WO2006057297A1 - Curable resin composition and antireflective film - Google Patents

Abstract

Disclosed is a curable resin composition containing a fluorine-containing polymer (A) with ethylenically unsaturated group, a (meth)acrylate compound (B) and an organic solvent (C) which enables to obtain a cured product having a low refractive index of not more than 1.50 and excellent abrasion resistance. The curable resin composition contains, as the organic solvent (C), an organic solvent (C1) having a boiling point of less than 100°C and a surface tension of 2.1 × 10-4 N/cm at 25°C, 1 atm (1.013 × 105 Pa), and another organic solvent (C2) having a boiling point of not less than 130°C and not more than 200°C at 25°C, 1 atm. Also disclosed is an antireflective film.

Description

 Specification

 Curable resin composition and antireflection film

 Technical field

 The present invention relates to a curable resin composition and an antireflection film. More specifically, a curable resin composition containing an ethylenically unsaturated group-containing fluorine-containing polymer, which, when cured, provides a cured product having excellent scratch resistance, coating properties, and durability. And an antireflection film comprising a low refractive index layer made of such a cured product.

 Background art

 In various display panels such as liquid crystal display panels, cold cathode ray tube panels, plasma displays (PDPs), etc., in order to prevent reflection of external light and improve image quality, low refractive index, scratch resistance, coating There is a demand for an antireflection film including a low refractive index layer made of a cured product excellent in workability and durability.

 These display panels are also required to have excellent coating properties without coating defects such as coating unevenness and repellency.

 In particular, in liquid crystal display panels and PDP panels, the coating properties of the antireflection film are an important factor that affects the appearance of the final product display.

[0003] As a material for a low refractive index layer of an antireflection film, for example, a fluorine-based resin coating containing a hydroxyl group-containing fluoropolymer is known (eg, Patent Documents 1 to 3).

 However, in such a fluorine-based resin coating, it is necessary to heat and crosslink a hydroxyl group-containing fluorine-containing polymer and a curing agent such as melamine resin under an acid catalyst in order to cure the coating film. Depending on the heating conditions, there are problems that the curing time becomes excessively long and the types of base materials that can be used are limited.

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

[0004] Therefore, in order to solve the above problems, an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. The ratio of the number of isocyanate groups to the number of Z hydroxyl groups is from 0.01 to 1.0. There has been proposed a coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio (for example, Patent Document 4).

[0005] However, in the above publication, when preparing an unsaturated group-containing fluorine-containing polymer, a sufficient amount of isocyanate groups is included to react all hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer. Without using an unsaturated compound, an unreacted hydroxyl group was positively left in the polymer.

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

[0006] In order to improve the scratch resistance of the antireflection film, a technique of adding silica particles to a low refractive index film that is the outermost layer of the antireflection film is widely used (for example, Patent Document 5). , 6)

Furthermore, in order to provide an antireflection film having a lower reflectance, a material for a low refractive index film having a lower refractive index than before is desired! Therefore, by utilizing the fact that the refractive index of air is lower than that of a cocoon resin component such as acrylic, particles having voids inside the particles such as porous particles and hollow particles (hereinafter collectively referred to as hollow particles) are used. The technique used is known (for example, Patent Documents 7 to 9).

 However, these conventional technologies use fluoropolymers, so it is difficult to obtain a uniform and defect-free coating immediately after coating due to repelling caused by foreign matter.

 [0008] Patent Document 1: Japanese Patent Application Laid-Open No. 57-34107

 Patent Document 2: JP-A-59-189108

 Patent Document 3: JP-A-60-67518

 Patent Document 4: Japanese Patent Application Laid-Open No. 61-296073

 Patent Document 5:: JP-A-2002-265866

 Patent Document 6:: Japanese Patent Laid-Open No. 10-316860

Patent Document 7:: Japanese Patent Laid-Open No. 2003-139906 Patent Document 8: Japanese Patent Laid-Open No. 2002-317152

 Patent Document 9: Japanese Patent Laid-Open No. 10-142402

[0009] Accordingly, the present invention provides a curable resin composition, a cured film, and an antireflection film including the same, which provide a cured film having excellent coatability, a low refractive index and excellent scratch resistance. With the goal.

 Disclosure of the invention

 [0010] According to the present invention, the following curable resin composition, a cured film comprising the same, and an antireflection film are provided.

 [1] The following components (A), (B) and (C):

 (A) an ethylenically unsaturated group-containing fluoropolymer,

 (B) (Meta) Atre relay toy compound,

 (C) Organic solvent

 Containing

 (C) the organic solvent contains the following organic solvents (C1) and (C2), and

 A curable resin composition that gives a cured product having a refractive index of 1.50 or less.

(C1) Organic solvent with a boiling point of less than 100 ° C and a surface tension of less than 2.5 X 10 ^_4 N / cm at 25 ° C and 1 atm (1.013 X 10 ⁵ Pa)

 (C2) Organic solvent having a boiling point of 130 ° C or higher and 200 ° C or lower at 25 ° C and 1 atmosphere [2] Furthermore, (C3) An organic solvent having a boiling point of 100 ° C and lower than 130 ° C at 25 ° C and 1 atmosphere The curable resin composition according to [1], which is contained.

 [3] The proportion of (C1) in the total amount of (C) organic solvent is 100 to 99.5% by weight, (C2) is 0.5 to 90% by weight, and (C3) The curable resin composition according to the above [1] or [2], which has a ratio power of ˜89.5% by weight.

 [4] A cured film obtained by heating the curable resin composition according to any one of [1] to [3] above and curing it by irradiation with Z or radiation.

 [5] An antireflection film having a low refractive index layer comprising the cured film as described in [4] above.

[0011] The curable resin composition of the present invention has a good coatability and is cured to produce a cured product (cured film) having a low refractive index and excellent scratch resistance. be able to. The cured film of the present invention has a low refractive index and excellent scratch resistance!

 The antireflection film of the present invention includes the cured film of the present invention having a low refractive index and scratch resistance, and has good antireflection characteristics and scratch resistance.

 Brief Description of Drawings

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

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0013] Embodiments of the curable resin composition and the antireflection film of the present invention will be described below.

 [0014] 1. Curable resin composition

 The curable resin composition of the present invention may contain the following components (A) to (F). The refractive index of the cured product obtained by curing the curable resin composition of the present invention with respect to light having a wavelength of 589 nm needs to be 1.50 or less. When the refractive index is within this range, the cured film obtained by curing the curable resin composition of the present invention is suitable as a low refractive index film constituting the antireflection film.

 (A) Ethylenically unsaturated group-containing fluoropolymer

 (B) (Meta) Atre relay toy compound

 (C) Organic solvent

 (D) particles mainly composed of silica,

 (E) Compounds that generate active species upon irradiation with active energy rays or heat

 (F) Other additives

 These components will be described below.

[0015] (A) Ethylenically unsaturated group-containing fluoropolymer

 The ethylenically unsaturated group-containing fluoropolymer (A) is a fluoroolefin polymer. By the component (A), the composition of the present invention exhibits basic performance as a low refractive index material for an antireflection film such as low refractive index, antifouling property, chemical resistance, and water resistance.

Preferably, the component (A) has a side chain hydroxyl group modified with a (meth) acrylic compound. More preferably, it is modified with a (meth) acrylic compound having an isocyanate group. Such modification enables co-crosslinking with the radically polymerizable (meth) acrylic compound and improves the scratch resistance. [0016] The ethylenically unsaturated group-containing fluorine-containing polymer is obtained by combining a compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer with an isocyanate group Z. It is obtained by reacting at a molar ratio of hydroxyl group of 1.1 to 1.9.

[0017] (1) Compound containing one isocyanate group and at least one ethylenically unsaturated group

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

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

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

 [0018] It should be noted that such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.

 Examples of diisocyanates include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate).

), 1,3-bis (isocyanatemethyl) cyclohexane is preferred.

[0019] Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate.

Pentaerythritol tri (meth) acrylate is preferred.

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

[0020] (2) Hydroxyl-containing fluoropolymer

The hydroxyl group-containing fluoropolymer preferably contains the following structural units (a), (b) and (c): It becomes.

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

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

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

[0021] [Chemical 1]

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

[0022] [Chemical 2]

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

 2

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

[0023] [Chemical 3]

HR ⁶

 — C-C—— (3)

H (CH ₂ ) _v OR ⁷

[In the formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and V represents a number of 0 or 1]

[0024] (i) Structural unit (a)

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

 [0025] The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule. Ethers: Perfluoro (alkyl butyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butinolevino reetenole), perfluoro (isobutino vinyl ether), etc. A single perfluoro (alkoxyalkyl butyl ether) such as perfluoro (propoxypropyl butyl ether) or a combination of two or more thereof.

 Of these, hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!

 [0026] The content of the structural unit (a) is 20 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. This is because when the content is less than 20 mol%, it may be difficult to develop a low refractive index, which is an optically characteristic of the fluorine-containing material as intended by the present invention. This is because if the content exceeds 70 mol%, the solubility of the hydroxyl-containing fluoropolymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.

 For these reasons, the content of the structural unit (a) is preferably 25 to 65 mol%, more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Power S is more preferable.

 [0027] (ii) Structural unit (b)

In the formula (2), as the alkyl group for R ⁴ or R ⁵ , a methyl group, an ethyl group, a propyl group C 1-12 alkyl groups such as hexyl group, cyclohexyl group, lauryl group and the like, and alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group and the like.

[0028] The structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component. Examples of such bur monomers include methyl vinyl ethere, ethino levinino le ethere, _n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert -Butyl vinyl etherenole, n-pentinolevinoreethenole, n-hexenolevinoreethenore, n-year-old cubinorebi-noreethenore, n-dodecinolevinorethenore, 2-ethinorehexinolevinoreteol, cyclohexyl vinyl ether Alkyl butyl ethers or cycloalkyl alkyl ethers such as: ethyl ether such as ethyl allyl ether, butyl allyl ether, etc .; acetate acetate, butyl propionate, butyl butyrate, pivalate butyl, strength benzoate, versatic Acid bull, Carboxylic acid butyl esters such as tea acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2-Methacrylic acid esters such as 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid , Single type or a combination of two or more types of unsaturated carboxylic acids such as itaconic acid.

 [0029] The content of the structural unit (b) is 10 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.

 For these reasons, the content of the structural unit (b) is preferably 20 to 60 mol%, more preferably 20 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Power S is more preferable.

 [0030] (iii) Structural unit (c)

In formula (3), the hydroxyalkyl group for R ⁷ includes a 2-hydroxyethyl group, 2-hydroxy group Examples include droxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group, and 6-hydroxyhexyl group.

 [0031] The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl. Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxy butyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned.

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

 [0032] The content of the structural unit (c) is preferably 5 to 70 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.

 For these reasons, it is more preferable that the content of the structural unit (c) is 5 to 40 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer. It is more preferable to do this.

 [0033] (iv) Structural unit (d) and structural unit (e)

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

 [0034] (d) A structural unit represented by the following formula (4).

[0035] [Chemical 4]

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

[0036] In the formula (4), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. A fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, or the like is a phenyl group or a benzyl group. A naphthyl group and the like.

 The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the above formula (4). Examples of such an azo group-containing polysiloxane compound include compounds represented by the following formula (5).

[0038] [Chemical 5]

 (Five)

[In the formula (5), R ^{1Q to} R ¹³ represent the same or different hydrogen atom, alkyl group or cyan group, and R ″ to R ¹⁷ may be the same or different. A hydrogen atom or an alkyl group, p and q are numbers from 1 to 6, s and t are numbers from 0 to 6, y is a number from 1 to 200, and z is a number from 1 to 20.]

 When the compound represented by the formula (5) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

[0040] (e) A structural unit represented by the following formula (6).

[0041] [Chemical 6]

[In the formula (6), R ^{1U to} R ″, R ^{14 to} R ″, p, q, s, t and y are the same as those in the above formula (5). [0042] In the formulas (5) and (6), the alkyl groups represented by R ^{1Q to} R ¹³ include carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. 1-12 alkyl groups are mentioned, R

The alkyl group represented by “˜R ¹⁷ ” includes an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group.

In the present invention, the azo group-containing polysiloxane compound represented by the above formula (5) is particularly preferably a compound represented by the following formula (7).

[0044] [Chemical 7]

[In the formula (7), y and z are the same as in the above formula (5). ]

 [0045] The content of the structural unit (d) is preferably 0.1 to 10 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the coated film after curing may be lowered, and the scratch resistance of the coated film may be lowered. If it exceeds 10 mol%, the transparency of the hydroxyl group-containing fluorine-containing polymer is inferior, and when used as a coating material, repelling or the like may easily occur during coating.

Moreover, such a reason, the content of the structural units (d), with respect to the total weight of the hydroxyl group-containing fluoropolymer, and more preferably to the 0.1 to 5 mole _^0/0 device 0. force to the 1-3 mole _^0/0 S more preferred. For the same reason, it is desirable that the content of the structural unit (e) should be determined so that the content of the structural unit (d) contained therein falls within the above range.

[0046] (V) structural unit (f) The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f).

 [0047] (f) A structural unit represented by the following formula (8).

[0048] [Chemical 8]

[In the formula (8), R ¹⁸ represents a group having an emulsifying action]

[0049] In the formula (8), the group having an emulsifying action of R ¹⁸ has both a hydrophobic group and a hydrophilic group, and the hydrophilic group is a polyether structure such as polyethylene oxide or polypropylene oxide. The group is preferred.

 [0050] Examples of the group having an emulsifying action include a group represented by the following formula (9).

[0051] [Chemical 9]

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

[0052] The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (10).

[0053] [Chemical 10]

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

[0054] The content of the structural unit (f) is preferably 0.1 to 5 mol% when the total amount of the hydroxyl group-containing fluoropolymer is 100 mol%. The reason for this is that when the content ratio is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. If the proportion is within 5 mol%, the tackiness of the curable resin composition will not increase excessively, it will be easy to handle, and even if it is used as a coating material, the moisture resistance will not decrease. Because.

Moreover, such a reason, the content of the structural unit (f), with respect to the total weight of the hydroxyl group-containing fluoropolymer, and more preferably to the 0.1 to 3 mole _^0/0 device 0. force to the 2-3 mole _^0/0 S more preferred.

[0055] (vi) Molecular weight

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

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

 [0056] (3) Reaction molar ratio

 The ethylenically unsaturated group-containing fluorine-containing polymer comprises the above-mentioned compound containing one isocyanate group, at least one ethylenically unsaturated group, and a hydroxyl group-containing fluorine-containing polymer. It is obtained by reacting at a molar ratio of hydroxyl group of 1.1 to 1.9. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be reduced. On the other hand, if the molar ratio exceeds 1.9, the application of the curable resin composition is not possible. This is because the scratch resistance of the membrane after immersion in an alkaline solution may be lowered.

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

[0057] The amount of component (A) to be added is not particularly limited, but is usually 10 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that when the amount added is less than 10% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. When the added amount exceeds 90% by weight, it is curable This is because the scratch resistance of the cured coating film of the resin composition may not be obtained.

Also, for this reason force, (A) rather more preferably that a 15 to 90% by weight添力卩量components, further preferably a value within the range of 20 to 85 weight _^0/0 .

 [0058] (B) (Meta) Attale Relay Toy Compound

 The (meth) acrylate compound is used for enhancing the scratch resistance of a cured product obtained by curing a curable resin composition and an antireflection film using the cured product.

 [0059] The compound is not particularly limited as long as it is a compound containing at least one (meth) attaroyl group in the molecule.

Monomers having one (meth) atallyloyl group include, for example, acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxetyl ( (Meth) Atarylate, Isovolyl (Meth) Atylate, 2-Ethylhexyl (Meth) Atylate, Ethyl Jetylene Glycol (Meth) Atylate, t-Octyl (Meth) acrylamide, Diacetone (Meth) Acrylate Mido, dimethylaminoethyl (meth) acrylate, jetylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentagen (meth) acrylate, dicyclopente-roxetyl (meth) acrylate, dicyclopentale (Meta) Atari , N, N— Dimethyl (meth) acrylamide tetraphenyl (meth) acrylate, 2-tetratalolof enochetyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromo (meth) attaly 2-Tetrabromophenoxychetyl (meth) ate, 2 -Trichlorophenoxy (meth) acrylate, Tribromophenol (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Bi -Lucaprolatatam, N-vinylpyrrolidone, phenoxychetyl (meth) acrylate, butoxychetil (meth) acrylate, pentachlorophenol (meth) acrylate, pentabromophenol (meth) acrylate, polyethylene glycol mono ( Meta) Atalylate, Polypro Examples thereof include compounds represented by pyrene glycol mono (meth) acrylate, borne (meth) acrylate, and methyltriethylene diglycol (meth) acrylate. Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxychetyl (meth) acrylate are particularly preferable.

 [0060] Commercially available products of these monofunctional monomers include, for example, Alonics M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, Toagosei) KAYARAD TC-110S, R-564, R-128H (Nippon Kayaku Co., Ltd.), biscoat 192, biscoat 220, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F Biscort 17F (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

[0061] Further, examples of the monomer having two or more (meth) atalyloyl groups include ethylene glycol di (meth) acrylate, dicyclopentadidi (meth) acrylate, triethylene glycol dialate, tetraethylene glycol diacrylate. (Meth) atalylate, tricyclodecandiyldimethylenedi (meth) atalylate, tris (2-hydroxyethyl) isocyanurate (meth) atalylate, tris (2-hydroxyethyl) isocyanuratetri (meth) Atalylate, Capacitor Rataton-modified tris (2-hydroxyethyl) isocyanurate tri (meth) atalylate, trimethylolpropane tri (meth) talylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylol Propane tri (meth) acrylate, propylene Oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ester (Meth) acrylic acid adduct, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta erythritol tetra (meta ) Atalylate, Polyester di (meth) acrylate, Polyethylene glycol di (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, Dipenta erythritol tetra (meth) acrylate Rate, power prola Taton-modified dipentaerythritol hexa (meth) acrylate, force prolatatone modified dipentaerythritol penta (meth) acrylate, ditrimethylol propane pantetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate Modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) attaly Rate, (Meth) Atalylate of phenol novolac polyglycidyl ether Etc. can be illustrated.

 [0062] Commercially available products of these polyfunctional monomers include, for example, SA1002 (manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295. , Biscoat 300, Biscoat 360, Biscoat G PT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Biscoat 370 0 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Carrad R-526, HDDA, NPGDA, TPG DA , MANDA, R-551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA ゝ DPHA-2H ゝ DPHA-2C ゝ DPHA-2I, D

— 310, D—330, DPCA—20, DPCA—30, DPCA—60, DPCA—120, DN

— 0075, DN—2475, T—1420, T—2020, T—2040, TPA—320, TPA—330, RP—1040, RP—2040, R—011, R—300, R—205 (above, Nippon Ayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M

— 309, M—310, M—315, M—325, M—400, M—6200, M—6400 (above, manufactured by Toagosei Co., Ltd.), Light Attallate BP—4EA, BP—4PA, BP— 2EA, BP—2P A, DCP—A (manufactured by Kyoeisha Co., Ltd.), New Frontier BPE—4, BR—42M, GX—8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF — 400 (above, manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP— 1506, SP-1507, SP-1509, VR-77, SP—4010, SP-4 060 (above, Showa Polymer Co., Ltd.) ), NK Estel A-BPE-4 (Shin Nakamura Chemical Co., Ltd.).

[0063] It should be noted that the composition of the present invention preferably contains a compound containing at least two (meth) atalyloyl groups in the molecule. More preferably, a compound containing at least 3 or more (meth) atalyloyl groups in the molecule is particularly preferable. Such three or more compounds include the tri (meth) atareto toy compounds exemplified above, tetra (meth) atta relay toy compounds, penta (meth) atalyto toy compounds, hexa ( It is possible to select from among the meta) talate toy compounds, among which trimethylol propane tri (meth) acrylate, EO-modified trimethylol propane tri (meth) acrylate, dipentaerythritol Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and ditrimethylol propanetetra (meth) acrylate are particularly preferred. Each of the above compounds alone Or two or more types can be used in combination.

 [0064] In addition, the (meth) atalytoy compound may contain fluorine. Examples of such compounds include perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like alone or in combination The combination of the above is mentioned.

 [0065] The amount of component (B) to be added is not particularly limited, but is usually 1 to 88% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount is less than 1% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained, while the addition amount exceeds 88% by weight. This is because the refractive index of the cured coating film of the curable resin composition becomes high and a sufficient antireflection effect may not be obtained.

 Further, for such reasons, the addition amount of the component (B) is more preferably 1 to 60% by weight, and further preferably 1 to 40% by weight.

 [0066] (C) Organic solvent

 The curable composition of the present invention needs to contain the following organic solvents (C1) and (C2). By containing these organic solvents, the coating properties of the curable composition can be improved.

(C1) Organic solvent with a boiling point of less than 100 ° C and a surface tension of less than 2.5 X 10 ^_4 N / cm at 25 ° C and 1 atm (1.013 X 10 ⁵ Pa)

(C2) An organic solvent having a boiling point of 130 ° C or higher and 200 ° C or lower at 25 ° C1 atm. [0067] The organic solvent (C1) reduces the surface tension of the curable resin composition of the present invention, Improve sex. Specific examples of the organic solvent (C1) include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2 dimethylbutane, 2,3 dimethylbutane, n-heptane, isooctane, and cyclopentane. Aliphatic hydrocarbons such as methylcyclopentane and cyclohexane, methyl chloride, acetyl chloride, chloropropyl chloride, isopropyl chloride, chlorobutyl chloride, isobutyl chloride, t-butyl chloride, sec butyl chloride, 1, Halogens such as 1-diclonal ethane, hexafluorobenzene, 1, 1, 2-trichloroeuro- 1, 2, 2, — trifluoroethane, 1, 1, 2, 2-tetrachloro-1, 2-difluoroethane Hydrocarbons, methyl ethyl ketone (MEK), ketones such as acetone, methanol, ethanol, 1 propanol , Isopropyl alcohol (IPA), 1-butanol, 2-butanol, t-butanol, alcohols such as 2, 2, 2-trifluoroethanol, jetyl ether, dipropyl ether, diisopropyl ether, butyl vinyl ether, 1, Ethers such as 2-dimethoxyethane and methylal, methyl formate, ethyl formate, isobutyl formate, methyl acetate, ethyl acetate, isopropyl butyrate, methyl propionate, ethyl ethyl propionate, methylamine, dimethylamine, trimethylamine, ethylamine, Examples thereof include amines such as jetylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, sec butylamine, and t-butylamine. Among these are, MEK (surface tension 2. 4 X 10 ^_4 NZcm), ketones such as acetone, IPA (surface tension ^{2. 2 X 10 _4 NZcm),} t chromatography butanol (surface tension 1. 9 X 10 ^_4 NZcm) and the like are more preferable, and t-butanol is more preferable.

The surface tension of the organic solvent (C1) must be less than 2.5 X 10 ^_4 NZcm at 25 ° C and 1 atm, and preferably less than 2.1 X 10 ^_4 NZcm. The surface tension is measured by the wall Helmi (plate) method.

The organic solvent (C2) prevents whitening of the coating film in the step of removing the organic solvent after applying the curable resin composition of the present invention. Specific examples of the organic solvent (C2) include aliphatic hydrocarbons such as nonane, decane, dodecane, ethylcyclohexane, p-menthane, o-xylene, m-xylene, p-xylene, ethylbenzene, tamen, mesitylene, n— Aromatic hydrocarbons such as butylbenzene, sec butylbenzene, tert-butylenebenzene, p-cymene, o-jetylbenzene, m-jetylbenzene, p-decylbenzene, n-pentylbenzene, 1, 1, 2, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 1, 2, 3 trichloroprone, black benzene, o dichlorobenzene, m-dichlorobenzene, p dichlorobenzene, o chlorotolenene, p chlorotolenene, etc. Halogenated charcoal hydrogen, 1-pentanol, 2-methoxyethanol, 2-ethoxyethanol, 1- Xyl-2-propanol, isopentyl alcohol, 1-hexanol, 2-methyl-1 pentanol, 4-methyl-2 pentanol, 2 ethyl 1-butanol, 1 heptanol, 2 heptanol, 3 heptanol, 1-octanol, 2— Octanol, 2 Ethyl 1 Hexanol, 3, 5, 5 Trimethylhexanol, Cyclohexano 1-methylcyclohexanol, 2-methylenohexanol, 3-methinohexanol, 4 methylhexanol, 1,2 ethanediol, 1,2 propanediol, 1,2 butanediol, 2-methyl-2, 4 Pentanediol, phenol, o-cresol, 2-ethoxyethanol, 2- (methoxyethoxy) ethanol, 2-isopropoxychetanol, 2-butoxyethanol, 2-isopentyloxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol , Diethylene glycol monomethyl ether, 1 ethoxy-2-propanol, dipropylene glycolenomonomethylenoether, dipropylene glycolenomonoethylenoether, diacetone alcohol, 1,3 dichloro-2-propanol, 2-aminoethane Lumpur, 2- (Jimetoruamino) ethanol, 2- (Jechiru Amino) ethanol, alcohols etc., zo ether, § - Saul, Fuenetoru

, O-methoxytoluene, m-methoxytoluene, ρ-methoxytoluene, benzylethylenolate, diethyleneglycolinoresmethinoleatenore, diethyleneglycololegetinoreuterate, ethers such as bis (2 chloroethyl) ether, 2 heptanone (MAK), 4 1-Heptanone, Diisoptyl ketone, Acetonylacetone, Cyclohexanone, Methyl ketone Hexanone and other ketones, pentyl formate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec Hexyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butyl propionate, isopentyl propionate, butyl butyrate, isobenzyl butyrate, isobutyl isobutyrate, ethyl isovalerate, isovaleric acid Isopentyl, D Tylene alcohol monoacetate, ethylene glycol diacetate, methyl lactate, ethyl lactate, butyl lactate, 2-ethoxyethyl acetate, 2-methoxyethyl acetate, 2-butoxetyl acetate, methyl acetoacetate, acetoethyl acetate, propylene Estenoles such as glycol monomethyl ether acetate (PGMEA), 1-nitropronone, 2-nitropronone, nore-trinole, benzonitrile, dibutylamine, diisobutylamine, tripentylamine, 2-ethylhexylamine, N-methyl-line, N-N-dimethyl-line, cyclohexylamine, pyrrole, N-methylformamide, N, N-dimethylformamide, N, N-deethylformamide, N, N-dimethylacetamide, N-methylpropionamide, N , N, Ν ', N'-tetramethylurea, nitrogen compounds such as cetylmorpholine, dimethyl sulfoxide, etc. And sulfur compounds. Among these, MA :, 4 monoheptanone, diisobutylketone, acetonylacetone, cyclohexanone, methylcyclohexanone and other ketons, lactic acid ethyl, butyl lactate, 2-ethoxyethyl acetate, 2-methoxyethylyl Esters such as cetate, 2-butoxychetyl acetate, methyl acetoacetate, ethyl acetoacetate, propylene glycol monomethyl ether acetate (PGMEA) are preferred, more preferably MA :, cyclohexanone, ethyl lactate, PGMEA It is.

Furthermore, the curable resin composition of the present invention has a boiling point at 25 ° C1 atm of 100 ° C or more and less than 130 ° C, in addition to the organic solvents (C1) and (C2), if necessary. The organic solvent which is can be mix | blended. By blending the organic solvent (C3), the curable composition after coating can be quickly dried. Specific examples of the organic solvent (C3) include aliphatic hydrocarbons such as octane, 2, 2, 3 trimethylpentane, 2, 2, 5 trimethylhexane and methylcyclohexane, aromatic hydrocarbons such as toluene, 1, Halogenated hydrocarbons such as 1,2-trichlorodiethane, 1,1,1,1,2-tetrachlorodiethane, 1-cyclopentane, benzotrifluoride, 1-bromo-2-chloroethane, 2 pentanone, 3 pentanone, 2 Ketones such as xanone, methyl isobutyl ketone (MIBK), 1-butanol, isobutyl alcohol, 2 pentanol, 3 pentanol, t-pentyl alcohol, 2-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 4-Methyl-2-pentanol, 2-methoxyethanol, 1-methoxy 2-propanol, 2-black mouth ethanol, 1 Alcohols such as Rollo 2-Prono Noreno, Propylene Glycolanol Monomethinoleetenole, Ethers such as Dioxane, Trioxane, 1,2-Diethoxyethane, Acetanol, etc., Butyl formate, Propyl acetate, Butyl acetate, Isobutyl acetate, Acetic acid se Esters such as c-butyl, methyl butyrate, ethyl butyrate, jetyl carbonate, pentyl lactate, nitromethane, nitroethane, butyronitrile, isobutyronitrile, pentylamine, dicyclohexylamine, pepyridine, pyridine, ethylenediamine, propylenediamine, mol Examples thereof include nitrogen compounds such as holin. Among these, ketones such as 2 pentanone, 3 pentanone, 2-hexanone, methyl isobutyl ketone (MIBK), butyrate formate, propyl acetate, butyl acetate, isobutyl acetate, sec butyl acetate, methyl butyrate, ethyl butyrate, More preferred are esters such as jetyl carbonate and pentyl lactate. Is butyl acetate, MIBK.

 [0070] The blending amount (total amount) of the (C) organic solvent in the curable resin composition of the present invention is not particularly limited, but all components other than the (C) organic solvent in the composition 100 The amount is usually 100 to 100,000 parts by weight, preferably 300 to 20000 parts by weight, and more preferably 1000 to 10,000 parts by weight with respect to parts by weight.

The amount of (C 1) component, (C2) component and (C3) component contained in 100% by weight of all (C) component is 10-99.5% by weight, 0.5-90% by weight and 0 to 89.5 percent by weight, good Mashiku is 20 to 98.5 wt _^0/0, a 0.5 to 80 weight _^0/0 and 1 to 79.5 wt _^0/0, more preferably 30 to 80% by weight, 1 to 60% by weight and 1 to 69% by weight.

 [0071] (D) Particles mainly composed of silica

 In the curable resin composition of the present invention, (D) particles containing silica as a main component can be blended. The particle size is measured with a transmission electron microscope.

 By blending the particles (D), the scratch resistance of the cured product of the curable resin composition of the present invention, particularly the steel wool resistance, can be improved.

 As these particles containing silica as a main component, known particles can be used. If the shape of the particles is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, core-shell type particles are used. And so on. However, it is particularly preferable that a part or all of the component (D) preferred by the hollow particles and the porous particles is hollow particles to reduce the refractive index of the obtained cured product. Moreover, it is not limited to a spherical shape, and may be an irregularly shaped particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.

[0072] The dispersion medium is water! /, And an organic solvent is preferred. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycolol, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene. Hydrogens; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and γ-butalate Rataton; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination as a dispersion medium. The

 Commercially available particles mainly composed of silica include, for example, colloidal silica manufactured by Nissan Chemical Industries, Ltd. Product names: Methanol silica sol, IPA—ST, MEK—ST, MEK-ST—S, ΜΕΚ—ST — L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ゝ ST— OUP ゝ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST— 50 , ST-OL, etc.

[0073] Further, the surface of the colloidal silica that has been subjected to a surface treatment such as chemical modification can be used. For example, it contains a hydrolyzable key compound having one or more alkyl groups in the molecule or a hydrolyzate thereof. Can be reacted. Examples of such hydrolyzable silicon compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxy. Silane, 1,1,1-trimethoxy-1,2,2,2 Trimethylmonodisilane, hexamethyl-1,3 disiloxane, 1,1,1-trimethoxy 3,3,3 trimethyl-1,3 disiloxane, α-trimethylsilyl ω -Dimethylmethoxysilyl-polydimethylsiloxane, (X-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3 disilazane, etc. In addition, it has one or more reactive groups in the molecule. Use hydrolyzable key compounds Also. Molecular hydrolyzable Kei-containing compound having one or more reactive groups in the as having ΝΗ group as the reactive group In example embodiment, urea propyltrimethoxysilane, Nyu-

 2

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

[0074] Particles (D) containing silica as a main component are organic compounds containing polymerizable unsaturated groups (hereinafter referred to as "special Sometimes referred to as “constant organic compound”. It is preferable that the surface treatment is performed by (). Powerful surface treatment enables co-crosslinking with UV curable acrylic monomers, improving scratch resistance.

 [0075] (2) Specific organic compound

 The specific organic compound used in the present invention is a polymerizable compound containing a polymerizable unsaturated group in the molecule. This compound is preferably a compound further containing a group represented by the following formula (11) in the molecule, and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.

[0076] [Chemical 11]

 Y

 [In the formula (11), X represents NH, 0 (oxygen atom) or S (ion atom), Y represents O or S o)

 [0077] (i) polymerizable unsaturated group

 The polymerizable unsaturated group contained in the specific organic compound is not particularly limited. For example, the polymerizable unsaturated group includes, but is not limited to, atalyloyl group, methacryloyl group, vinyl group, probe group, butagel group, styryl group, ethynyl group, cinnamoyl group, Maleate groups and acrylamide groups can be mentioned as preferred examples.

 This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

[0078] (ii) a group represented by formula (11)

The specific organic compound preferably further contains a group represented by the formula (11) in the molecule. Specifically, the group [—X—C (= Y) —NH—] represented by the above formula (11) is specifically represented by [—O—C (= 0) —NH—], [one O—C (= S ) —NH—], [One S—C (= 0) —NH—], [One NH One C (= 0) —NH—], [One NH—C (= S) —NH—], and [ One S—C (= S) —NH—]. These groups can be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, [—O—C (= 0) —NH—] group, [—O—C (= S) —NH—] group and [—S—C (= 0) — Preferably combined with at least one of the NH—] groups That's right.

 The group [—X—C (= Y) —NH—] represented by the formula (11) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength when formed into a cured product. It is thought to impart properties such as adhesion to the substrate and heat resistance.

[Iii] (iii) a silanol group or a group that generates a silanol group by hydrolysis

 The specific organic compound is a compound having a silanol group in the molecule (hereinafter referred to as “silanol group-containing compound” t) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). Is preferred). Examples of such a silanol group-generating compound include compounds having an alkoxy group, an aryloxy group, a acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An alkoxy group or an aryloxy group is formed on the silicon atom. A compound containing the compound, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.

 The silanol group-generating site of the silanol group or silanol group-generating compound is a structural unit that binds to particles containing silica as a main component by a condensation reaction that occurs following a condensation reaction or hydrolysis.

[0080] (iv) Preferred embodiment

 Preferable specific examples of the specific organic compound include, for example, a compound represented by the following formula (12).

[0081] [Chemical 12]

[0082] R ¹ and R ^2U are the same or different hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or aryl groups, and a represents a number of 1, 2 or 3.

Examples of R ¹⁹ and R ² ° include methyl, ethyl, propyl, butyl, octyl, phenol, xylyl group and the like.

[0083] Examples of the group represented by [(R ¹⁹ 0) R ²⁰ Si—] include, for example, a trimethoxysilyl group, a triethoxy group, and the like.

a 3 ~ a Examples thereof include a silyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

[0084] R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, and phenylene.

[0085] R ²² is a divalent organic group, and usually a molecular weight of 14 to 10,000, preferably a molecular force of 76 or 500, and the medium force of a divalent organic group is selected. For example, chain polyalkylene groups such as hexamethylene, otatamethylene, dodecamethylene, etc .; alicyclic or polycyclic divalent organic groups such as cyclohexylene, norvolylene, etc .; phenylene, naphthylene, biphenylene, And divalent aromatic groups such as polyphenylene, and these alkyl group-substituted and aryl-substituted groups. In addition, these divalent organic groups may include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, which may contain an atomic group containing an element other than carbon and hydrogen atoms, and further in the above formula (11). Indicating groups can also be included.

[0086] R ²³ is (b + 1) -valent organic group, preferably a linear, branched or cyclic saturated hydrocarbon group, selected from unsaturated hydrocarbon group.

 [0087] Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, ataryloyl (oxy) group, meta-atallyloyl (oxy) group, bur (oxy) group, probe (oxy) group, butagel (oxy) group, styryl (oxy) group, ethur ( Oxy) group, cinnamoyl (oxy) group, maleate group, allylamido group, methacrylamide group and the like. Of these, an allyloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

[0088] For the synthesis of the specific organic compound used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) an addition reaction between a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. More can be done. Alternatively, the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can be synthesized directly by addition reaction of a compound having a polymerizable unsaturated group and isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

 [0089] Of these methods, (i) is preferably used to synthesize the compound represented by the formula (12). More specifically, for example,

 Method (a): First, by reacting a mercaptoalkoxysilane with a polyisocyanate compound, an intermediate containing an alkoxysilyl group, [S—C (= 0) —NH] group and an isocyanate group in the molecule. And then reacting the isocyanate remaining in the intermediate with an active hydrogen-containing polymerizable unsaturated compound, the unsaturated compound is converted via the [0-c (= o) -NH] group. To combine them,

 Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, a [—0—C (= 0) —NH] group in the molecule, and Examples include a method of forming an intermediate containing an isocyanate group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via an [S—C (= 0) —NH] group. . Furthermore, among them, the method (a) is preferred in that the polymerizable unsaturated group is not reduced by the Michael addition reaction.

 [0090] In the synthesis of the compound represented by the formula (12), the reaction with an isocyanate group [S

As an example of an alkoxysilane capable of forming a —C (= 0) NH] group, a compound having at least one alkoxysilyl group and one mercapto group in the molecule can be given. Examples of such mercaptoalkoxysilanes include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxysilane, mercapto And propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Also, a product of addition of an amino-substituted alkoxy silane and an epoxy group-substituted mercaptan, an epoxy silane and α, _ω -dimethyl An addition product with a Lukaptoi compound can also be used.

 [0091] The polyisocyanate compound used in the synthesis of the specific organic compound can be selected from the polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.

 [0092] Examples of such polyisocyanate compounds include, for example, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, 1,3 xylylene diisocyanate, 1,4-xylylene Range isocyanate, 1,5 Naphthalene diisocyanate, m-Phenol-diisocyanate, p-Phenol-diisocyanate, 3,3, -dimethinoleol 4,4, -diphenylmethane diisocyanate, 4,4'-diphenyl- L-methane diisocyanate, 3,3, -dimethylphenol diisocyanate, 4,4, -biphenol-diisocyanate, 1,6 hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclo Hexinoreisocyanate), 2,2,4 Trimethylhexamethylene diisocyanate, bis (2-isocyanateethyl) fumarate, 6-isopropyl 1,1,3-diphenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane And tetramethynolexylylene diisocyanate, 2, 5 (or 6) -bis (isocyanate methyl) monobicyclo [2.2.1] heptane, and the like. Among these, 2,4 tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate), 1, 3 bis (isocyanate) Nate methyl) cyclohexane, etc. are preferred. These can be used alone or in combination of two or more.

 [0093] In the synthesis of the specific organic compound, by addition reaction with the polyisocyanate compound.

 An example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded via an [OC (= 0) —NH—] group is the [— 0— C (= 0) by an addition reaction with an isocyanate group in the molecule. — Compounds having at least one active hydrogen atom capable of forming an NH group and at least one polymerizable unsaturated group.

[0094] Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2 Hydroxy 1 3 Phenyloxypropyl (meth) acrylate, 1,4 —Butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) attaylyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexane monomono (meth) acrylate , Neopentyl alcohol mono (meth) attairelate, trimethylol propanedi (meth) atelier, trimethy mouth-lugetane (meth) atelate, pentaerythritol tri (meth) attalierate, dipentaerythritol penta (Meta) Attalinate etc. can be mentioned. In addition, compounds obtained by addition reaction of glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and pentaerythritol (meth) acrylate are preferred.

 These compounds can be used alone or as a mixture of two or more.

[3] (3) Surface treatment method of particles mainly composed of silica (hereinafter also referred to as particles) with a specific organic compound

 The surface treatment method of the particles with the specific organic compound is not particularly limited, but it can also be produced by mixing the specific organic compound and particles, heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the specific organic compound with the particles. However, when the specific organic compound has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the specific organic compound.

[0096] The reaction amount of the particles and the specific organic compound is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably, with the total of the particles and the specific organic compound being 100% by weight. Is 1% by weight or more. If it is less than 0.01% by weight, the resulting cured product may not have sufficient transparency and scratch resistance due to insufficient dispersibility of the particles in the composition.

 [0097] Hereinafter, the alkoxysilyl group-containing compound represented by the formula (12) as the specific organic compound

Taking the (alkoxysilane compound) as an example, the surface treatment method will be described in more detail. The amount of water consumed by hydrolysis of the alkoxysilane compound during the surface treatment should be such that at least one alkoxy group on the silicon in one molecule is hydrolyzed. Yes. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably two minutes of the number of moles of all alkoxy groups. 1 to less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface. In the cured product of the composition containing the composed particles, the effect of developing high hardness and scratch resistance is low.

[0098] In the surface treatment, the alkoxysilane compound is separately subjected to hydrolysis, and then mixed with powder particles or solvent dispersion sol of particles, followed by heating and stirring. A method of hydrolyzing the alkoxysilane compound in the presence of particles; or a method of surface-treating the particles in the presence of other components such as a polymerization initiator can be selected. Among these, a method in which the alkoxysilane compound is hydrolyzed in the presence of particles is preferable. During the surface treatment, the temperature is preferably 0 ° C or higher and 150 ° C or lower, more preferably 20 ° C or higher and 100 ° C or lower. The processing time is usually in the range of 5 minutes to 24 hours.

 [0099] When a powdery powder is used during the surface treatment, an organic solvent is added for the purpose of smoothly and uniformly carrying out the reaction with the alkoxysilane compound. Also good. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, and lactic acid. Esters such as ethyl and y butyrolatatatone; Ethers such as ethylene glycol monomethyl ether and polyethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. The amides can be mentioned. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

 The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

[0100] When a solvent-dispersed sol is used as particles, a small amount of the solvent-dispersed sol and the specific organic compound are used. It can be produced by mixing at least. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

 [0101] In order to promote the reaction during the surface treatment, an acid, salt or base may be added as a catalyst.

 Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, An unsaturated organic acid such as itaconic acid, as a salt, for example, an ammonium salt such as tetramethyl ammonium hydrochloride, tetraptyl ammonium hydrochloride, etc., and as a base, for example, Ammonia water, jetylamine, triethylamine, dibutylamine, primary amines such as cyclohexylamine, secondary or tertiary aliphatic amines, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, Examples include quaternary ammonium hydroxides such as tetrabutyl ammonium hydroxide. Among these, preferred examples are: The organic acid, unsaturated organic acid, as the base tertiary Amin or quaternary ammonium - a Umuhidorokishido. The amount of addition of these acids, salts or bases is preferably 0.001 to 1.0 parts by weight, more preferably 0.01 parts by weight and 0.1 parts by weight with respect to 100 parts by weight of the alkoxysilane compound.

[0102] It is also preferable to add a dehydrating agent to accelerate the reaction.

 As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, orthoesters such as methyl orthoformate and ethyl orthoformate are preferred.

 The amount of the alkoxysilane compound bound to the particles is usually 110 ° C to 800 ° C in air as a constant value of weight loss% when the dry powder is completely burned in air. It can be determined by thermogravimetric analysis.

[0103] The blending amount of component (D) in the resin composition is usually 0 to 40% by weight, preferably 1 to 30% by weight, based on the total amount of the composition other than the organic solvent. Weight percent is even more preferred. The amount of particles means solid content, and the particles are used in the form of a solvent dispersion sol. Sometimes the amount does not include the amount of solvent.

 [0104] (E) Compound that generates active species upon irradiation with active energy rays or heat

 A compound that generates active species upon irradiation with active energy rays or heat is used to cure the curable resin composition.

[0105] (1) Compounds that generate active species upon irradiation with active energy rays

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

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

[0106] (i) Kind

Examples of photo radical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenol) 2 hydroxy-1-methylpropanone 1-on, carbazole, xanthone, 4-clobenbenzophenone. 4, 4'-mino minobenzophenone, 1, 1-dimethoxydeoxybenzoin, 3, 3, 1-dimethyl-4-methoxybenzophenone, dianthus xanthone, 2, 2-dimethoxy-2-phenacetophenone, 1— (4-Dodecylphenol) 2-hydroxy-1-2-methylpropane-1-one, 2-methyl-11- [4- (methylthio) phenol] 2 morpholinopropane 1-one, triphenylamine, 2 , 4, 6 Trimethyl benzoyl diphosphine phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy 2- Tilu 1 Phenyl Propane 1 ON, Fluorenone, Fluorene, Benzaldehyde, Benzoin Ether, Benzoin Propyl Ether, Benzophenone, Michler's Ketone, 3-Methylacetophenone, 3, 3 ', 4, 4'-Tetra (tert butyl peroxycarbo- ) Benzophenone (BTTB), 2- (dimethylamino) — 1— [4— (morpholol) phenol] —2-phenol methyl) 1-butanone, 4 Benzoyl 4′-methyldisulfide sulfide, benzil Or combinations of BTTB with xanthene, thixanthene, coumarin, ketocoumarin, and other dye sensitizers.

 [0107] Among these photopolymerization initiators, 2, 2 dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 (methylthio) phenol] 2 Morpholinopropane 1-one, 2 (dimethylamino) 1 4 (morpholinyl) phenol] 2 methanol 1) -butanone and the like are more preferable, 1-hydroxycyclohexylphenylketone, 2-methyl-11 [4 (methylthio) phenol] 2 morpholinopropane 1-ion, 2- (dimethylamino) ) -1- [4- (morpholol) phenol] -2 phenolmethyl) -1-butanone and the like.

 [0108] (ii) Amount added

 The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the amount of the additive is less than 0.1% by weight, the curing reaction becomes insufficient and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may decrease.

 For this reason, it is more preferable that the addition amount of the photopolymerization initiator is 15% by weight with respect to the total amount of the composition other than the organic solvent.

[0109] (2) Compounds that generate active species by heat

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

[0110] (i) Kind

Examples of thermal radical generators include benzoyl peroxide, tert-butyloxybenzoate, azobisisobutyoxy-tolyl, acetylyl peroxide, lauryl peroxide, tert butyl peracetate, tamil peroxide, tert butyl peroxide, tert butyl hydride peroxide 2, 2, azobis (2, 4 dimethyl vale Mouth-tolyl), 2,2, -azobis (4-methoxy-2,4-dimethylvale mouth-tolyl) and the like may be used alone or in combination of two or more.

[0111] (ii) Addition amount

 The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight based on the total amount of the composition other than the organic solvent. This is because if the amount added is less than 0.1% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, if the addition amount of the photopolymerization initiator exceeds 10% by weight, the refractive index of the cured product increases and the antireflection effect may decrease.

 For these reasons, it is more preferable to add 1 to 8% by weight of the thermal polymerization initiator based on the total amount of the composition other than the organic solvent.

[0112] (F) Additive

 In the curable resin composition, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, a surfactant, an acceptable agent are used as long as the objects and effects of the present invention are not impaired. It is also preferable to further contain additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the components (C) and (D), pigments, and dyes.

 [0113] Next, a preparation method and curing conditions for the curable resin composition of the present invention will be described.

 The curable resin composition of the present invention comprises the above (A) ethylenically unsaturated group-containing fluoropolymer, the above (B) component and (C) component or, if necessary, the above (D) component, (E) It can be prepared by adding the components and (F) additive, respectively, and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

[0114] There are no particular restrictions on the curing conditions of the curable rosin yarn and the composition. For example, when an active energy ray is used, the exposure amount is within a range of 0.01 to 10 j / cm ^2. It is preferable that

This is because when the exposure amount is less than 0. OljZcm ² , curing failure may occur. On the other hand, if the exposure amount exceeds lOjZcm ² , the curing time may become excessively long.

For this reason, it is more preferable to set the exposure amount to a value in the range of 0.05 to 5jZcm ² , and more preferably to a value in the range of 0.1 to 3j / cm ² .

[0115] When the curable resin composition is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 1 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.

 For this reason, it is more preferable to heat for 2 to 120 minutes at a temperature in the range of 50 to 180 ° C. Heat for 5 to 60 minutes at a temperature in the range of 80 to 150 ° C. Is even better.

[0116] 2. Anti-reflective coating

 The antireflection film of the present invention includes a low refractive index layer made of a cured product obtained by curing the curable resin composition. Furthermore, the antireflection film of the present invention can contain a high refractive index layer, a hard coat layer, and z or a substrate under the low refractive index layer.

 Figure 1 shows a powerful antireflection coating 10. As shown in FIG. 1, a hard coat layer 14 and a low refractive index layer 18 are laminated on a substrate 12.

 At this time, a high refractive index layer 16 (not shown) may be formed between the hard coat layer 14 and the low refractive index layer 18. Alternatively, the low refractive index layer 18 may be formed directly on the substrate 12 without providing the hard coat layer 14.

 Further, an intermediate refractive index layer (not shown) may be provided between the high refractive index layer 16 and the low refractive index layer 18 or between the high refractive index layer 16 and the hard coat layer 14. Good.

[0117] (1) Low refractive index layer

 The low refractive index layer is composed of a cured product obtained by curing the curable resin composition of the present invention. Since the configuration and the like of the curable resin composition are as described above, a specific description thereof will be omitted, and the refractive index and thickness of the low refractive index layer will be described below.

[0118] The refractive index of the cured product obtained by curing the curable resin composition (the refractive index of Na—D line, measured Constant temperature 25 ° C.), that is, the refractive index of the low refractive index film is 1.50 or less, preferably 1.45 or less. This is because when the refractive index of the low refractive index film exceeds 1.45, the antireflection effect may be significantly reduced when combined with a high refractive index film. Therefore, it is more preferable that the refractive index of the low refractive index film is 1.44 or less.

 When providing a plurality of low refractive index films, it is sufficient that at least one of them has a refractive index value within the above-mentioned range. Therefore, the other low refractive index films exceed 1.45. It may be a value.

 [0119] Further, when a low refractive index layer is provided, a better antireflection effect can be obtained, so that the refractive index difference from the high refractive index layer is preferably 0.05 or more. The reason for this is that 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 of these antireflective film layers cannot be obtained, and instead the antireflective effect. This is because there is a case where the value decreases.

 Therefore, it is more preferable to set the difference in refractive index between the low refractive index layer and the high refractive index layer to a value within the range of 0.1 to 0.5. More preferably, the value of

[0120] The thickness of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example. 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 a base may decrease, whereas when the thickness exceeds 300 nm, optical interference does not occur. This is because the antireflection effect may be reduced, and therefore the thickness of the low refractive index layer is more preferably 50 to 250 nm, more preferably 60 to 200 nm.

 In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness may be 50 to 300 nm.

[0121] (2) High refractive index layer

In the antireflection film of the present invention, a high refractive index layer may be formed between the hard coat layer and the low 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-type resin, phenol-type resin, melamine-type resin It is preferable to include one kind or a combination of two or more kinds such as alkyd series resin, cyanate series resin, acrylic series resin, polyester series resin, urethane series resin and siloxane series resin. This is because such a resin can form a strong thin film as the high refractive index layer, and as a result, the scratch resistance of the antireflection film can be remarkably improved. However, normally, the refractive index of these resins alone is 1.45 to L62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Further, as a curing form, a curable composition capable of thermosetting, ultraviolet curing, and electron beam curing can be used, but an ultraviolet curable composition having good productivity is more preferably used.

[0122] The thickness of the high refractive index layer is not particularly limited, but is preferably, for example, 50-30, OOOnm. 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 may decrease the adhesion to the substrate, while the thickness If the thickness exceeds 30, OOOnm, optical interference may occur and the antireflection effect may be reduced.

 Therefore, the thickness of the high refractive index layer is more preferably 50 to: L, OOOnm, and more preferably 60 to 500 nm.

 In addition, in order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be 50 to 30 and OOOnm.

 In addition, 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.

[0123] (3) Hard coat layer

 The constituent material of the hard coat layer used for the antireflection film of the present invention is not particularly limited. As such a material, siloxane resin, acrylic resin, melamine resin, epoxy resin, etc. can be used alone or in combination of two or more.

[0124] The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 50 / ζ πι and more preferably 5 to 10 m. The reason for this is that when the thickness of the hard coat layer is less than 1 μm, the adhesion of the antireflection film to the substrate may not be improved, whereas the thickness exceeds 50 / zm. And form uniformly This is because it may be difficult.

 [0125] (4) Base material

 The type of substrate used in the antireflection film of the present invention is not particularly limited. For example, glass, polycarbonate-based resin, polyester-based resin, acrylic-based resin, triacetylcellulose-based resin (TAC) Examples of such a base material include: By using anti-reflective coatings containing these base materials, it can be used in a wide range of applications for anti-reflective coatings such as color filters in camera lens units, television (CRT) screen display units, or liquid crystal display devices. In this case, an excellent antireflection effect can be obtained.

 [Example]

 [0126] Hereinafter, the ability of the present invention to be described more specifically with reference to examples. The scope of the present invention is not limited to the description of these examples.

 [0127] (Production Example 1)

 Synthesis of hydroxyl-containing fluoropolymers

 A 2.0-liter stainless steel autoclave with a magnetic stirrer was thoroughly replaced with nitrogen gas, and then 1200 g of ethyl acetate, 346 g of perfluoro (propyl butyl ether), 94 g of ethyl vinyl ether, 115 g of hydroxy ethyl vinyl ether, 4 g of lauryl oxide, 23 g of a polydimethylsiloxane containing an azo group represented by the above formula (7) (VPS 1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and a nonionic reactive emulsifier (NE— 30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.) was charged with 450 g, cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.

[0128] Next, 215 g of hexafluoropropylene was charged, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C was 5.3 X 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours, and when the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 30%. The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 850 g of a hydroxyl group-containing fluoropolymer. Table 1 shows the monomers and solvents used. [0129] [Table 1]

 table 1

[0130] With respect to the obtained hydroxyl group-containing fluoropolymer, the polystyrene-equivalent number average molecular weight by gel permeation chromatography and the fluorine content by the alizarin complexon method were measured. In addition, the ratio of each monomer component constituting the hydroxyl group-containing fluoropolymer was determined from both NMR analysis results of —NMR and ¹³ C-NMR, elemental analysis results, and fluorine content. The results are shown in Table 2.

 [0131] [Table 2]

 Table 2

[0132] VPS1001 is an azo group-containing polydimethylsiloxane represented by the above formula (7) having a number average molecular weight of 70 to 90,000 and a polysiloxane moiety having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier wherein n is 9, m is 1 and u is 30 in the above formula (10). Furthermore, in Table 2, the correspondence between the monomer and the structural unit is as follows.

 Monomer structural unit

 Hexafluoropropylene (a)

 Perfluoro (propyl butyl ether) (a)

 Etheryl ether (b)

Hydroxyethyl vinyl ether ( _c )

 NE-30 (f)

 Polydimethylsiloxane skeleton (d)

[0133] (Production Example 2)

 Synthesis of ethylenically unsaturated group-containing fluoropolymer (methacryl-modified fluoropolymer) Hydroxyl group obtained in Production Example 1 in a 1 liter separable flask equipped with an electromagnetic stirrer, glass condenser and thermometer 50.0 g of fluorinated polymer as a polymerization inhibitor

2, 6 G t-Butylmethylphenol 0. Olg and methyl isobutyl ketone (MIBK)

370 g was charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer dissolved in MIBK and the solution became clear and uniform.

 Next, 13.2 g of 2-methacryloyloxychetinoleisocyanate is added to this system, and the mixture is stirred until the solution becomes homogeneous. Then, 0.1 g of dibutyltin dilaurate is added to start the reaction, Was maintained at 55 to 65 ° C. and stirring was continued for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer.

 The obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at room temperature to obtain a methacryl group-containing fluoropolymer. Table 3 shows the raw material monomers used.

[0134] [Table 3] Table 3

[0135] (Production Example 3)

 Preparation of composition for hard coat layer In a container shielded from ultraviolet rays, 86 parts of MEK-dispersed nanosilica sol (MEK-ST manufactured by Nissan Chemical Industries, 30 parts as solids), 65 parts of dipentaerythritol hexaatalylate (Japan) DPHA), 2-Methyl-1 [4 (Methylthio) phenyl] 2 Morpholinopropan-1-one 5 parts (Chinoku 'Specialty' Irgacure 907), MIB K44 part at 50 ° C for 2 hours By stirring, a composition for a hard coat layer having a uniform solution was obtained. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by weight.

[0136] (Production Example 4)

 Preparation of substrate for coating curable resin composition

A4 size single-sided easy-adhesive polyethylene terephthalate film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) is coated with the silica particle-containing hard coat layer composite material prepared in Production Example 3. The film was coated with a wire bar coater to a thickness of 6 m and dried in an oven at 80 ° C for 1 minute to form a coating film. Next, using a high pressure mercury lamp in the air, ultraviolet rays were irradiated under the light irradiation condition of ljZcm ² to prepare a substrate for coating a curable resin composition.

 [Example 1]

8.25 g of the (A) ethylenically unsaturated group-containing fluoropolymer obtained in Production Example 2, (B) 1.25 g of dipentaerythritol pentaatalylate (SR399E manufactured by Sartoma I), photopolymerization initiator 2-Methyl- 1 1 [4 (Methylthio) phenol] 2 Morpholinopropane 1-one (Ciba 'Specialty' Irgacure 907) 0.5 g, (C) Methyl ethyl ketone (MEK) as organic solvent A total of 190 g of 114 g, methyl isobutyl ketone (MIBK) 38 g and propylene glycol monomethyl ether acetate (PGMEA) 38 g was charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour. A composition was obtained. In addition, the solid content concentration determined by the method of Production Example 3 was 5% by weight.

The curable resin composition obtained here was applied onto a silicon wafer with a spin coater so that the thickness after drying was about 0.1 m, and then 0.3 J using a high-pressure mercury lamp under nitrogen. the UV cured by irradiation with light irradiation condition of ZCM ^2. The resulting cured product was measured for refractive index (n ²⁵ ) at a wavelength of 589 nm at 25 ° C using an ellipsometer.

 D

 As a result, the refractive index was 1.43.

[0138] Further, the film was coated on the hard coat obtained in Production Example 4 with a wire bar coater to a thickness of 0.1 m, and dried at 50 ° C for 1 minute to form a coating film. Next, an antireflection film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.2 jZcm ² using a high-pressure mercury lamp under a nitrogen stream. As a result of evaluating the reflectance of the obtained antireflection film with a reflection spectrometer, the minimum reflectance was 2.5%.

 [0139] (Examples 2 to 6, Comparative Examples 1 to 7)

 (C) Each curable composition was obtained in the same manner as in Example 1 except that the solvents shown in Table 4 and Table 5 were used as the organic solvent. The composition unit in the table is% by weight.

 [0140] [Table 4]

[0141] [Table 5]

 Table 5

 [0142] The boiling points and surface tensions of the organic solvents listed in Tables 4 and 5 at 25 ° C and 1 atm are as follows.

Methyl ethyl ketone (MEK): Boiling point 79.6 ° C; Surface tension 2.4 X 10 " ⁴ N / cm Isopropyl alcohol (IPA): Boiling point 82.4 ° C; Surface tension 2.2 X 10" ⁴ N / cm t-butanol: boiling point 82.4 ° C; surface tension 1.9 X 10 " ⁴ N / cm

 Methyl isobutyl ketone (MIBK): Boiling point 116. 2 ° C

 Methyl amyl ketone (MAK): Boiling point 151.5 ° C

 Propylene glycol monomethyl ether acetate (PGMEA): Boiling point 146 ° C

[0143] (Evaluation example 1)

 Evaluation of coating liquid uniformity

 Each curable composition obtained in Examples 1 to 6 and Comparative Examples 1 to 7 was prepared, and then allowed to stand at 25 ° C. for 24 hours. Thereafter, the uniformity was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.

 ○: Uniform transparency

 Slightly cloudy

 X: Strongly turbid or partially sedimented

[0144] (Evaluation example 2)

 Evaluation of coatability

On the hard coat obtained in Production Example 4, each curable resin composition was coated with a wire bar coater to a film thickness of 0.1 / xm, dried at 50 ° C for 1 minute, and then coated. Formed. Next Then, under a nitrogen stream, a low-refractive-index film layer was formed by irradiating ultraviolet rays under a light irradiation condition of 0.2 jZcm ² using a high-pressure mercury lamp. To make it easy to see coating film defects, the back surface (base material side) of the obtained antireflection film is completely painted with black spray, and from the low refractive index film side under the three-wavelength white fluorescent lamp (Toshiba EX-N) The appearance was visually evaluated. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.

 ○: No coating unevenness and noise

 Δ: Slightly uneven coating and repelling

 X: There are uneven coating, unevenness and unevenness on the entire surface.

[0145] (Evaluation example 3)

 Haze measurement

 The haze of the antireflection film obtained in Evaluation Example 2 was measured with a color haze meter. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.

 0: 0.5 or less

 △: 0.5 to 1.0

 X: l. 0 or more

 [0146] (Evaluation example 4)

 Drying evaluation

 Each curable resin composition was coated on the hard coat under the same conditions as in Evaluation Example 2, allowed to stand at room temperature, and the time until drying was visually evaluated. The evaluation criteria are as follows. The results are shown in Table 4 and Table 5.

 ○: Dried within 30 seconds

 Δ: Dried in 30-2 minutes

 X: It took more than 2 minutes to dry

 Industrial applicability

[0147] The curable resin composition of the present invention is a uniform liquid composition, and has excellent scratch resistance, antifouling properties, and coating properties, and the cured film has excellent transparency, particularly an antireflection film. Useful as.

Claims

Claims [1] The following components (A), (B) and (C): (A) a fluorine-containing polymer containing an ethylenically unsaturated group, (B) a (meth) ataretoy compound, (C) A curable resin composition containing an organic solvent, wherein (C) the organic solvent contains the following organic solvents (C1) and (C2), and gives a cured product having a refractive index of 1.50 or less.

(C1) Organic solvent with a boiling point of less than 100 ° C and a surface tension of less than 2.5 X 10 ^_4 N / cm at 25 ° C and 1 atm (1.013 X 10 ⁵ Pa)

 (C2) Organic solvent having a boiling point of 130 ° C or higher and 200 ° C or lower at 25 ° C1 atm. [2] Furthermore, (C3) An organic solvent having a boiling point of 100 ° C or higher and lower than 130 ° C at 25 ° C1 atm. The curable resin composition according to claim 1, which is contained.

[3] The proportion of (C1) in the total amount of (C) organic solvent is 100 to 99.5% by weight, (C2) is in the range of 0.5 to 90% by weight, and (C3) 3. The curable resin composition according to claim 1 or 2, wherein the ratio power is 8 to 89.5% by weight.

[4] A cured film obtained by curing the curable resin composition according to any one of claims 1 to 3 by heating and irradiating with Z or radiation.

[5] An antireflection film having a low refractive index layer comprising the cured film according to claim 4.