a component (A), it has a function which provides the outstanding antistatic performance to the cured film containing the liquid curable composition obtained.

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

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

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

As a photoinitiator which can be used as a component (C), 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- ( 4- (1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1- On etc. can be mentioned.

The compounding quantity of component (C) becomes like this. Preferably it is 0.1-15 weight% with respect to 100 weight% of total amounts of solids other than component (D), More preferably, it is 0.5-10 weight%. A component (C) can be used individually by 1 type or in combination of 2 or more type.

4. Component (D) Solvent

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

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

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

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

5. Compounds having other polymerizable unsaturated groups

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

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

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

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

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

6. Additive

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

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

7. Non-Conductive Particles

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

By using the non-conductive particles in combination with the phosphorus-containing tin oxide particles as the component (A), the scratch resistance can be improved while maintaining an antistatic function, that is, a value of 10 ¹² Ω / □ or less as a surface resistance when the cured film is used. have.

The non-conductive particles are not particularly limited as long as they are particles other than the phosphorus-containing tin oxide particles which are the component (A). Preferably, these are oxide particles or metal particles other than the component (A). Specifically, oxide particles containing silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, or the like, or oxide particles containing two or more elements selected from the group consisting of silicon, aluminum, zirconium, titanium, and cerium Can be mentioned.

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

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

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

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

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

8. Manufacturing method of composition for antistatic layer formation

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

9. Formation method of cured film layer

The cured film layer of the laminated body of this invention can be obtained by apply | coating and drying the above-mentioned composition for antistatic layer formation to the said base material, irradiating a radiation, and hardening a composition.

The surface resistance of the obtained cured film layer is 1x10 <^12> ohm / square or less, Preferably it is 1x10 <^10> ohm / square or less, More preferably, it is 1x10 <^8> ohm / square or less. When surface resistance exceeds 1x10 <^{12> (} ohm) / (square), antistatic performance may not be enough and it may become easy to adhere dust or the attached dust may not be easy to remove.

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

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

As a source of visible light, for example, direct sunlight, a lamp, a fluorescent lamp, a laser, and the like, and as a source of ultraviolet light, for example, a mercury lamp, a halide lamp, a laser, and the like, and a commercial source as an electron beam, for example, are commercially available. And a method of using a hot electron generated from a tungsten filament, a cold cathode method generated by a high voltage pulse to a metal, and a secondary electron method using a secondary electron generated by a collision of ionized gaseous molecules with a metal electrode. .

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

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

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

III. Low refractive index layer

In order to use the laminated body of this invention as an antireflection film, it is necessary to form a low refractive index layer on the said cured film layer at least. The low refractive index layer formed in the laminate of the present invention is a curable resin composition containing a (E) ethylenically unsaturated group-containing fluorine-containing polymer and (F) silica particles (hereinafter referred to as "composition for forming a low refractive index layer"). It is preferable that it is a hardened | cured material containing).

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

1. Ingredient (E)

The ethylenically unsaturated group-containing fluorine-containing polymer (E) used in the composition for forming the low refractive index layer is obtained by reacting a compound containing one isocyanate group and one or more ethylenically unsaturated groups with a hydroxyl group-containing fluorine-containing polymer.

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

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

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

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

As such a compound, 1 type (s) or 2 or more types of combinations of 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate are mentioned.

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

As an example of diisocyanate, 2, 4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), and 1, 3-bis (isocyanate methyl) cyclohexane are preferable.

As an example of hydroxyl group containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.

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

(2) hydroxyl-containing fluorine-containing polymer

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

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

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

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

<Formula 2>

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

<Formula 3>

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

&Lt; Formula 4 >

In formula (4), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(i) structural units (a)

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

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

Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxy alkyl vinyl ether) are more preferable, and it is more preferable to use them in combination.

On the other hand, the content rate of the structural unit (a) is 20 to 70 mol% when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mol%. The reason for this is that if the content is less than 20 mol%, it may be difficult to express low refractive index, which is a characteristic of the optically fluorine-containing material, as intended by the present application. It is because the solubility, transparency, or adhesiveness to a base material of a hydroxyl-containing fluorine-containing polymer may fall.

For this reason, the content rate of the structural unit (a) is more preferably 25 to 65 mol%, more preferably 30 to 60 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(ii) structural units (b)

In the formula 3, R ³ or R ⁴ as an alkyl group methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, la may be mentioned an alkyl group having 1 to 12 carbon atoms such as a lauryl group, a methoxy alkoxy group of R ⁵ An oxycarbonyl group, an ethoxycarbonyl group, etc. are mentioned.

The structural unit (b) can be introduced by using the above-described vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether and n- Alkyl vinyl ethers or cycloalkyl vinyl ethers such as hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether; Allyl ethers such as ethyl allyl ether and butyl allyl ether; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl pivalate, a vinyl caproate, a vinyl versatate, and a vinyl stearate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) (Meth) acrylic acid esters such as acrylate and 2- (n-propoxy) ethyl (meth) acrylate; 1 type single or 2 types or more combinations, such as unsaturated carboxylic acids, such as (meth) acrylic acid, a crotonic acid, a maleic acid, a fumaric acid, and itaconic acid, are mentioned.

On the other hand, the content rate of the structural unit (b) is 10 to 70 mol% when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mol%. The reason is that the solubility of the hydroxyl group-containing fluorine-containing polymer in the organic solvent may be lowered if the content is less than 10 mol%. On the other hand, if the content is more than 70 mol%, the transparency of the hydroxyl-containing fluorine-containing polymer, And optical properties such as low reflectivity may be deteriorated.

For this reason, the content of the structural unit (b) is more preferably 20 to 60 mol%, more preferably 30 to 60 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(iii) structural units (c)

In the general formula (4), the hydroxyalkyl group of R ⁷ is 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxy A pentyl group, 6-hydroxyhexyl group, etc. are mentioned.

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

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

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

For this reason, the content rate of the structural unit (c) is more preferably 5 to 40 mol%, more preferably 5 to 30 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer.

(iv) structural units (d) and structural units (e)

It is also preferable that the hydroxyl-containing fluorine-containing polymer further comprises the following structural unit (d).

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

&Lt; Formula 5 >

[In Formula 5, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

In formula (5), an alkyl group of R ⁸ or R ⁹ is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group, and a halogenated alkyl group is a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluoro group. Examples of the aryl group include a fluoroalkyl group such as a robutyl group and the like, and a phenyl group, benzyl group, naphthyl group and the like can be given.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (5). As an example of such an azo group containing polysiloxane compound, the compound represented by following formula (11) is mentioned.

In Formula 11, R ¹⁸ to R ²¹ may be the same or different, and represent a hydrogen atom, an alkyl group or a cyano group, R ²² to R ²⁵ may be the same or different, and represent a hydrogen atom or an alkyl group, p, q is a number from 1 to 6, s, t is a number from 0 to 6, y is a number from 1 to 200, z is a number from 1 to 20]

In the case of using the compound represented by the formula (11), the structural unit (d) is included in the hydroxyl group-containing fluorine-containing polymer as part of the structural unit (e).

(e) The structural unit represented by following formula (12).

[Formula 12, R ¹⁸ to R ²¹ , R ²² to R ²⁵ , p, q, s, t and y are the same as in the general formula (11)]

In formulas (11) and (12), examples of the alkyl group of R ¹⁸ to R ²¹ include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group, and a methyl group as the alkyl group of R ²² to R ²⁵ . And alkyl groups having 1 to 3 carbon atoms such as ethyl group and propyl group.

In this invention, the compound represented by following formula (13) is especially preferable as an azo-group containing polysiloxane compound represented by said Formula (11).

[In Formula 13, y and z are the same as those of Formula 11]

On the other hand, when the content rate of the structural unit (d) is 100 mol% when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mol%, it is preferable to be 0.1 to 10 mol%. The reason is that if the content is less than 0.1 mol%, the surface slip resistance of the coating film after curing may be lowered, and the scratch resistance of the coating film may be lowered. This is because the transparency of the polymer is poor, and when used as a coating material, repulsion or the like may easily occur during coating.

For this reason, the content of the structural unit (d) is more preferably 0.1 to 5 mol%, more preferably 0.1 to 3 mol% with respect to the total amount of the hydroxyl group-containing fluorine-containing polymer. For the same reason, the content rate of the structural unit (e) is preferably determined so that the content rate of the structural unit (d) contained therein is within the above range.

(v) structural units (f)

It is also preferable that the hydroxyl-containing fluorine-containing polymer further comprises the following structural unit (f).

(f) The structural unit represented by following formula (14).

In formula (14), R ²⁶ represents a group having an emulsifying action.

In the formula (14), a group having an emulsifying action of R ²⁶ is preferably a group having both a hydrophobic group and a hydrophilic group while the hydrophilic group is a polyether structure such as polyethylene oxide and polypropylene oxide.

As an example of group which has such an emulsification effect, group represented by following formula (15) is mentioned.

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

The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following general formula (16).

[In Formula 16, n, m and u are the same as in Formula 15]

On the other hand, when the total amount of the hydroxyl group-containing fluorine-containing polymer is 100 mol%, the content rate of the structural unit (f) is preferably 0.1 to 5 mol%. The reason is that when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluorine-containing polymer in the solvent is improved. On the other hand, when the content is within 5 mol%, the adhesiveness of the curable resin composition does not increase excessively and is easy to handle. This is because the moisture resistance does not decrease even when used as a coating material.

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

(vi) molecular weight

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

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

(3) reaction molar ratio

The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting a compound containing one isocyanate group and at least one ethylenically unsaturated group described above with a hydroxyl group-containing fluorine-containing polymer. The compound containing one isocyanate group and at least one ethylenically unsaturated group and the hydroxyl group-containing fluorine-containing polymer are preferably reacted at a ratio in which the molar ratio of the isocyanate group / hydroxyl group is 1.1 to 1.9. This is because if the molar ratio is less than 1.1, the scratch resistance and durability may decrease. On the other hand, if the molar ratio exceeds 1.9, the scratch resistance after immersion of the aqueous alkali solution of the coating film of the curable resin composition may decrease. .

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

Although it does not restrict | limit especially about the addition amount of (E) component in curable resin composition, It is 1-95 mass% normally with respect to composition whole quantity other than the organic solvent. The reason for this is that when the addition amount is less than 1% by mass, the refractive index of the cured coating film of the curable resin composition may increase, and a sufficient antireflection effect may not be obtained. On the other hand, when the addition amount exceeds 95% by mass, This is because the scratch resistance of the cured coating film may not be obtained.

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

2. Ingredient (F)

(1) Particles based on silica

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

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

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

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

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

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

It is preferable that the silica particle used for this invention has an ethylenically unsaturated group (henceforth "reactive silica particle"). Although the manufacturing method of a reactive silica particle is not specifically limited, For example, it can obtain by making the above-mentioned number average particle diameter silica particle and the reactive surface treating agent react with 10-100 nm.

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

As a specific example of a surface treating agent, The compound which has an unsaturated double bond in molecules, such as (gamma)-methacryloxypropyl trimethoxysilane, (gamma) -acryloxypropyl trimethoxysilane, and vinyl trimethoxysilane, is represented by following formula (9). The compound which becomes.

In formula, R <^12> is a methyl group, R <^13> is a C1-C6 alkyl group, R <^14> is a hydrogen atom or a methyl group, a is 1 or 2, b is an integer of 1-5, A is a C1-C6 divalent alkyl A benzene group, B is a divalent hydrocarbon group having 3 to 14 carbon atoms in any one of a chain, cyclic or branched phase, and Z is a divalent hydrocarbon group having 2 to 14 carbon atoms in any one of a (b + 1) valent chain, cyclic and branched phase. . In Z may include an ether bond.

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

(3) Preferred Embodiments (Porous Silica Particles)

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

As the porous silica particles, it is more preferable to use the first porous silica particles (F1) or the second porous silica particles (F2). The first porous silica particles (F1) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (6) and a silicon compound represented by the following formula (7). That is, it is obtained by hydrolyzing and / or hydrolytically condensing the silicon compound represented by the general formula (7) while hydrolyzing and / or hydrolytically condensing the silicon compound represented by the general formula (6). The silicon compound represented by the formula (6) and the silicon compound represented by the formula (7) may be mixed and hydrolyzed and / or hydrolyzed condensed simultaneously, and the silicon compound represented by the formula (6) is hydrolyzed and / or hydrolyzed condensed, and then The silicon compound represented by the formula (7) may be added to further hydrolyze and / or hydrolyzed condensation. The second porous silica particles (F2) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (6), a silicon compound represented by the following formula (7) and a silicon compound represented by the following formula (8). That is, hydrolyzing and / or hydrolytically condensing the silicon compound represented by the formula (6), hydrolyzing and / or hydrolytically condensing the silicon compound represented by the formula (7), and further hydrolyzing the silicon compound represented by the formula (8) and And / or hydrolytic condensation. The silicon compound represented by the formula (6), the silicon compound represented by the formula (7) and the silicon compound represented by the formula (8) may be mixed and hydrolyzed and / or hydrolyzed condensed at the same time, and hydrolyzed and And / or hydrolytic condensation, and then a silicon compound represented by the formula (7) and a silicon compound represented by the formula (8) may be added to further hydrolyze and / or hydrolytic condensation.

(6)

SiX ₄

&Lt; Formula 7 >

R ¹⁰ _j SiX _{4 -j}

(8)

R ¹¹ _k SiX _{4 -k}

In the formulas (6), (7) and (8), each X independently represents an alkoxy group, a halogeno group, an isocyanate group, a carboxyl group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, preferably Is an alkoxy group and a halogeno group, More preferably, it is an alkoxy group. In addition, X in Chemical Formulas 6, 7 and 8 may be the same or different.

As a compound represented by General formula (6), tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane, etc. are mentioned, for example.

In formula (7), R ¹⁰ is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a vinyl group, allyl group, acryloxyethyl group, or acryloxy Propyl group, acryloxybutyl group, methacryloxyethyl group, methacryloxypropyl group, and methacryloxybutyl group.

In Formula 7, j is an integer of 1-3, Preferably it is 1-2.

As a compound represented by General formula (7), vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, acryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, etc. are mentioned, for example.

By using the compound represented by General formula (7), porous silica particle can be made to contain an ethylenically unsaturated group. By including an ethylenically unsaturated group, the scratch resistance of the antireflection film of this invention which has the cured film which hardened | cured the curable composition improves.

In formula (8), R ¹¹ is a C1-C12 fluorine-substituted alkyl group, Preferably it is a C3-C12 fluorine-substituted alkyl group, More preferably, it is a C3-C10 fluorine-substituted alkyl group.

In formula (8), k is an integer of 1-3, Preferably it is 1-2.

Examples of the compound represented by the formula (8) include 3,3,3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, 2-perfluorohexylethyltrimethoxysilane, 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 3,3-di (trifluoromethyl) -3-fluoropropyltriethoxysilane, etc. are mentioned. .

By using the compound represented by General formula (8), porous silica particle can be made to contain a fluorine-containing alkyl group. By containing a fluorine-containing alkyl group, the stain resistance of the cured film which hardened the curable composition can be improved.

In addition, the silicon compound represented by the formula (6), the silicon compound represented by the formula (7), and the silicon compound represented by the formula (8) may each be used two or more kinds.

In the first porous silica particles (F1), when the total of the silicon compound represented by the formula (6) and the silicon compound represented by the formula (7) is 100 mol%, the silicon compound represented by the formula (6) / silicon represented by the formula (7) The compound is preferably hydrolyzed and / or hydrolyzed condensed at a ratio of preferably 67 to 99/1 to 33 (mol%), more preferably 70 to 98/2 to 30 (mol%).

In the second porous silica particles (F2), when the total of the silicon compound represented by the formula (6), the silicon compound represented by the formula (7) and the silicon compound represented by the formula (8) is 100 mol%, the silicon represented by the formula (6) The silicon compound represented by the compound / Formula 7 / the silicon compound represented by the formula 8 is preferably 60 to 98/1 to 30/1 to 20 (mol%), more preferably 65 to 96/2 to 20 / Hydrolysis and / or hydrolysis condensation at a ratio of 2 to 15 (mol%).

The first and second porous silica particles (F1) and (F2) used in the present invention have an average particle diameter of 5 to 50 nm, preferably 5 to 45 nm, and more preferably 5 to 40 nm. An average particle diameter is a number average particle diameter, and is measured by a transmission electron microscope observation image. In addition, "porous" means that the specific surface area is 50 to 1000 m ² / g, preferably 50 to 800 m ² / g, more preferably 100 to 800 m ² / g. The specific surface area is measured by the BET method.

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

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

The first or second porous silica particles (F1), (F2) are each represented by the above chemical formula in the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and half ethers of acid amides, diols and diols. Hydrolysis and / or hydrolysis condensation of a silicon compound represented by 6 and a silicon compound represented by Formula 7, or a silicon compound represented by Formula 6, a silicon compound represented by Formula 7 and a silicon compound represented by Formula 8 It can manufacture.

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

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

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

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

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

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

The total concentration of the silicon compound of the formula (6) and the silicon compound of the formula (7) or the silicon compound of the formulas (6) to (8) is usually 0.5 to 10% by mass, preferably 1 to 8% by mass, in terms of complete hydrolysis condensate. Here, "complete hydrolysis condensate conversion" is a theoretical value calculated on the assumption that the silicon compound is completely hydrolytically condensed, and X of the silicon compound of Formula 6 and the silicon compound of Formula 7 or the silicon compound of Formula 6 to 8 It corresponds to the mass in the case of substituting with 1/2 mol of oxygen atom of X. By making the density | concentration of the silicon compound at the time of particle | grain synthesis into the said range, coarsening of a particle can be prevented and it can be set as the particle | grains of 5-50 nm of average particle diameters.

The silicon compound of formula 6 and the silicon compound of formula 7, or the silicon compound of formula 6, the silicon compound of formula 7 and the silicon compound of formula 8 may be simultaneously mixed to hydrolyze and / or hydrolyze condensate, and also water, In the presence of one or more selected from alcohols, basic compounds, and half ethers of acid amides, diols and diols, the silicon compounds represented by the formula (6) are hydrolyzed and / or hydrolyzed condensed, and then respectively The silicon compound represented by 7, or the silicon compound represented by the formula (7) and the silicon compound represented by the formula (8) can be added to further hydrolyze and / or hydrolytic condensation.

The reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acid amides to be used. The reaction time depends on the kind of silicon compound represented by the formula (6), the silicon compound represented by the formula (7), and the silicon compound represented by the formula (8), the reaction rate, the type and amount of the base, etc. It doesn't work.

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

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

The blending amount of the porous silica particles (F) in the resin composition is usually blended in an amount of from 5 to 99 mass%, preferably from 10 to 98 mass%, more preferably from 15 to 97 mass%, based on the total amount of the composition other than the organic solvent. If it is less than 5 mass%, the hardness at the time of setting it as a cured film may become inadequate, and if it exceeds 99 mass%, sufficient film strength may not be obtained. On the other hand, the amount of particles means a solid content, and when the particles are used in the form of a solvent dispersion, the amount of the particles does not include the amount of the solvent.

(4) optional additive ingredients

The following components can be added to the composition for low refractive index layers used by this invention as needed.

(H) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group

The curable resin composition includes a polyfunctional (meth) acrylate compound containing at least two or more (meth) acryloyl groups and / or a fluorine-containing (meth) acryl containing at least one or more (meth) acryloyl groups. You may also add a rate compound.

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

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

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

(2) Fluorine-containing (meth) acrylate compounds containing at least one (meth) acryloyl group

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

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

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

(I) Compounds that generate active species by irradiation or heat of active energy rays

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

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

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

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

(i) Type

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

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

(ii) added amount

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

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

(2) Compounds that generate active species by heat

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

(i) Type

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

(ii) added amount

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

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

(J) organic solvent

It is preferable to add an organic solvent further to curable resin composition. By adding an organic solvent in this way, the anti-reflection film of a thin film can be formed uniformly. As such an organic solvent, an organic solvent having an alcohol of 1 to 8 carbon atoms, a ketone having 3 to 10 carbon atoms, and an ester having 3 to 10 carbon atoms can be preferably used, and methyl isobutyl ketone, methyl ethyl ketone, methyl amyl ketone, Methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol monopropyl ether, etc. are mentioned as a particularly preferable example. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

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

(K) additive

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

(5) Manufacturing method of composition for low refractive index layer formation

Curable resin composition used by this invention is the said (E) ethylenically unsaturated group containing fluorine-containing polymer and the said (F) component, or the said (H) component, (I) component, (J) organic solvent, and ( K) Additives, respectively, can be prepared by mixing at room temperature or under heating conditions. Specifically, it can manufacture using mixers, such as a mixer, a kneader, a ball mill, and a triaxial roll. However, when mixing under heating conditions, it is preferable to carry out below the decomposition start temperature of a thermal polymerization initiator.

(6) Hardening method of the composition for low refractive index layer formation

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

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

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

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

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

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

Example 1

(1) Preparation of Liquid Curable Composition

Phosphorus-containing tin oxide dispersion liquid (ELCOM JX-1001PTV, manufactured by Shokubai Kasei Kogyo Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30 wt%, average primary particle size 20 nm, in a container shielding ultraviolet rays) 200 parts of a dispersing agent) 200 parts, 31.2 parts of dipentaerythritol hexaacrylate (The brand name KAYARAD DPHA by Nippon Kayaku Co., Ltd., hereafter, may refer to B-1), 1-hydroxycyclohexylphenyl 4.5 parts of ketones (it may be called C-1 hereafter), and 50 parts of propylene glycol monomethyl ethers were stirred at 50 degreeC for 2 hours, and the composition of a uniform solution was obtained.

After weighing 2 g of the obtained composition on an aluminum plate, the resultant was dried and weighed on a hot plate at 140 ° C. for 1 hour to obtain a solid content, which was 35% by weight. Furthermore, after weighing 2 g of the composition in a magnetic crucible, the inorganic content in the solid content was determined from the inorganic residue after preliminary drying for 30 minutes on a hot plate at 80 ° C and calcining for 1 hour in a muffle at 750 ° C. %.

(2) Production of Cured Film

The composition obtained in the above (1) was coated on an ARTON film G7810 (manufactured by JSR Co., Ltd., film thickness of 188 μm) using a wire bar coater, and dried in an oven at 80 ° C. for 3 minutes. . Subsequently, using a metal halide lamp in the air, the coating film was ultraviolet cured under light irradiation conditions of 1 J / cm ² to prepare a film having a cured film (hard coating layer) having a thickness of 3 μm.

(3) Evaluation of physical properties of cured film

The total light transmittance, haze, pencil hardness, and surface resistance of the cured film film obtained in the above (2) were evaluated based on the following criteria.

(a) Total light transmittance and haze

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

(b) pencil hardness

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

(c) surface resistance

The voltage applied to the cured film by using a high resistance meter (Agilent 4339B manufactured by Agilent Technologies Co., Ltd.) and resistance cell 16008B (manufactured by Agilent Technologies Co., Ltd.) It measured on the conditions of 100V. The obtained results are shown in Table 1.

Examples 2 to 7 and Comparative Examples 1 to 3

Except having used the component shown in Table 1, the liquid curable compositions of Examples 2-7 and Comparative Examples 1-3 were produced like Example 1, the cured film was produced, and the physical property evaluation of the cured film was performed.

The obtained results are shown in Table 1.

The symbol in Table 1 shows the following, respectively.

B-1: dipentaerythritol hexaacrylate

B-2: tricyclodecanediyl dimethanol diacrylate

C-1: 1-hydroxycyclohexylphenyl ketone (molar extinction coefficient at 313 nm 80 L / molcm)

C-2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (molar extinction coefficient at 313 nm: 3,000 L / molcm)

C-3: oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) (molar extinction coefficient at 313 nm: 230 L / molcm)

C'-4: 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one (molar extinction coefficient at 313 nm: 17,000 L / molcm)

C'-5: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (molar extinction coefficient at 313 nm: 17,000 L / molcm)

Dispersant: Dispersant included in phosphorus-containing tin oxide dispersion ELCOM JX-1001PTV

PGME: Propylene glycol monomethyl ether

From the results in Table 1, the total light transmittance and the pencil hardness do not show a significant difference between the examples and the comparative examples, but the photopolymerization initiator C'- with a molar extinction coefficient at 313 nm exceeding 5,000 L / mol · cm. in Comparative example 4, or with the C'-5 cured film surface resistance value of the counter to 10 ^14-order, the molar extinction coefficient at 313 ㎚ 5,000 L / mol · cm or less photopolymerization initiator C-1 to C-3 (the In the Example using the component (C) in this invention, it is remarkably low in order of 10 <^6> -10 <^9> , and it turns out that it is excellent in antistatic performance.

Preparation Example 1 Synthesis of Organic Compound Having Polymeric Unsaturation

To the solution containing 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate were dripped at 50 degreeC over 1 hour, stirring at 70 degreeC, The mixture was heated and stirred for 3 hours. Shin Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N (60 weight% of pentaerythritol triacrylate and 40 weight% of pentaerythritol tetraacrylate is contained, Among these, it is a hydroxyl group 549 parts of pentaerythritol triacrylate which has the following) was dripped at 30 degreeC over 1 hour, and the organic compound which has a polymerizable unsaturated group was obtained by heating and stirring at 60 degreeC for 10 hours. Analysis of the amount of remaining isocyanate in the reaction solution by FT-IR showed 0.1% or less, indicating that the reaction was almost quantitatively terminated. Infrared absorption spectra of the product lose the absorption peak of the 2550 kaiser characteristic of the mercapto group in the raw material and the absorption peak of the 2260 kaiser characteristic of the raw isocyanate compound and newly 1660 characteristic of the urethane bond and S (C═O) NH-group. The peak of Kaiser and the peak of 1720 Kaiser characteristic of the acryloxy group were observed, indicating that an acryloxy group-modified alkoxysilane having an acryloxy group, -S (C = 0) NH-, and a urethane bond as a polymerizable unsaturated group was produced. It was. By the above, in addition to the compound represented by the following general formula (17-1) and (17-2) obtained 773 parts in total (henceforth this compound may be called "alkoxysilane (1)"), 220 parts of pentaerythritol tetraacrylate which is not involved are mixed.

<Formula 17-1>

<Formula 17-2>

[In Formula 17-1 and 17-2, "Acryl" represents acryloyl group and "Me" represents a methyl group.]

Preparation Example 2 Preparation of a Compound Represented by Formula 18

[In Formula 18, "Acryl" represents an acryloyl group.]

For a solution containing 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container with a stirrer, NK ester A-TMM-3LM-N manufactured by Shinnakamura Chemical Co., Ltd. 93 parts of pentaerythritol triacrylate which had only) was dripped under the conditions of 10 degreeC and 1 hour, and it stirred on the conditions of 60 degreeC and 6 hours, and set it as the reaction liquid.

The amount of remaining isocyanate in this reaction solution was measured by FT-IR in the same manner as in Production Example 1, and it was confirmed that the reaction was almost quantitatively performed at 0.1 wt% or less. In addition, it was confirmed that the molecule contains a urethane bond and acryloyl group (polymerizable unsaturated group).

As mentioned above, 37 parts of pentaerythritol tetraacrylate which did not participate in reaction were mixed in addition to 75 parts of compounds represented by the said Formula (18).

Preparation Example 3 Preparation of Composition for Silica Particle-Containing Hard Coating Layer

2.32 parts of solution of alkoxysilane (1) prepared in Production Example 1, silica particle sol (methyl ethyl ketone silica sol, MEK-ST manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.022 µm, silica concentration 30%) After stirring the mixture liquid of 91.3 parts (27 parts as silica particles), 0.12 parts of ion-exchange water, and 0.01 parts of p-hydroxyphenyl monomethyl ether at 60 degreeC for 4 hours, 1.36 parts of methyl ortho formates are added, and it is further 1 The reactive silica particle dispersion liquid was obtained by heat-stirring at the same temperature for time. In the same manner as in Example 1, the solid content and the inorganic content in the solid content were determined to be 30.7 wt% and 90 wt%, respectively.

98.6 g of this dispersion, 3.4 g of a solution containing the compound represented by formula (18) obtained in Production Example 2, 2.1 g of 1-hydroxycyclohexylphenylketone (C-1), 2-methyl-1- [4- (methyl Thio) phenyl] -2-morpholinopropane-1-one (C-2) 1.2 g, dipentaerythritol hexaacrylate 33.2 g, and cyclohexanone 7 g were mixed and stirred, and the composition for hard-coat layers containing silica particles ( 145 g of solid content concentration 50%) were obtained.

Preparation Example 4 Preparation of Reactive Silica Particle Sols with Organic Compounds Having Polymeric Unsaturation

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

Production Example 5: Preparation of hydroxyl-containing fluorine-containing polymer

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L stirrer with nitrogen gas, 465 g of ethyl acetate, 138.5 g of perfluoro (propyl vinyl ether), 37.5 g of ethyl vinyl ether, and hydroxy 46.0 g of ethyl vinyl ether, 180.0 g of "adekariasof ER-30" (manufactured by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, "VPS-1001" as azo group-containing polydimethylsiloxane (Wako Pure Chemical Industries, Ltd.) 9.0 g and Lauroyl peroxide 1.5 g were added, cooled to -50 ° C with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

Subsequently, 86.0 g of hexafluoropropylene were added, and the temperature was started. The pressure at the point where the temperature in the autoclave reached 60 ° C. was 2.9 × 10 ⁵ Pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was cooled with water at the time when the pressure dropped to 2.0 × 10 ⁵ Pa to stop the reaction. After reaching room temperature, the unreacted monomer was released, the autoclave was opened, and the polymer solution of 30.0% of solid content concentration was obtained. The obtained polymer solution was thrown into methanol, and the polymer was deposited, washed with methanol, and dried in vacuo at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluorine-containing polymer.

Preparation Example 6 Preparation of Ethylenic Unsaturation-Containing Fluorine-Containing Polymer

In a 1-liter separate flask equipped with an electronic stirrer, a glass cooling tube, and a thermometer, 70.0 g of the hydroxyl group-containing fluorine-containing polymer obtained in Production Example 5 and 0.01 g of 2,6-di-t-butylmethylphenol as a polymerization inhibitor And 520 g of MIBK were added and stirred until the hydroxyl group-containing fluorine-containing polymer was dissolved in MIBK at 20 ° C, and the solution became transparent and uniform. Subsequently, 22 g of 2-methacryloyloxyethyl isocyanate was added to this system, stirred until the solution became uniform, and then 0.2 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was 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 fluorine-containing polymer. After weighing 2 g of this solution to the aluminum dish, it dried for 5 minutes on the 150 degreeC hotplate, and weighed and calculated | required solid content, and it was 15.0%.

Preparation Example 7 Preparation of Composition 1 for Forming Low Refractive Index Layer

20 g of reactive silica particle sol obtained in Production Example 4 (6.2 g as reactive particles), 101.0 g of ethylenically unsaturated group-containing fluorine-containing polymer obtained in Production Example 6 (15.2 g as ethylenically unsaturated group-containing fluoropolymer), dipentaeryte Lithol pentaacrylate 1.7 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (C-2) 1.2 g, represented by the formula (18) obtained in Production Example 2 0.4 g of a compound, 0.1 g of an organic copolymer-containing special silicone (Florene AC-901, Kyoeisha Chemical Co., Ltd.) and 505.6 g of methyl isobutyl ketone are added, and the mixture is stirred at room temperature for 1 hour to form a low refractive index layer. Composition 1 was obtained. Solid content was calculated | required similarly to Example 1, and it was 4 weight%.

Preparation Example 8 Synthesis of Porous Silica Particles

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

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

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

Preparation Example 9 Preparation of Composition 2 for Forming Low Refractive Index Layer

56 g of the MIBK solution of the ethylenically unsaturated group-containing fluorine-containing polymer obtained in Production Example 6 (8.5 g as the ethylenically unsaturated group-containing fluorine-containing polymer) and 1750 g of the porous silica particle dispersion obtained in Production Example 8 as the porous silica particles 87.5 g), 4-g of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (C-2) as a photoinitiator, 700 g of MIBK were attached to the stirrer. It put in the glass separating flask, and it stirred at 23 degreeC for 1 hour, and obtained the composition 2 for low refractive index layer formation. Solid content was calculated | required similarly to Example 1, and it was 4 weight%.

Example 8

Preparation of Anti-Reflective Laminates (1)

The composition 1 for antistatic layer formation obtained in Example 3 was coated on Aton film G7810 (manufactured by JSR Corporation, a film thickness of 188 μm) using a wire bar coater # 12, and the conditions were 80 ° C. for 3 minutes in an oven. Dried. Subsequently, using a metal halide lamp in the air, the coating film was UV cured under light irradiation conditions of 1 J / cm ² to prepare a film having a hard coating layer. It was 3 micrometers when the film thickness of the hard coat layer was measured by the stylus type surface shape measuring instrument. On the film with a hard coat, the composition 1 for low refractive index layer formation obtained by the manufacture example 7 was coated using wire bar coater # 3, and it dried on the conditions of 80 degreeC and 1 minute in oven. Subsequently, under a nitrogen atmosphere, the coating film was ultraviolet-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp to form a low refractive index layer to prepare an antireflective laminate 1. It was 0.1 micrometer when the film thickness of the low refractive index layer was computed from the reflectance of the obtained antireflective laminated body 1.

Example 9

Preparation of Anti-Reflective Laminate 2

An anti-reflective laminate 2 was prepared in the same manner as in Example 8 except that the low refractive index layer-forming composition 2 obtained in Production Example 9 was used instead of the low refractive index layer-forming composition 1. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 8.

Example 10

Preparation of Anti-Reflective Laminate 3

The composition for the silica particle-containing hard coat layer obtained in Production Example 3 was coated on Aton film G7810 (manufactured by JSR Co., Ltd., film thickness of 188 μm) using a wire bar coater # 6, and then heated at 80 ° C. for 3 minutes in an oven. It dried on condition of. Subsequently, using a metal halide lamp in the air, the coating film was UV-cured under light irradiation conditions of 1 J / cm ² to prepare a film having a hard coating layer. It was 3 micrometers when the film thickness of the hard coat layer was measured by the stylus type surface shape measuring instrument. On the film with a hard coat, the composition 1 for antistatic layer formation obtained in Example 3 was diluted to 5% of solid content concentration with propylene glycol monomethyl ether, and it coats using wire bar coater # 6, and is 80 in an oven It dried on the conditions of 1 degreeC. Subsequently, under nitrogen atmosphere, the coating film was ultraviolet-cured by the light irradiation conditions of 1 J / cm <^2> using a metal halide lamp, and the high refractive index layer was formed. It was 0.1 micrometer as a result of calculating the film thickness of the high refractive index layer similarly to Example 8. The composition 1 for low refractive index layer formation obtained by the manufacture example 7 was coated on the obtained laminated body using the wire bar coater # 3, and it dried on the conditions of 80 degreeC and 1 minute in oven. Subsequently, under a nitrogen atmosphere, the coating film was ultraviolet-cured under light irradiation conditions of 1 J / cm ² using a metal halide lamp to form a low refractive index layer to prepare an antireflective laminate 3. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer from the reflectance of the obtained antireflective laminated body 3.

Example 11

Preparation of Antireflective Laminate 4

An anti-reflective laminate 4 was prepared in the same manner as in Example 10 except that the low refractive index layer-forming composition 2 obtained in Production Example 9 was used instead of the low refractive index layer-forming composition 1. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 8.

Comparative Example 4

Preparation of Antireflective Laminate 5

An antireflective laminate 5 was prepared in the same manner as in Example 8 except that the composition 2 for forming an antistatic layer obtained in Comparative Example 3 was used instead of the composition 1 for forming an antistatic layer. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 8.

Comparative Example 5

Preparation of Antireflective Laminate 6

An antireflective 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 9 was used instead of the low refractive index layer-forming composition 1. It was 0.1 micrometer as a result of calculating the film thickness of the low refractive index layer similarly to Example 8.

Evaluation example

The following characteristics were evaluated about the antireflective laminated bodies 1-6 obtained in Examples 8-11 and Comparative Examples 4-5.

(a) Total light transmittance and haze

The total light transmittance (%) and haze (%) of the cured film were measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Shikeki Co., Ltd.). The results obtained are shown in Table 2 below.

(b) pencil hardness

The cured film was placed on a glass substrate, and the pencil hardness was evaluated based on JIS K5600-5-4. The obtained results are shown in Table 2.

(c) surface resistance

The voltage applied to the cured film by using a high resistance meter (Agilent 4339B manufactured by Agilent Technologies Co., Ltd.) and resistance cell 16008B (manufactured by Agilent Technologies Co., Ltd.) It measured on the conditions of 100V. The obtained results are shown in Table 2.

(d) reflectance

The reflectance of the obtained antireflective laminate was measured using a spectral reflectance measuring device (magnetic spectrophotometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd.) incorporating a large sample chamber integrating sphere accessory 150-09090. The reflectance was measured and evaluated in the 700 nm range. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured based on the reflectance in the vapor deposition film of aluminum. The reflectance at wavelength 550 nm is shown in Table 2.

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

The steel wool resistance test of the antireflective laminate was conducted by the following method. That is, a steel wool (Bonstar No.0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Hakjin type friction fastness tester (AB-301, Tester Sangyo Co., Ltd.), and the surface of the cured film has a load of 500 g. Ten times of repetition was performed under the conditions, and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated based on the following criteria. The results are shown in Table 2.

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

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

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

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

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

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

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

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

(g) Chemical resistance test (ethanol resistance test)

The ethanol tolerance test of the cured film was implemented by the method shown next. That is, a nonwoven fabric (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) infiltrated with ethanol was attached to a school-type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was subjected to a load of 500 g. After 20 times of repeated abrasion, the presence or absence of the flaw in the surface of the said cured film was visually confirmed, and the following references | standards evaluated. The results are shown in Table 2.

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

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

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

From the result of Table 2, from the liquid curable composition (composition for antistatic layer formation) containing the photoinitiator whose molar extinction coefficient in 313 nm (C) 313 nm which comprises the laminated body of this invention is 5,000 L / mol * cm or less. It is understood that the antireflective laminate having the antistatic layer formed has a small surface resistance and has excellent antistatic performance.

ADVANTAGE OF THE INVENTION According to this invention, the liquid curable composition and cured film which can form the coating film (film | film | coat) which is excellent in curability and excellent in antistatic property, hardness, abrasion resistance, and transparency on the surface of various base materials can be provided.

The cured film of this invention mainly scratches product surfaces, such as a protective film for touch panels, the transfer foil, the hard coating for optical disks, the windscreen for automobiles, the antistatic protective film for lenses, and the surface protective film of highly decorative containers, such as a cosmetic container. It can be used as a hard coating performed for the purpose of preventing or preventing dust adhesion by static electricity.

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

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

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

Claims (23)

Liquid curable composition containing following component (A)-(D). (A) Spherical phosphorus-containing tin oxide particles having a primary particle diameter of 10 nm to 100 nm (B) a compound selected from the group consisting of (meth) acrylic esters and vinyl compounds (C) Photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less (D) Solvent delete The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator of (C) is 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1 -(4- (1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane- Liquid curable composition which is 1 or more types chosen from 1-one. The cured film formed by hardening | curing the liquid curable composition of Claim 1, and whose surface resistance value is 1 * 10 <^{12> (} ohm) / square or less. The manufacturing method of the cured film which has a process of irradiating a liquid curable composition of Claim 1 to harden the said composition. At least with the base material, The laminated body which has a cured film layer formed by hardening | curing the liquid curable composition containing following component (A)-(D). [Liquid curable composition] (A) Spherical phosphorus-containing tin oxide particles having a primary particle diameter of 10 nm to 100 nm (B) a compound selected from the group consisting of (meth) acrylic esters and vinyl compounds (C) Photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less (D) Solvent delete The antistatic laminate according to claim 6, wherein the cured film layer has a thickness of 0.05 to 20 µm. The laminated body of Claim 6 which is an optical component which has an antistatic function. The laminated body of Claim 9 which is an anti-reflective film. The laminate according to claim 6, wherein the surface resistance is 1 × 10 ¹² Ω / square or less. The said laminated body is an anti-reflective film of Claim 10 in which the antistatic layer and the low refractive index layer are laminated | stacked in this order from the side near a base material on a base material, The laminated body whose said cured film layer is an antistatic layer. The laminate according to claim 12, wherein a refractive index of the antistatic layer is higher than that of the low refractive index layer. The laminate according to claim 6, wherein a hard coat layer is further formed on the substrate. The method of claim 12, wherein the low refractive index layer The laminated body which is hardened | cured material of curable resin composition containing following component (E) and (F). (E) a compound containing one isocyanate group and one or more (meth) acryloyl groups, and 20 to 70 mol% of the structural unit (a) represented by the following formula (2), 10 to 70 mol% of the structural unit (b) represented by the following Formula (3) and 5 to 40 mol% of the structural unit (c) represented by the following Formula (4) Including, and also Hydroxyl group-containing fluorine-containing polymer having a polystyrene reduced number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography. Ethylenically unsaturated group-containing fluorine-containing polymer obtained by reacting (F) particles comprising silica <Formula 2>

[In Formula 2, R ¹ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ² (R ² represents an alkyl group or a fluoroalkyl group.) <Formula 3>

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

In formula (4), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1] delete The laminate according to claim 15, wherein the hydroxyl group-containing fluorine-containing polymer further comprises 0.1 to 10 mol% of the structural unit (d) represented by the following general formula (5) derived from an azo group-containing polysiloxane compound. &Lt; Formula 5 >

[In Formula 5, R ⁸ and R ⁹ may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.] The laminated body of Claim 15 whose said component (F) is a silica particle which has an ethylenically unsaturated group on the surface. The method of claim 15 wherein said component (F) is A laminate comprising the hydrolyzate and / or hydrolysis condensate of a silicon compound represented by the following formula (6) and a silicon compound represented by the following formula (7), and having an average particle diameter of 5 to 50 nm. (6) SiX ₄ &Lt; Formula 7 > R ¹⁰ _j SiX _4-j (X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, and R ¹⁰ is an alkenyl group having 2 to 8 carbon atoms) , An acryloxyalkyl group having 4 to 8 carbon atoms or a methacryloxyalkyl group having 5 to 8 carbon atoms, j represents an integer of 1 to 3, X in Formula 6 and X in Formula 7 may be the same or different) The method of claim 15 wherein said component (F) is A porous silica having a silicon compound represented by the following formula (6), a silicon compound represented by the following formula (7) and a silicon compound represented by the following formula (8), and a hydrolyzate and / or a hydrolysis condensate, having an average particle diameter of 5 to 50 nm. The laminated body which is particle | grain (F2). (6) SiX ₄ &Lt; Formula 7 > R ¹⁰ _j SiX _4-j (8) R ¹¹ _k SiX _4-k (X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbonyl group having 2 to 4 carbon atoms or an alkylamino group having 1 to 4 carbon atoms, and R ¹⁰ is an alkenyl group having 2 to 8 carbon atoms) , represents a methacryloxy alkyl group having acryloxy group or a carbon number of 5 to 8 having a carbon number of 4 to 8, j is an integer of 1 to 3, R ¹¹ represents a fluorine-substituted alkyl group having 1 to 12, k is 1 to An integer of 3, wherein X in Formula 6, X in Formula 7, and X in Formula 8 may be the same or different) 20. The hydrolyzate and / or hydrolysis condensation according to claim 19, wherein the porous silica particles (F1) have a total sum of the silicon compound represented by the formula (6) and the silicon compound represented by the formula (7) as 100 mol%. A laminate comprising water reacting 67 to 99 mol% of the silicon compound represented by the formula (6) and 33 to 1 mol% of the silicon compound represented by the formula (7). The said porous silica particle (F2) is a sum of the silicon compound represented by the said Formula (6), the silicon compound represented by the said Formula (7), and the silicon compound represented by the said Formula (8) as 100 mol%, 60 to 98 mol% of the silicon compound represented by the formula (6), 1 to 30 mol% of the silicon compound represented by the formula (7), and 1 to 20 mol% of the silicon compound represented by the formula (8). A laminate comprising a reactant. The manufacturing method of the laminated body containing the process of forming the cured film layer obtained by apply | coating the liquid curable composition containing the following components (A)-(D) on a base material, and irradiating a radiation, and hardening the said composition. [Liquid curable composition] (A) Spherical phosphorus-containing tin oxide particles having a primary particle diameter of 10 nm to 100 nm (B) a compound selected from the group consisting of (meth) acrylic esters and vinyl compounds (C) Photoinitiator whose molar extinction coefficient in 313 nm is 5,000 L / mol * cm or less (D) Solvent

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