KR20070091164A - Antireflective film - Google Patents

Abstract

Disclosed is an antireflective film comprising a conductive layer and a low-refractive index layer arranged on a base. The conductive layer is formed through vapor phase polymerization of a monomer such as pyrrole or thiophene, while the low-refractive index layer is made of a cured product of a curable resin composition containing the following components (A) and (B1). (A) A fluorine-containing polymer having an ethylenically unsaturated group. (B1) Porous silica particles composed of hydrolysis products and/or hydrolysis-condensation products of silicon compounds represented by the formulae (1) and (2) below and having an average particle diameter of 5-50 nm. R1hSiX4-h (1) R2jSiX4-j (2) (In the above formulae, R1 represents an alkyl group having 1-8 carbon atoms; Xs independently represent an alkoxy group having 1-4 carbon atoms or the like; h represents an integer of 0-1; R2 represents an alkenyl group having 2-8 carbon atoms, an acryloxyalkyl group having 4-8 carbon atoms or a methacryloxyalkyl group having 5-8 carbon atoms; and j represents an integer of 1-3.)

Description

Anti-reflective coating {ANTIREFLECTIVE FILM}

The present invention relates to an antireflection film. More specifically, the present invention relates to an antireflection film excellent in antistatic property, scratch resistance and fouling resistance.

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

In these display panels, the surface is often wiped off with 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. As the substrate, for example, triacetyl cellulose or the like is used. In the anti-reflection film using such a substrate, it is usually necessary to saponify with an aqueous alkali solution in order to increase the adhesiveness when bonding to a polarizing plate.

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

As the material for the low refractive index layer of the antireflection film, for example, a fluororesin paint containing a hydroxyl group-containing fluorine-containing polymer is known (for example, Patent Documents 1 to 3 below).

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

Moreover, also about the obtained coating film, although it was excellent in weather resistance, there existed a problem that it was lacking in abrasion resistance and durability.

Therefore, in order to solve the above problem, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition polymerizable unsaturated group and a hydroxyl group-containing fluorine-containing polymer have a ratio of the number of the number of hydroxyl / hydroxyl groups of the isocyanate group of 0.01 to 1.0. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a phosphorus ratio has been proposed (for example, Patent Document 4 below).

However, in Patent Document 4, when producing an unsaturated group-containing fluorine-containing vinyl polymer, an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer is not actively used in the polymer. It was to leave reaction hydroxyl group.

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 Application Laid-Open No. 57-34107

<Patent Document 2> Japanese Unexamined Patent Publication No. 59-189108

<Patent Document 3> Japanese Unexamined Patent Publication No. 60-67518

<Patent Document 4> Japanese Unexamined Patent Publication No. 61-296073

This invention is made | formed in view of the said subject, Comprising: It aims at providing the antireflection film excellent in especially antistatic property, abrasion resistance, and stain resistance.

According to the present invention, the following antireflection film is provided.

1. A conductive layer formed by vapor-phase polymerizing at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof on a substrate, and the following components ( The antireflection film which has a low refractive index layer containing the hardened | cured material of curable resin composition containing A) and (B1).

(A) an ethylenically unsaturated group containing fluorine-containing polymer,

(B1) Porous silica particles containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1) and a silicon compound represented by the formula (2), and having an average particle diameter of 5 to 50 nm.

R ¹ _h SiX _{4 -h}

R ² _j SiX _{4 -j}

(R ¹ represents an alkyl group having 1 to 8 carbon atoms, X each independently represents an alkoxy group, halogeno group, isocyanate group (-N = C = O), carboxyl group, alkyloxy group having 2 to 4 carbon atoms). A carbonyl group or an alkylamino group having 1 to 4 carbon atoms, h represents an integer of 0 to 1, R ² is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or methacryloxy having 5 to 8 carbon atoms Alkyl group, j represents an integer of 1 to 3, while X in formula 1 and X in formula 2 may be the same or different)

2. A conductive layer formed by vapor-phase polymerization of at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof on the substrate, and the following components ( The antireflection film which has a low refractive index layer containing the hardened | cured material of curable resin composition containing A) and (B2).

(A) an ethylenically unsaturated group containing fluorine-containing polymer,

(B2) A porous compound containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1), a silicon compound represented by the formula (2) and a silicon compound represented by the formula (3), and having an average particle diameter of 5 to 50 nm. Silica particles.

 <Formula 1>

R ¹ _h SiX _{4 -h}

<Formula 2>

R ² _j SiX _{4 -j}

R ³ _k SiX _{4 -k}

(R ¹ represents an alkyl group having 1 to 8 carbon atoms, X each independently represents an alkoxy group, halogeno group, isocyanate group (-N = C = O), carboxyl group, alkyloxy group having 2 to 4 carbon atoms). A carbonyl group or an alkylamino group having 1 to 4 carbon atoms, h represents an integer of 0 to 1, R ² is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or methacryloxy having 5 to 8 carbon atoms An alkyl group, j represents an integer of 1 to 3, R ³ represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 3, on the other hand, X in Formula 1, X in Formula 2 and X in Formula 3 may be the same or different)

3. When the porous silica particles (B1) have a total sum of the silicon compound represented by the formula (1) and the silicon compound represented by the formula (2) at 100 mol%, the hydrolyzate and / or the hydrolyzed condensate are represented by the formula (1). The anti-reflective film of said 1 which consists of 67-99 mol% of silicon compounds represented by (A), and 33-1 mol% of silicon compounds represented by Formula (2).

4. When said porous silica particle (B2) makes the sum total of the silicon compound represented by the said Formula (1), the silicon compound represented by the formula (2), and the silicon compound represented by the formula (3) 100 mol%, the said hydrolyzate and / Or the hydrolyzed condensate comprises a reactant of 60 to 98 mol% of the silicon compound represented by the formula (1), 1 to 30 mol% of the silicon compound represented by the formula (2) and 1 to 20 mol% of the silicon compound represented by the formula (3). The antireflection film of 2 described above.

5. The antireflection film according to any one of 1 to 4 above, wherein h is 0 in the silicon compound represented by the formula (1).

6. The porous silica particles (B1) or (B2) are hydrolyzed in the presence of at least one member selected from the group consisting of water, alcohols having 1 to 3 carbon atoms, basic compounds, and half ethers of acid amides, diols and diols, and And / or the antireflection film according to any one of 1 to 5 above, which is hydrolytically condensed.

7. The ratio of molar ratio of isocyanate group / hydroxy group to isocyanate group / hydroxyl group in the compound containing hydroxyl group-containing fluorine-containing polymer and hydroxyl group-containing fluorine-containing polymer (A) is one isocyanate group and at least one ethylenically unsaturated group The antireflection film in any one of said 1-6 which is an ethylenically unsaturated group containing fluorine-containing polymer obtained by making it react.

8. 20-70 mol% of structural units (a) and 10-70 mol of structural units (b) with respect to the said hydroxyl-containing fluorine-containing polymer in total of 100 mol% of the following structural units (a), (b) and (c). % And the structural unit (c) The antireflection film according to the above 7, wherein the polystyrene reduced number average molecular weight is 5,000 to 500,000, which is contained at a ratio of 5 to 70 mol% and is measured by gel permeation chromatography.

(a) The structural unit represented by following formula (4)

(b) a structural unit represented by the following formula (5)

(c) a structural unit represented by the following formula (6)

[In Formula 4, R ⁴ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group.)

In formula (5), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group,-(CH ₂ ) _x -OR ⁸ or a group represented by -OCOR ⁸ (R ⁸ represents an alkyl group or glycidyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

[In Formula 6, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

9. 0.1-10 mol part of the following structural units (d) which the said hydroxyl-containing fluorine-containing polymer further derives from an azo group containing polysiloxane compound with respect to 100 mol part of said structural units (a), (b), and (c) in total. The antireflection film of 8 described above.

(d) a structural unit represented by the following formula (7)

[In Formula 7, R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

10. The antireflection film according to any one of 1 to 9 above, further comprising a hard coating layer between the conductive layer and the low refractive index layer.

According to the antireflection film of the present invention, excellent scratch resistance and stain resistance are obtained.

1 is a cross-sectional view according to an embodiment of the antireflection film of the present invention.

Best Mode for Carrying Out the Invention

Embodiments of the antireflection film of the present invention will be described below.

1. conductive layer

The conductive layer in the antireflection film of the present invention functions as an antistatic layer. The conductive layer formed by gas phase polymerization can be manufactured by the method of Unexamined-Japanese-Patent No. 2003-82105, etc., for example, and can be specifically formed from a conductive polymer. That is, an oxidizing agent is applied to the base layer in a thickness of several micrometers, and the monomer (monomer) is brought into contact with the oxidizing agent coating film in a gaseous state to advance polymerization to form a conductive polymer film on the substrate. At this time, in the sense of improving the adhesive force, it is also possible to use a polymer such as polyurethane, polyvinyl chloride, polyvinyl alcohol, methyl cellulose, chitosan together with the organic solvent.

In this invention, although the monomer is vapor-phase-polymerized on the base layer to which the oxidizing agent was apply | coated, the conductive layer containing a conductive polymer is formed, It is preferable that reaction temperature at this time is 0-140 degreeC. Hereinafter, although the polymerization method is demonstrated in detail, this invention is not limited to this.

Specifically, first, as a first step, 0.5 to 10% by mass of an oxidizing agent is applied to the surface of the base layer in units of several micrometers. As the oxidizing agent, for example, a compound selected from the group consisting of CuCl ₂ , iron toluene sulfonate (III), iron perchlorate, FeCl ₂ and Cu (ClO ₄ ) ₂ · 6H ₂ O may be used alone or in combination. . The solvent conditions at this time vary depending on the type of base layer used, but are selected from, for example, methyl alcohol, 2-butyl alcohol, ethyl cellosolve, ethyl alcohol, cyclohexane, acetone, ethyl acetate, toluene and methyl ethyl ketone. Organic solvents can be used. These can be used individually or in mixture of 2 or more types, For example, the organic solvent which consists of methyl alcohol, 2-butyl alcohol, and ethyl cellosolve is 7: 2: 1, 6: 2: 2, 6: 3: 1, 5: 3: 2, etc. are mixed and used. The base layer coated with the oxidizing agent is dried in a hot air dryer of 80 ° C. or less in consideration of decomposition of the oxidizing agent.

Next, as a second step, a base layer coated with an oxidizing agent is contacted by vaporizing a monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof, and The polymerization reaction is carried out on the surface of the layer. At this time, as a method of vaporizing a monomer, the method of distilling a monomer at 0-140 degreeC in the sealed chamber, the method by CVD (chemical vapor deposition), etc. are mentioned. At this time, it is preferable to adjust the temperature conditions and the reaction time, and the polymerization reaction is carried out for about 10 seconds to 40 minutes, and generally varies depending on the type of monomer, but until the film thickness, the surface resistance, and the like reach the target values. Do it.

Next, as a third step, after the polymerization is completed, a washing step for removing unreacted monomers and oxidants is performed. As the solvent used at this time, alcohols such as methanol are usually used, and in some cases, the solvent may be washed with water.

The series of steps as described above can be carried out stepwise or continuously, and can be processed in a series of working steps from the polymerization of the monomer to the formation of the conductive film. The obtained conductive polymer film has good adhesiveness to the base layer and also has sufficient resistance to an alcohol solvent.

It is preferable that the film thickness of a conductive layer is 1-2000 nm. At a film thickness of less than 1 nm, pinholes are likely to occur, and film formation is difficult, surface resistance is also increased, and there is a fear that the antistatic property is inferior. Moreover, in the film thickness exceeding 2000 nm, although surface resistance is favorable, transparency and color tone fall remarkably, and it may be difficult to use it as an antireflection film. Particularly preferred film thickness is 5 to 300 nm in terms of balance of transparency, color tone and surface resistance.

The surface resistance of the conductive layer is usually 10 ² Ω / □ to 10 ¹² Ω / □.

2. Curable Resin Composition

Curable resin composition used by this invention can contain the following components (A)-(F). Among these components, (A) and (B) are essential components, and (C) to (F) are optional components that may be appropriately included.

(A) Ethylenic unsaturated group containing fluorine-containing polymer

(B) the following first porous silica particles (B1) or the following second porous silica particles (B2)

[First Porous Silica Particles (B1)]

Porous silica particles containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1) and a silicon compound represented by the formula (2), and having an average particle diameter of 5 to 50 nm.

<Formula 1>

R ¹ _h SiX _{4 -h}

<Formula 2>

R ² _j SiX _{4 -j}

Second Porous Silica Particles (B2)

Porous silica particles comprising a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1), a silicon compound represented by the formula (2) and a silicon compound represented by the formula (3), and having an average particle diameter of 5 to 50 nm.

<Formula 1>

R ¹ _h SiX _{4 -h}

<Formula 2>

R ² _j SiX _{4 -j}

<Formula 3>

R ³ _k SiX _{4 -k}

In Formulas 1 to 3, R ¹ , R ² , R ³ , X, h, j, and k are the same as described above.

(C) 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

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

(E) organic solvent

(F) additive

These components are demonstrated below.

(A) Ethylenic unsaturated group containing fluorine-containing polymer

The ethylenically unsaturated group-containing fluorine-containing polymer 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 in a ratio of a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9.

(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 of 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate alone, or 2 or more types of combinations 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 the Osaka Yuki Kagaku Co., Ltd. brand name KAYARAD DPHA, PET-30, Toagosei (Note) (Trade name) Aronix M-215, M-233, M-305, M-400, etc. can be obtained.

(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 (4).

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

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

<Formula 4>

[In Formula 4, R ⁴ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group.)

<Formula 5>

In formula (5), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group,-(CH ₂ ) _x -OR ⁸ or a group represented by -OCOR ⁸ (R ⁸ represents an alkyl group or glycidyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group]

<Formula 6>

[In Formula 6, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(i) structural units (a)

In the general formula (4), as the fluoroalkyl group of R ⁴ and R ⁵ , a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluorocyclohex C1-C6 fluoroalkyl groups, such as a real group, are mentioned. Moreover, as an alkyl group of R <^5> , C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group, are mentioned.

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

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

In addition, the content rate of a structural unit (a) is 20-70 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c). The reason for this is that when the content is less than 20 mol%, the expression of low refractive index, which is an optical characteristic of the fluorine-containing material intended by the present invention, may be difficult. On the other hand, when the content is more than 70 mol%, the hydroxyl group content is included. It is because solubility, transparency, or adhesiveness with respect to a base material of a fluorine-containing polymer may fall.

For this reason, the content of the structural unit (a) is more preferably 25 to 65 mol% with respect to 100 mol% of the total of the structural units (a), (b) and (c), more preferably 30 to 60. It is more preferable to set it as mol%.

(ii) structural units (b)

In the general formula (5), examples of the alkyl group of R ⁷ or R ⁸ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group and lauryl group, and examples of the alkoxycarbonyl group of R ⁷ include A methoxy carbonyl group, an ethoxy carbonyl 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 basatic acid, 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.

In addition, the content rate of a structural unit (b) is 10-70 mol% with respect to a total of 100 mol% of structural units (a), (b), and (c). This is because the solubility with respect to the organic solvent of a hydroxyl-containing fluorine-containing polymer may fall when content rate is less than 10 mol%, On the other hand, when content rate exceeds 70 mol%, transparency of a hydroxyl-containing fluoropolymer, and It is because optical characteristics, such as low reflectivity, may fall.

For this reason, the content of the structural unit (b) is more preferably 20 to 60 mol% with respect to 100 mol% of the total of the structural units (a), (b) and (c), more preferably 30 to 60 It is more preferable to set it as mol%.

(iii) structural units (c)

In the general formula (6), as the hydroxyalkyl group of R ¹⁰ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxy A hydroxypentyl 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, it is preferable to make content rate of a structural unit (c) into 5 to 70 mol% with respect to a total of 100 mol% of structural units (a), (b) and (c). This is because 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, if the content is more than 70 mol%, the transparency and low It is because optical characteristics, such as reflectivity, may fall.

For this reason, the content of the structural unit (c) is more preferably 5 to 40 mol% with respect to 100 mol% of the total of the structural units (a), (b) and (c), more preferably 5 to 30. It is more preferable to set it as mol%.

(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 (7).

<Formula 7>

[In Formula 7, R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.]

In the general formula (7), alkyl groups of R ¹¹ and R ¹² include alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group, and trifluoromethyl group, perfluoroethyl group, perfluoropropyl group and perfluoro group as halogenated alkyl group. A phenyl group, a benzyl group, a naphthyl group etc. are mentioned as an aryl group etc. as a C1-C4 fluoroalkyl group, such as a robutyl group, respectively.

The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (7). As an example of such an azo-group containing polysiloxane compound, the compound represented by following formula (8) is mentioned.

In formula (8), R <^13> -R <^16> may be the same or different, and represents a hydrogen atom, an alkyl group, or a cyano group, R <^17> -R <^20> may be the same or different, represents 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 (8), the structural unit (d) is included in the hydroxyl group-containing fluorine-containing polymer as part of the following structural unit (e).

(e) The structural unit represented by following formula (9).

[Formula 9, R ¹³ to R ¹⁶ , R ¹⁷ to R ²⁰ , p, q, s, t and y are the same as in the general formula (8)]

In formulas (8) and (9), examples of the alkyl group represented by R ¹³ to R ¹⁶ 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 ¹⁷ to R ²⁰ . And alkyl groups having 1 to 3 carbon atoms such as ethyl group and propyl group.

In the present invention, the compound represented by the following formula (10) is particularly preferable as the azo group-containing polysiloxane compound represented by the formula (8).

[In Formula 10, y and z are the same as those of Formula 8]

In addition, it is preferable to make content rate of a structural unit (d) into 0.1-10 mol part with respect to a total of 100 mol parts of a structural unit (a), (b), and (c). The reason is that if the content is less than 0.1 molar parts, the surface slip resistance of the coating film after curing may be lowered and the scratch resistance of the coating film may be reduced. On the other hand, if the content is more than 10 molar parts, the transparency of the hydroxyl group-containing fluoropolymer It is because it may fall easily and a repulsion etc. may arise at the time of application | coating, when using as a coating material.

For this reason, it is more preferable that the content of the structural unit (d) is 0.1 to 5 mol parts with respect to 100 mol parts of the total of the structural units (a), (b) and (c), and is 0.1 to 3 mol parts. More preferably. For the same reason, it is preferable that the content rate of the structural unit (e) is 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 (11).

[In Formula 11, R ²¹ represents a group having an emulsifying action.]

In the formula (11), a group having an emulsifying action of R ²¹ 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.

Examples of the group having such an emulsifying action include groups represented by the following general formula (12).

[Wherein n is a number from 1 to 20, m is a number from 0 to 4, 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 (13).

[In Formula 13, n, m and u are the same as in Formula 12]

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

For this reason, the content of the structural unit (f) is more preferably from 0.1 to 3 moles, based on 100 moles of the total of the structural units (a), (b) and (c), more preferably 0.2 to 3 moles. It is more preferable to make it rich.

(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, measured by gel permeation chromatography using tetrahydrofuran as a solvent. The reason is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluorine-containing polymer may be lowered. On the other hand, when the number average molecular weight is more than 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 reacted with a compound containing one isocyanate group and one or more ethylenically unsaturated groups and a hydroxyl group-containing fluorine-containing polymer in a ratio in which the molar ratio of isocyanate group / hydroxyl group is 1.1 to 1.9. Obtained. This is because the scratch resistance and durability may decrease when the molar ratio is less than 1.1. On the other hand, when 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 (A) component in curable resin composition, It is 1-95 mass% normally with respect to composition whole quantity other than the organic solvent. The reason 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 be high, and a sufficient antireflection effect may not be obtained. This is because the scratch resistance of the coating film may not be obtained.

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

(B) porous silica particles

A porous silica particle (B) is mix | blended with curable resin composition used by this invention for the purpose of improving the scratch resistance of the cured film of the said curable resin composition, especially the scratch resistance with respect to steel wool. As the porous silica particles (B), the first porous silica particles (B1) or the second porous silica particles (B2) are used. The first porous silica particles (B1) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (1) and a silicon compound represented by the following formula (2). That is, it is obtained by hydrolyzing and / or hydrolytically condensing the silicon compound represented by the formula (1), and further hydrolyzing and / or hydrolytically condensing the silicon compound represented by the formula (2). The silicon compound represented by the formula (1) and the silicon compound represented by the formula (2) may be mixed and hydrolyzed and / or hydrolyzed condensation simultaneously, and the silicon compound represented by the formula (1) is hydrolyzed and / or hydrolyzed condensed, and then The silicon compound represented by the formula (2) may be added to further hydrolyze and / or hydrolyzed condensation. The second porous silica particles (B2) are obtained by hydrolysis and / or hydrolysis condensation of a silicon compound represented by the following formula (1), a silicon compound represented by the following formula (2) and a silicon compound represented by the following formula (3). That is, hydrolysis and / or hydrolytic condensation of the silicon compound represented by the formula (1), hydrolysis and / or hydrolytic condensation of the silicon compound represented by the formula (2), and hydrolysis of the silicon compound represented by the formula (3) And / or hydrolytic condensation. The silicon compound represented by the formula (1), the silicon compound represented by the formula (2) and the silicon compound represented by the formula (3) may be mixed and hydrolyzed and / or hydrolyzed condensed at the same time, and the hydrolyzed and And / or hydrolytic condensation, followed by further hydrolysis and / or hydrolytic condensation by adding a silicon compound represented by the formula (2) and a silicon compound represented by the formula (3).

<Formula 1>

R ¹ _h SiX _{4 -h}

<Formula 2>

R ² _j SiX _{4 -j}

<Formula 3>

R ³ _k SiX _{4 -k}

In general formula (1), R <^1> is a C1-C8 alkyl group, Preferably it is a C1-C4 alkyl group, More preferably, they are a methyl group, an ethyl group, and a propyl group.

In the formulas (1), (2) and (3), 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 Formulas 1, 2 and 3 may be the same or different.

In Formula 1, h is an integer of 0-1, Preferably it is 0.

Examples of the compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrachlorosilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane and ethyltrichloro. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, and the like.

In formula (2), R <^2> is a C2-C8 alkenyl group, a C4-C8 acryloxyalkyl group, or a C5-C8 methacryloxyalkyl group, Preferably a vinyl group, an allyl group, an acryloxyethyl group, and acryloxy Propyl group, acryloxybutyl group, methacryloxyethyl group, methacryloxypropyl group, and methacryloxybutyl group.

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

As a compound represented by General formula (2), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, acryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, etc. are mentioned, for example.

By using the compound represented by General formula (2), a 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 general formula (3), R <^3> 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 (3), k is an integer of 1-3, Preferably it is 1-2.

As the compound represented by the formula (3), for example, 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 (3), 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 General formula (1), the silicon compound represented by General formula (2), and the silicon compound represented by General formula (3) can use 2 or more types, respectively.

In the first porous silica particles (B1), when the total of the silicon compound represented by the formula (1) and the silicon compound represented by the formula (2) is 100 mol%, the silicon compound represented by the formula (1) / formula (2) The silicon compound is preferably hydrolyzed and / or hydrolyzed condensed at a ratio of 67 to 99/1 to 33 (mol%), more preferably 70 to 98/2 to 30 (mol%).

In the second porous silica particles (B2), when the total of the silicon compound represented by the formula (1), the silicon compound represented by the formula (2) and the silicon compound represented by the formula (3) is 100 mol%, the silicon represented by the formula (1) The silicon compound represented by the compound / Formula 2 / silicon compound represented by the formula 3 is preferably 60 to 98/1 to 30/1 to 20 (mol%), more preferably 65 to 96/2 to 20/2 Hydrolysis and / or hydrolysis condensation at a ratio of from 15 (mol%).

The first and second porous silica particles (B1) and (B2) used in the present invention have an average particle diameter of 5 to 50 nm, preferably 5 to 45 nm, and more preferably 5 to 40 nm. An average particle diameter is a number average particle diameter, and is measured by a transmission electron microscope observation image. In addition, "porous" means that the specific surface area is 50 to 1000 m 2 / g, preferably 50 to 800 m 2 / g, and more preferably 100 to 800 m 2 / g. The specific surface area is measured by the BET method.

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

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

The first or second porous silica particles (B1), (B2) are each represented by the above formula in the presence of at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and half ethers of acid amides, diols and diols. Hydrolysis and / or hydrolysis condensation of the silicon compound represented by 1 and the silicon compound represented by Formula 2, or the silicon compound represented by Formula 1, the silicon compound represented by Formula 2, and the silicon compound represented by Formula 3, It can manufacture.

As the basic compound, for example, an amine compound is used, and as a specific example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanol Amine, 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, triethylamine , Tripropylamine, tributylamine and the like. Preferably, ammonia, ethanolamine, tetramethylamine hydroxide or the like is 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-dimethylacetyl Amides are 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 (1) and the silicon compound of the formula (2) or the total concentration of the silicon compound of the formulas (1) to (3) in the reaction solution is usually 0.5 to 10% by mass, preferably 1 to 8, in terms of complete hydrolysis condensate. It is mass%. Here, the term "complete hydrolysis condensate conversion" is a theoretical value calculated on the assumption that the silicon compound is completely hydrolyzed condensation, and the X of the silicon compound of Formula 1 and the silicon compound of Formula 2, or of the silicon compounds of It corresponds to the mass when X is substituted with 1/2 mol of oxygen atom of X. By making the concentration of the silicon compound at the time of particle synthesis into the above range, coarsening of the particles can be prevented and particles having an average particle diameter of 5 to 50 nm can be obtained.

The silicon compound of formula (1) and the silicon compound of formula (2), or the silicon compound of formula (1), the silicon compound of formula (2), and the silicon compound of formula (3) can be mixed simultaneously to hydrolyze and / or hydrolyze condensation, and also water, carbon number Hydrolysis and / or hydrolysis condensation of the silicon compound represented by the formula (1) in the presence of at least one alcohol selected from alcohols of 1 to 3, basic compounds, and half ethers of acid amides, diols and diols, and then to The silicon compound represented, or the silicon compound represented by the formula (2) and the silicon compound represented by the formula (3) may be added to further hydrolyze and / or hydrolyzed condensation.

The reaction temperature of hydrolysis and / or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of alcohol and acid amides to be used. The reaction time depends on the type of silicon compound represented by the formula (1), the silicon compound represented by the formula (2), and the silicon compound represented by the formula (3), the reaction rate, the type and amount of the base, and the like. It doesn't work.

By adding an organic solvent to the obtained hydrolysis and / or hydrolysis condensation reaction liquid, and removing unnecessary components by distillation or liquid extraction, if necessary, a dispersion liquid in which the porous silica particles are dispersed in the organic solvent can be obtained. .

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 (B) 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. In addition, the quantity of particle means solid content, and when particle | grains are used in the form of a solvent dispersion liquid, the compounding quantity does not contain the quantity of a solvent.

(C) 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 1 type single, or 2 or more types of combinations, etc. are manufactured.

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

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

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

Although it does not restrict | limit especially about the addition amount of (C) component, It is 0-90 mass parts normally with respect to 100 mass parts of compositions whole quantity other than the organic solvent. The reason for this is that when the addition amount exceeds 90 parts by mass, the refractive index of the cured coating film of the curable resin composition may be high, and a sufficient antireflection effect may not be obtained.

For this reason, the addition amount of the component (C) is more preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.

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

In this invention, the compound which generate | occur | produces an active species by irradiation or heat of an active energy ray can also be added. Compounds which generate active species by irradiation or heat of active energy rays are used to cure the 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 visible energy rays such as visible light, ultraviolet rays, infrared rays, X rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays in view of having a constant energy level, fast curing speed, and in addition, the irradiation apparatus is relatively inexpensive and compact.

(i) Type

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

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

(ii) added amount

Although the addition amount of a photoinitiator is not specifically limited, It is preferable to set it as 0.01-20 mass parts with respect to 100 mass parts of compositions whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 0.01 part 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 parts, it is because the refractive index of a cured film may increase and the antireflection effect may fall.

For this reason, the amount of the photopolymerization initiator added is more preferably 0.05 to 15 parts by mass, and even more preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the total amount of the composition other than the organic solvent.

(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 parts with respect to 100 mass parts of compositions whole quantity other than an organic solvent. The reason for this is that when the addition amount is less than 0.01 part 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 parts, 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 parts with respect to 100 mass parts of compositions whole quantities other than an organic solvent, and it is still more preferable to set it as the value within the range of 0.1-15 mass parts.

(E) organic solvent

It is preferable to add an organic solvent further to curable resin composition. Thus, the anti-reflective film of a thin film can be formed uniformly by adding an organic solvent. As such an organic solvent, the organic solvent of a C1-C8 alcohol system, a C3-C10 ketone system, and a C3-C10 ester system can be used preferably, Methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol , t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol monopropyl ether and the like are particularly preferred examples. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

Although it does not restrict | limit especially also about the addition amount of an organic solvent, It is preferable to set it as 100-100,000 mass parts with respect to 100 mass parts of compositions other than an organic solvent. The reason is that when the 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 amount is more than 100,000 parts by mass, the storage stability of the curable resin composition is lowered or the viscosity is too low. This is because the handling may be difficult.

(F) additive

In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improving agent, an interface activator, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, and a silane in a range that does not impair the object or effect of the present invention. You may further contain additives, such as a coupling agent and inorganic fillers other than (B) component, or a pigment and dye.

Next, the manufacturing method and hardening conditions of curable resin composition used by this invention are demonstrated.

Curable resin composition used by this invention is the said (A) ethylenically unsaturated group containing fluorine-containing polymer and the said (B) component, or the said (C) component, (D) component, (E) organic solvent, if needed, and It can manufacture by adding each (F) additive and mixing on room temperature or heating conditions. Specifically, it can manufacture using mixers, such as a mixer, a kneader, a ball mill, and a triaxial roll. However, when mixing under heating conditions, it is preferable to carry out below the decomposition start temperature of a thermal polymerization initiator.

Although it does not restrict | limit especially about the hardening conditions of curable resin composition, For example, when using an active energy ray, it is preferable to make an exposure amount into the value within the range of 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, the exposure amount is more preferably in the range of 0.1 to 5 J / cm 2, and more preferably in the range of 0.3 to 3 J / cm 2.

In addition, when heating and hardening curable resin composition, it is preferable to heat for 1 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 2 to 120 minutes at a temperature in the range of 50 to 180 ° C, and even more preferably 5 to 60 minutes at a temperature in the range of 80 to 150 ° C.

3. Anti-reflection film

The antireflection film of this invention can be manufactured including the low refractive index layer containing the cured film of the said curable resin composition on a base material. In addition, the antireflection film may include a high refractive index layer, a medium refractive index layer, a hard coating layer, an antistatic layer, and the like under the low refractive index layer.

1 shows such an antireflection film 10. As shown in FIG. 1, the antistatic layer 14, the hard coating layer 16, and the low refractive index layer 18 are laminated on the substrate 12.

In addition, a high refractive index layer (not shown) may be further provided between the hard coating layer 16 and the low refractive index layer 18.

In addition, the low refractive index layer 18 can be formed directly on the antistatic layer 14 without providing the hard coating layer 16.

(1) low refractive index layer

The low refractive index layer is composed of a cured film obtained by curing the curable resin composition. Since the structure of curable resin composition etc. are as above-mentioned, the detailed description here is abbreviate | omitted and the refractive index and thickness of a low refractive index layer are demonstrated below.

It is preferable that the refractive index (refractive index of Na-D line (589 nm), measurement temperature 25 degreeC) of the cured film obtained by hardening | curing curable resin composition, ie, the refractive index of a low refractive index film shall be 1.45 or less. The reason is that when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be remarkably lowered in combination with the high refractive index film.

Therefore, the refractive index of the low refractive index film is more preferably 1.44 or less, and even more preferably 1.43 or less.

On the other hand, in the case where a plurality of low refractive index films are provided, at least one of them may have a value of the refractive index within the above-described range, and thus the other low refractive index films may have a value exceeding 1.45.

In addition, when providing a low refractive index layer, since the outstanding antireflection effect is acquired, it is preferable to make the refractive index difference between a high refractive index layer and a value 0.05 or more. This is because if the difference in refractive index between the low refractive index layer and the high refractive index layer is less than 0.05, the synergistic effect in these antireflection film layers is not obtained, but the antireflection effect may be lowered.

Therefore, it is more preferable that the refractive index difference between the low refractive index layer and the high refractive index layer is in the range of 0.1 to 0.5, and more preferably in the range of 0.15 to 0.5.

The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index film as the base may be lowered. On the other hand, when the thickness exceeds 300 nm, optical interference occurs and the antireflection effect is lowered. Because there are cases.

Therefore, the thickness of the low refractive index layer is more preferably 50 to 250 nm, and more preferably 60 to 200 nm.

On the other hand, in order to obtain a higher antireflection property, in the case where a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness thereof is preferably set to 50 to 300 nm.

(2) high refractive index layer

Although it does not restrict | limit especially as a curable composition for forming a high refractive index layer, As a film formation component, Epoxy resin, a phenol resin, melamine resin, alkyd resin, cyanate resin, acrylic resin, polyester resin, It is preferable to include 1 type individually or 2 or more types of combinations, such as a urethane type resin and a siloxane resin. It is because if it is these resin, a strong thin film can be formed as a high refractive index layer, and as a result, the scratch resistance of an antireflection film can be improved significantly.

However, the refractive index of these resins alone is 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to mix | blend high refractive index inorganic particle, for example, metal oxide particle. Specific examples of metal oxide particles include antimony doped tin oxide (ATO) particles, tin doped indium oxide (ITO) particles, ZnO particles, antimony doped ZnO, Al doped ZnO particles, phosphorus doped tin oxide (PTO) particles, and 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 doped tin oxide (ATO) particles, tin doped indium oxide (ITO) particles, Al doped ZnO particles, phosphorus doped tin oxide (PTO) particles, Al ₂ O ₃ / ZrO ₂ coated TiO ₂ particles. These metal oxide particles can be used individually by 1 type or in combination of 2 or more types.

In addition, the high refractive index layer may have a function of a hard coating layer or an antistatic layer. In addition, although the curable composition which can thermoset, ultraviolet-ray curing, and electron beam hardening can be used as a hardening form, the ultraviolet curable composition with favorable productivity is used more suitably.

The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 30,000 nm. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, when combined with the low refractive index layer, the antireflection effect and the adhesion to the substrate may decrease, while when the thickness exceeds 30,000 nm, This is because interference may occur, and conversely, the antireflection effect may be lowered.

Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, more preferably 60 to 500 nm.

In addition, in order to obtain a higher antireflection property, when providing a multi-layered structure by providing two or more high refractive index layers, it is preferable to make the sum total the thickness into 50-30,000 nm.

On the other hand, when providing a hard-coat layer between a high refractive index layer and a base material, the thickness of a high refractive index layer can be 50-300 nm.

(3) hard coating layer

It does not restrict | limit especially about the structural material of the hard coat layer used for the antireflection film of this invention. As such a material, single 1 type, or 2 or more types of combinations, such as a siloxane resin, an acrylic resin, a melamine resin, an epoxy resin, are mentioned. In addition, silica particles or metal oxide particles may be added to increase scratch resistance, and antioxidants or light stabilizers may be added to avoid deterioration of the oxide layer.

Specific examples of the antioxidant and the light stabilizer include, for example, Smizer BHT, Smizer R, Smizer BP-76, Smizer MDP-S, Smizerizer GM, Smizer BBM-S, Smizer WX-R, Smizer NW, Sumiiser BP-179, Sumiiser BP-101, Sumiris GA-80, Sumiris TNP, Sumiris TPP-R, Sumiris P-16 (above, Sumitomo Chemical Co., Ltd.), Tinubin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292 (manufactured by Shiba Specialty Chemicals), Pancrill FA-711M, FA-712HM (Hitachi Kasei High School ( Note) manufacture) etc. are mentioned.

Although it does not restrict | limit especially about the thickness of a hard coat layer, It is preferable to set it as 1-50 micrometers, and it is more preferable to set it as 1-10 micrometers. The reason is that if the thickness of the hard coating layer is less than 1 m, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, if the thickness exceeds 50 m, it may be difficult to form uniformly. Because there is.

(4) conductive layer

The conductive layer is as described above, and detailed description is not given here, but by providing the conductive layer, the laminate is provided with conductivity, thereby preventing static electricity from being generated and adhesion of dust and the like.

(5) mention

Although the kind of base material used for an anti-reflection film is not restrict | limited, For example, triacetyl cellulose, polyethylene terephthalate resin (lumila etc. made by Toray Co., Ltd.), glass, a polycarbonate resin, an acrylic resin, a styryl resin , Arylate resins, norbornene-based resins (Aton manufactured by JSR Co., Ltd., Xeonex manufactured by Nippon Xeon Co., Ltd.), methyl methacrylate / styrene copolymer resin, polyolefin resin, and various transparent plastic plates, films Etc. can be mentioned. Preferably, triacetyl cellulose, polyethylene terephthalate resin (Lumiella, etc. by Toray Corporation), norbornene-type resin (Aton etc. by JSR Corporation) can be illustrated. By using the antireflection film containing these base materials, excellent antireflection effects can be obtained in the field of use of a wide range of antireflection films such as a lens part of a camera, a screen display part of a television (CRT), or a color filter in a liquid crystal display device.

Hereinafter, although an Example is shown and this invention is demonstrated in detail, the scope of the present invention is not limited to description of these Examples. In addition, unless otherwise indicated, the compounding quantity of each component in an Example means a "part" and a mass part and "%" means the mass%.

(Manufacture example 1)

Synthesis of hydroxyl-containing fluorine-containing polymer 1

After fully replacing a 2.0 liter stainless steel autoclave with an electronic stirrer with nitrogen gas, 400 g of ethyl acetate, 53.2 g of perfluoro (propyl vinyl ether), 36.1 g of ethyl vinyl ether, and 44.0 g of hydroxyethyl vinyl ether , 1.00 g of lauroyl peroxide, 6.0 g of an azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and a nonionic reactive emulsifier (NE-30 (trade name), Asahi) 20.0 g of Denka Kogyo Co., Ltd.) was put in, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed with nitrogen gas again.

Subsequently, 120.0 g of hexafluoropropylene was put, and temperature rising was started. The pressure at the point where the temperature in the autoclave reached 60 ° C. showed 5.3 × 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 1.7 × 10 ⁵ Pa, and the reaction was stopped. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. 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. This was set as the hydroxyl-containing fluorine-containing polymer 1. The monomers and solvents used are shown in Table 1 below.

About the obtained hydroxyl-containing fluorine-containing polymer 1, the polystyrene conversion number average molecular weight by gel permeation chromatography and the fluorine content by the alizarin complexon method were respectively measured. Moreover, the ratio of each monomer component which comprises the hydroxyl-containing fluorine-containing polymer 1 was determined from the results of two NMR analysis, elemental analysis, and fluorine content of ¹ H-NMR and ¹³ C-NMR. The results are shown in Table 2 below.

On the other hand, VPS1001 is an azo group-containing polydimethylsiloxane represented by the formula (8) wherein the number average molecular weight is 7 to 90,000 and the molecular weight of the polysiloxane moiety is about 10,000. In formula 13, NE-30 is a nonionic reactive emulsifier in which n is 9, m is 1, and u is 30.

In addition, in Table 2, the correspondence relationship of a monomer and a structural unit is as follows.

Monomeric structural units

Hexafluoropropylene (a)

Perfluoro (propylvinylether) (a)

Ethyl vinyl ether (b)

Hydroxyethyl vinyl ether (c)

NE-30 (f)

Polydimethylsiloxane skeleton (d)

(Manufacture example 2)

Synthesis of hydroxyl-containing fluorine-containing polymer 2

A hydroxyl group-containing fluorine-containing polymer was synthesized in the same manner as in Production Example 1 except that the amounts of ethyl vinyl ether and hydroxyethyl vinyl ether were changed as shown in Table 1. This was set as the hydroxyl-containing fluorine-containing polymer 2. The ratio of each monomer component is shown in Table 2.

(Manufacture example 3)

Synthesis of ethylenically unsaturated group-containing fluorine-containing polymer (A-1)

In a 1-liter separate-type flask equipped with an electronic stirrer, a glass cooling tube, and a thermometer, 50.0 g of the hydroxyl group-containing fluorine-containing polymer 1 obtained in Production Example 1 and 2,6-di-t-butylmethylphenol 0.01 as a polymerization inhibitor g and 370 g of methyl isobutyl ketone (hereinafter referred to as MIBK) were added thereto, and agitation was performed until the hydroxyl group-containing fluorine-containing polymer 1 was dissolved in MIBK at 20 ° C, and the solution became transparent and uniform.

Subsequently, 15.1 g of 2-methacryloyloxyethyl isocyanate is added to the system, the solution is stirred until the solution becomes uniform, and then 0.1 g of dibutyltin dilaurate is added to start the reaction, and the temperature of the system is increased. The MIBK solution of the ethylenically unsaturated group containing fluorine-containing polymer (A-1) was obtained by maintaining stirring at 55-65 degreeC for 5 hours.

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 15.2 mass%. The compound, solvent and solid content used are shown in Table 3 below.

(Manufacture example 4)

Synthesis of ethylenically unsaturated group-containing fluorine-containing polymer (A-2)

As shown in Table 3, in Production Example 3, the same as in Production Example 3 except that the type of hydroxyl group-containing fluorine-containing polymer and the molar ratio of 2-methacryloyloxyethyl isocyanate, MIBK and isocyanate group / hydroxyl group were changed. The MIBK solution of the ethylenically unsaturated group containing fluorine-containing polymer (A-2) was obtained.

(Manufacture example 5)

Synthesis of Porous Silica Fine Particles (B-1)

64.85 g of tetraethoxysilane (Toray Dow Corning Silicone Co., Ltd., AY43-101), 692.72 g of ethanol, 40.00 g of N, N-dimethylacetamide were added to a quartz separation flask, and the mixture was mixed uniformly. 200.00 g of a 25% aqueous solution of was added. Thereafter, the solution was reacted at 50 ° C for 6 hours with stirring, and further, 2.43 g of vinyltrimethoxysilane (SZ6300, manufactured by Toray Dow Corning Silicon Co., Ltd.) was added thereto and reacted at 50 ° C for 2 hours. After cooling the reaction solution to room temperature, 1000.00 g of MIBK and 1000.00 g of a 0.1% aqueous solution of oxalic acid were added, followed by stirring and standing. The upper layer separated into two layers was separated, and concentrated to a solid concentration of 5% by a rotary evaporator to obtain a porous silica particle solution (B-1).

After adding 10 g of ethanol to 1 g of the obtained solution (B-1) and mixing, one drop was added dropwise onto the carbon grid for transmission electron microscope, and then dried at room temperature for 24 hours, followed by a field emission from Nippon Denshi Co., Ltd. It observed using the electron microscope JEM-2010F, and measured the average particle diameter of porous silica particle.

10 g of the obtained solution (B-1) 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 particles (1). The BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 by Quantachrome Instruments.

The measurement results are shown in Table 4 below.

(Manufacture example 6)

Synthesis of Porous Silica Fine Particles (B-2)

48.58 g of tetramethoxysilane (made by Shin-Etsu Chemical Co., Ltd., KBM-04), 20.28 g of vinyl trimethoxysilanes, 328.14 g of ethanol, and 300.00 g of ethylene glycol are added uniformly to a quartz separation flask. After mixing, 303.00 g of a 1% aqueous solution of tetramethylammonium hydroxide were added. Then, it stirred for 4 hours at 60 degreeC, stirring a solution. After cooling the reaction liquid to room temperature, 1000.00 g of ethyl acetate 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 separated, 500.00 g of propylene glycol monoethyl ether was added, and concentrated to a solid concentration of 5% by a rotary evaporator to obtain a porous silica particle solution (B-2).

As in Preparation Example 5, the average particle diameter and the specific surface area were measured. The measurement results are shown in Table 4.

(Manufacture example 7)

Synthesis of Porous Silica Fine Particles (B-3)

27.99 g of tetraethoxysilane, 838.05 g of methanol, and 30.00 g of propylene glycol were added to a split flask made of quartz, and after mixing uniformly, 101.00 g of a 1% aqueous solution of ammonia was added. Thereafter, the solution was reacted at 40 ° C. for 8 hours while stirring, and further 1.85 g of vinyltrimethoxysilane and 1.85 g of methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Silicon Co., Ltd., SZ-6030) were added. It was added and reacted at 40 degreeC for 2 hours. After cooling the reaction solution to room temperature, 1000.00 g of MIBK and 1000.00 g of a 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 (B-3) was obtained.

As in Preparation Example 5, the average particle diameter and the specific surface area were measured. The measurement results are shown in Table 4.

(Manufacture example 8)

Synthesis of Porous Silica Fine Particles (B-4)

106.24 g of tetraethoxysilane, 420.49 g of methanol, and 200.00 g of 1,2-butanediol were added to a separate quartz flask, and 100.00 g of a 10% aqueous solution of ammonia and 160.00 g of ultrapure water were added. Thereafter, the solution was reacted at 30 ° C for 12 hours while stirring, and 13.28 g of acryloxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd., AY43-310M) was further added and reacted at 60 ° C for 1 hour. . After cooling the reaction solution to room temperature, 1000.00 g of propylene glycol methyl ether acetate 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 separated, and concentrated to a solid concentration of 5% by a rotary evaporator to obtain a porous silica particle solution (B-4).

As in Preparation Example 5, the average particle diameter and the specific surface area were measured. The measurement results are shown in Table 4.

(Manufacture example 9)

Synthesis of Porous Silica Fine Particles (B-5)

50.96 g of tetraethoxysilane (AY43-101 manufactured by Toray Dow Corning Silicone Co., Ltd.), 700.98 g of ethanol, 40.00 g of N, N-dimethylacetamide were added to a quartz split flask, and the mixture was mixed uniformly. 200.00 g of a 25% aqueous solution of was added. Thereafter, the solution was reacted at 50 ° C for 6 hours with stirring, and further, 2.11 g of vinyltrimethoxysilane (SZ6300 manufactured by Toray Dow Corning Silicone Co., Ltd.) and 3,3,3-trifluoropropyltrimethoxy 5.95 g of silane (KBM 7103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and reacted at 50 degreeC for 2 hours. After cooling the reaction solution to room temperature, 1000.00 g of MIBK and 1000.00 g of a 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 (B-5) was obtained.

As in Preparation Example 5, the average particle diameter and the specific surface area were measured. The measurement results are shown in Table 4.

(Manufacture example 10)

Synthesis of Specific Organic Compound (S-1)

222 parts of isophorone diisocyanate were dripped at 50 degreeC over 1 hour in drying air in the mixed solution of 221 parts of mercaptopropyl trimethoxysilane and 1 part of dibutyltin dilaurates in the container with a stirrer, and further 70 Stir at 3 ° C. for 3 hours.

Subsequently, it consists of NK ester A-TMM-3LM-N (60 mass% of pentaerythritol triacrylate and 40 mass% of pentaerythritol tetraacrylates) by Shin-Nakamura Chemical Co., Ltd. in this reaction solution. 549 parts of pentaerythritol triacrylate which has a hydroxyl group) were dripped at 30 degreeC over 1 hour, and also it stirred at 60 degreeC for 10 hours, and obtained the reaction liquid.

As a result of measuring the amount of remaining isocyanate in the product in this reaction liquid, ie, the organic compound which has a polymerizable unsaturated group, by FT-IR, it confirmed that each reaction was performed almost quantitatively as 0.1 mass% or less. 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 acryloxy group -S (C = 0) NH- and a urethane bond as a polymerizable unsaturated group was produced. It was. Thus, 773 parts of compounds which have a thiourethane bond, a urethane bond, an alkoxy silyl group, and a polymerizable unsaturated group and the composition (S-1) of 220 parts of pentaerythritol tetraacrylate which did not participate in reaction were obtained.

(Manufacture example 11)

Synthesis of Polyfunctional Acrylate

NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (manufactured to have a hydroxyl group) in a solution containing 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container with a stirrer. 93 parts of pentaerythritol triacrylates) were dripped at the conditions of 10 degreeC and 1 hour, and it stirred on the conditions of 60 degreeC and 6 hours, and used as the reaction liquid.

In the same manner as in Production Example 10, the amount of the remaining isocyanate in the product, that is, the polyfunctional acrylate, was measured by FT-IR, and it was confirmed that the reaction was performed almost quantitatively at 0.1 mass% or less. Furthermore, it was confirmed that a urethane bond and acryloyl group (polymerizable unsaturated group) are contained in a molecule | numerator.

By the above, 75 parts of hexaacrylate compounds were obtained and the composition (S-2) in which 37 parts of pentaerythritol tetraacrylates which did not participate in reaction was mixed was obtained.

(Manufacture example 12)

Preparation of Composition (H-1) for Zirconia-containing Hard Coating Layer

300 parts of zirconia particles (UEP-100 (primary particle size 10-30 nm) by Daiichi Kigso Kagaku Kogyo Co., Ltd.) are added to 700 parts of methyl ethyl ketone (MEK), and it disperse | distributes for 168 hours with glass beads, The glass beads were removed to obtain 950 parts of a zirconia dispersion sol. After weighing 2 g of zirconia dispersion sol in an aluminum dish, it was dried and weighed for 1 hour on a 120 degreeC hotplate, and solid content was calculated | required and it was 30%. 0.86 g of the composition (S-1) containing the specific organic compound synthesized in Production Example 10 to 100 g of this zirconia dispersion sol, 13.4 g of dipentaerythritol hexaacrylate (DPHA), 0.016 g of p-methoxyphenol, and an ion After stirring the liquid mixture of 0.033 g of exchange water at 60 degreeC for 3 hours, 0.332 g of methyl orthoformate esters were added, and it stirred further at the same temperature for 1 hour, and obtained 114.6 g of dispersion liquid of surface modified zirconia particle. 114.6 g of this dispersion, 1.34 g of composition (S-2) synthesized in Production Example 11, 1.26 g of 1-hydroxycyclohexylphenyl ketone, Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, from Ciba Specialty Chemicals) 0.76 g, Tinuvin 144 (bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[( 2.51 g of 3,5-di-t-butyl-4-hydroxyphenyl) methyl] butyl malonate, manufactured by Ciba Specialty Chemicals, and 46.6 g of MEK were mixed and stirred to prepare a composition for hard coating containing zirconia particles (H-1: 167g of solid content concentration 30%) was obtained.

(Manufacture example 13)

Preparation of the silica particle-containing hard coating layer composition (H-2)

2.32 parts of compositions (S-1) containing a polymerizable unsaturated group prepared in Production Example 10, 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-methoxy phenol at 60 degreeC for 4 hours, 1.36 parts of methyl ortho formates are added, and Reactive particles (dispersion (S-3)) were obtained by heating and stirring at the same temperature for 1 hour. After weighing 2g of this dispersion liquid (S-3) in the aluminum dish, it dried for 1 hour and weighed on the 175 degreeC hotplate, and calculated | required solid content, and it was 30.7%. Furthermore, after weighing 2 g of the dispersion liquid (S-3) in a magnetic crucible, preliminarily drying for 30 minutes on a hot plate at 80 ° C, and burning the inorganic content in the solid content from the inorganic residue after firing for 1 hour in a muffle furnace at 750 ° C. It was 90% as a result.

98.6 g of this dispersion (S-3), 3.4 g of compositions (S-2), 2.1 g of 1-hydroxycyclohexylphenyl ketone, Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, manufactured by Ciba Specialty Chemicals) 1.2 g, 33.2 g of dipentaerythritol hexaacrylate (DPHA), thybinin 144 (bis (1,2,2,6,6-) 3.7 g of pentamethyl-4-piperidinyl)-[(3,5-di-t-butyl-4-hydroxyphenyl) methyl] butyl malonate manufactured by Ciba Specialty Chemicals) and 6 g of cyclohexanone are mixed It stirred and 148g of compositions for silica particle containing hard-coat layers (H-2: 50% of solid content concentration) were obtained.

(Production Example 14)

Preparation of the film (b-1) which has a conductive layer (antistatic layer)

The catalyst solution was prepared by dissolving FeCl ₂ as an oxidizing agent in a solvent in which methyl alcohol, 2-butyl alcohol, and ethyl cellosolve were each mixed at a ratio of 6: 3: 1.

After spin-coating the catalyst solution prepared above on the surface of an aton film (trade name, manufactured by JSR, film thickness of 100 μm), the obtained catalyst coating film was dried at 60 ° C. for 3 minutes.

Subsequently, the polyester film having the hard coating layer and the catalyst coating film formed thereon was mounted in a CVD chamber designed to produce a saturated 3,4-ethylenedioxythiophene monomer, and the 3,4-ethylenedioxythiophene was polymerized for 30 seconds. In order to remove unreacted material, the film was washed with a methanol solvent to prepare a film (b-1) having a conductive layer.

(Production Example 15)

Preparation of the film (b-2) which has a conductive layer (antistatic layer)

A film (b-2) having a conductive layer was produced in the same manner as in Example 14 except that a triacetylcellulose film (LOFO manufactured, film thickness of 80 μm) was used instead of the aton film.

(Manufacture example 16)

Preparation of low refractive index layer coating base (G-1)

A wire bar coater (# 7) was used for the zirconia-containing hard coating layer composition (H-1: 30% solid content concentration) prepared in Preparation Example 12 on the film (b-1) having the conductive layer prepared in Preparation Example 14. Coating was carried out and dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, using a high pressure mercury lamp under air, ultraviolet rays were irradiated under light irradiation conditions of 0.9 mJ / cm 2 to form a hard coat layer. It was 3 micrometers when the film thickness of the hard-coat layer on this base material was measured by the stylus type surface shape measuring instrument.

The base (G-1) in which the conductive layer and the hard coat layer were formed on the base material by the above operation was manufactured.

(Manufacture example 17)

Preparation of low refractive index layer coating base (G-2)

The wire bar coater (# 12) was placed on the film (b-1) having the conductive layer prepared in Production Example 14 with the silica particle-containing hard coating layer prepared in Production Example 13 (H-2: 50% solid content). Coating was carried out, and the coating was dried in an oven at 80 ° C. for 1 minute.

Subsequently, ultraviolet rays were irradiated under a light irradiation condition of 0.6 mJ / cm 2 using a high pressure mercury lamp under air to form a hard coating layer. It was 5 micrometers when the film thickness of the hard coat layer on this base material was measured by the stylus type surface shape measuring instrument.

The base (G-2) in which the conductive layer and the hard coat layer were formed on the base material by the above operation was manufactured.

(Manufacture example 18)

Preparation of low refractive index layer coating base (G-3)

A conductive layer and a hard coat layer were formed on the substrate by the same operation as in Production Example 17 except that the film (b-2) having the conductive layer prepared in Production Example 15 was used instead of the film (b-1) having the conductive layer. Base (G-3) was prepared.

(Manufacture example 19)

Preparation of Curable Resin Composition

As shown in Table 5 below, 197 g (30 g as A-1) of the MIBK solution of the ethylenically unsaturated group-containing fluorine-containing polymer (A-1) obtained in Production Example 3, and the porous silica particle dispersion obtained in Production Example 5 1440 g (70 g as B-1), Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Ciba specialty as a photoinitiator 2 g of Chemicals) and 903 g of MIBK (2,400 g in combination with MIBK added as a solvent included in A-1 and B-1 above) were placed in a glass separate flask equipped with a stirrer and stirred at 23 ° C. for 1 hour. To obtain a uniform curable resin composition. Furthermore, solid content was calculated | required by the method of manufacture example 3.

This curable resin composition was applied onto a silicon wafer by a spin coater so as to have a thickness of about 0.1 μm after drying, and then cured by irradiating ultraviolet light under a light irradiation condition of 0.5 mJ / cm 2 using a high pressure mercury lamp under nitrogen. . Using an ellipsometer with respect to the obtained cured film was measured for a refractive index (n _D ²⁵⁾ at a wavelength of 589 ㎚ at 25 ℃. The results are shown in Table 5.

(Production Examples 20 to 31)

Preparation of Curable Resin Composition

Except according to the composition of Table 5, it carried out similarly to manufacture example 19, and obtained curable resin composition. Moreover, about the obtained curable resin composition, the refractive index was measured similarly to manufacture example 19. The results are shown in Table 5.

(Examples 1 to 7, Comparative Examples 1 and 2)

Manufacture of antireflection film

As shown in Table 5, on the curable resin composition coating bases (G-1 to 3) prepared in Production Examples 16 to 18, the wire bar coater (# 3) was used to form the curable resin composition prepared in Production Examples 19 to 29. Coating was carried out, and the coating was dried in an oven at 80 ° C. for 1 minute. Subsequently, an anti-reflection film was prepared by irradiating ultraviolet rays under a light irradiation condition of 0.5 mJ / cm 2 using a high pressure mercury lamp under nitrogen. It was about 100 nm when the film thickness of the hardened | cured material layer on a base was computed roughly by reflectance measurement.

(Comparative Example 3)

An antireflection film was obtained in the same manner as in Example 1 except that an atone film (trade name, manufactured by JSR, and a film thickness of 100 μm) was used instead of the film (b-1) having a conductive layer (antistatic layer).

(Comparative Example 4)

A laminated film was obtained in the same manner as in Example 1 except that the curable resin composition prepared in Production Example 19 was not used.

The following evaluation was performed about the obtained antireflection film.

(1) Scratch resistance test 1 (cloth friction resistance test)

200 round trips were carried out using the cellulose nonwoven fabric (trade name Bencote S-2, Asahi Kasei Co., Ltd.) in which the surface of the antireflection film prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was impregnated with ethanol. Rubbing was carried out, and the scratch resistance of the antireflection film surface was visually evaluated by the following criteria. The results are shown in Table 5.

(Double-circle): No flaw in the surface of the sample for evaluation.

○: Fine scratches on the surface of the sample for evaluation.

(Triangle | delta): The surface of a sample for evaluation has a flaw.

X: Peeling of a coating film is seen.

(2) scratch resistance test 2 (steel wool resistance test)

The steel wool resistance test of the anti-reflective film manufactured in Examples 1-7 and Comparative Examples 1-4 was implemented by the method shown next. 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 is loaded under a condition of 200 g. The presence or absence of scratches on the surface of the cured film was checked visually by rubbing 10 times repeatedly. The results are shown in Table 5.

(Double-circle): Peeling of a cured film and a generation of a scratch are hardly seen.

(Circle): 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.

(3) pollution resistance

Fingerprints were applied to the coating film surfaces of the antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4, and the coating film surfaces were wiped off with a nonwoven fabric (trade name Bencote S-2, Asahi Kasei Co., Ltd.). The stain resistance was evaluated by the following criteria. The results are shown in Table 5.

(Double-circle): Wipe clean and cannot visually confirm the fingerprint mark on the surface of a coating film.

(Circle): The fingerprint mark on the surface of a coating film is wiped almost completely.

X: Fingerprint marks remain on the sample surface without wiping.

(4) antireflection

Antireflection properties of the antireflective films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 (magnetic spectrophotometer U-3410, Hitachi Seisakusho, incorporating a large sample chamber integrating sphere accessory 150-09090) Co., Ltd.) was used to measure and evaluate the reflectance with a wavelength of 550 nm. Specifically, the reflectance of the antireflection film was measured by using the reflectance in the vapor deposition film of aluminum as a reference (100%), and the case where the reflectance at a wavelength of 550 nm was 1% or less was defined as ○ or more than 1%. .

(5) antistatic

The surface resistance of the antireflection film prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was measured at an applied voltage of 100 V using a high resistance meter (Agilent 4339B) and a resistance cell (Agilent 16008B), and the surface resistance was 10 ¹⁰ Ω. (Circle) and the case of 10 <^10> ohm / square or more were made into the case below / (square).

The antireflection film of the present invention is useful as an antireflection film excellent in antistatic property, scratch resistance and fouling resistance.

Claims (10)

A conductive layer formed by vapor-phase polymerizing at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof on the substrate, and the following component (A) And a low refractive index layer containing a cured product of the curable resin composition comprising (B1). (A) an ethylenically unsaturated group containing fluorine-containing polymer, (B1) Porous silica particles containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1) and a silicon compound represented by the formula (2), and having an average particle diameter of 5 to 50 nm. <Formula 1> R ¹ _h SiX _{4 -h} <Formula 2> R ² _j SiX _{4 -j} (R ¹ represents an alkyl group having 1 to 8 carbon atoms, X each independently represents an alkoxy group, halogeno group, isocyanate group (-N = C = O), carboxyl group, alkyloxy group having 2 to 4 carbon atoms). A carbonyl group or an alkylamino group having 1 to 4 carbon atoms, h represents an integer of 0 to 1, R ² is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or methacryloxy having 5 to 8 carbon atoms Alkyl group, j represents an integer of 1 to 3, X in formula 1 and X in formula 2 may be the same or different) A conductive layer formed by vapor-phase polymerizing at least one monomer selected from the group consisting of pyrrole, thiophene, furan, selenophene and 3,4-ethylenedioxythiophene and derivatives thereof on the substrate, and the following component (A) And a low refractive index layer containing a cured product of the curable resin composition comprising (B2). (A) an ethylenically unsaturated group containing fluorine-containing polymer, (B2) A porous compound containing a hydrolyzate and / or a hydrolysis condensate of a silicon compound represented by the following formula (1), a silicon compound represented by the formula (2) and a silicon compound represented by the formula (3), and having an average particle diameter of 5 to 50 nm. Silica particles.  <Formula 1> R ¹ _h SiX _{4 -h} <Formula 2> R ² _j SiX _{4 -j} <Formula 3> R ³ _k SiX _{4 -k} (R ¹ represents an alkyl group having 1 to 8 carbon atoms, X each independently represents an alkoxy group, halogeno group, isocyanate group (-N = C = O), carboxyl group, alkyloxy group having 2 to 4 carbon atoms). A carbonyl group or an alkylamino group having 1 to 4 carbon atoms, h represents an integer of 0 to 1, R ² is an alkenyl group having 2 to 8 carbon atoms, an acryloxyalkyl group having 4 to 8 carbon atoms or methacryloxy having 5 to 8 carbon atoms An alkyl group, j represents an integer of 1 to 3, R ³ represents a fluorine-substituted alkyl group having 1 to 12 carbon atoms, k represents an integer of 1 to 3, X in Formula 1, X in Formula 2 and Formula 3 May be the same or different) The said hydrolyzate and / or hydrolysis condensation of Claim 1 in which the said porous silica particle (B1) made the sum total of the silicon compound represented by the said General formula (1) and the silicon compound represented by General formula (2) 100 mol%. An anti-reflection film comprising water as a reactant of 67 to 99 mol% of silicon compound represented by formula (1) and 33 to 1 mol% of silicon compound represented by formula (2). The said porous silica particle (B2) is the said, When the sum total of the silicon compound represented by the said General formula (1), the silicon compound represented by General formula (2), and the silicon compound represented by General formula (3) is 100 mol%, The said 60 to 98 mol% of the silicon compound represented by the formula (1), 1 to 30 mol% of the silicon compound represented by the formula (2) and 1 to 20 mol% of the silicon compound represented by the formula (3) An antireflection film made of a reactant. The antireflection film according to any one of claims 1 to 4, wherein h is 0 in the silicon compound represented by the formula (1). 6. The porous silica particle (B1) or (B2) according to any one of claims 1 to 5, comprising water, an alcohol having 1 to 3 carbon atoms, a basic compound, and a half ether of acid amides, diols, and diols. An anti-reflection film which is hydrolyzed and / or hydrolyzed condensed in the presence of at least one selected from the group. The compound according to any one of claims 1 to 6, wherein the ethylenically unsaturated group-containing fluorine-containing polymer (A) isocyanates a compound containing one isocyanate group and at least one ethylenically unsaturated group and a hydroxyl group-containing fluorine-containing polymer. The antireflection film which is an ethylenically unsaturated group containing fluorine-containing polymer obtained by making it react by the ratio whose molar ratio of group / hydroxyl group is 1.1-1.9. The sum of the structural unit (a) represented by the following general formula (4), the structural unit (b) represented by the following general formula (5), and the structural unit (c) represented by the following general formula (6) according to claim 7 It consists of 20 to 70 mol% of structural units (a), 10 to 70 mol% of structural units (b), and 5 to 70 mol% of structural units (c) with respect to 100 mol%, and also gel permeation chromatography. The polystyrene reduced number average molecular weight measured by the antireflection film of 5,000-500,000. <Formula 4>

[In Formula 4, R ⁴ represents a fluorine atom, a fluoroalkyl group, or a group represented by -OR ⁵ (R ⁵ represents an alkyl group or a fluoroalkyl group.) <Formula 5>

In formula (5), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group,-(CH ₂ ) _x -OR ⁸ or a group represented by -OCOR ⁸ (R ⁸ represents an alkyl group or glycidyl group, x Represents a number of 0 or 1), a carboxyl group or an alkoxycarbonyl group] <Formula 6>

[In Formula 6, R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1] The structural unit represented by the following formula (7) according to claim 8, wherein the hydroxyl group-containing fluorine-containing polymer is further derived from an azo group-containing polysiloxane compound based on 100 moles in total of the structural units (a), (b) and (c). (d) Antireflection film containing 0.1-10 mole parts. <Formula 7>

[In Formula 7, R ¹¹ and R ¹² may be the same or different and represent a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.] The antireflection film according to any one of claims 1 to 9, further comprising a hard coating layer between the conductive layer and the low refractive index layer.

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