JP2010095695A - Curable composition for forming layer with low reflective index - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition imparting cured films having not only a low refractive index, excellent scratch resistance and antifouling properties but excellent abrasion resistance at the same time. <P>SOLUTION: The curable composition for forming layers with low reflective index includes (A) a compound expressed by general formula (1) [wherein R<SP>11</SP>=1-3C alkyl; R<SP>12</SP>=a divalent aliphatic, alicyclic or aromatic group which may have a substituent; R<SP>13</SP>=a single bond, methylene or ethylene; R<SP>14</SP>and R<SP>15</SP>=fluorinated methylene or 2-4C perfluoroalkylene; R<SP>17</SP>=a (meth)acroyl group-bearing group; R<SP>18</SP>=a P+1 valent organic group which may contain a hetero atom; m=10-100; n=5-50; P=1 or 2] and (B) a compound except (A), having ≥2 ethylenically unsaturated groups and ≥20 mass% fluorine content. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition for forming a low refractive index layer. More specifically, the present invention relates to a curable composition for forming a low refractive index layer containing a slip agent having a specific structure.

  In recent years, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of each substrate has hardness, Curing composition capable of forming a cured film excellent in any of scratch resistance, antifouling property, abrasion resistance, surface slipperiness, low curling property, adhesion, transparency, chemical resistance and appearance of coating surface Things are requested.

In order to satisfy such a request, various compositions have been proposed, but have excellent coating properties as a curable composition, and when it is a cured film, has high hardness and scratch resistance, At present, no product with the characteristics of excellent transparency and antifouling properties has been obtained.
As a method for imparting antifouling properties, for example, Patent Document 1 describes a curable composition containing a polysiloxane having a (meth) acryloyl group, but it is further improved from the viewpoint of the wipeability of oily markers. There was room.

  Patent Document 2 discloses a composition for forming an antireflection film that can improve the slipperiness of the surface of the antireflection film, is soluble in a non-fluorine general-purpose solvent, and is easy to form a thin film. This composition for forming an antireflection film is a composition comprising a reactive surface modifier (I) and an antireflection film material (II), of which the reactive surface modifier (I) is (A A reactive group-containing composition comprising a reaction product of a triisocyanate trimerized from a diisocyanate and (B) at least two active hydrogen-containing compounds, wherein the component (B) is (B-1) The composition comprises a perfluoropolyether having at least one active hydrogen and (B-2) a monomer having an active hydrogen and a self-crosslinkable functional group. By adding such a reactive surface modifier (I), the surface properties of the antireflection film, especially surface slipperiness (lower coefficient of friction), surface hardness, wear resistance, chemical resistance, contamination wiping It is described that the surface property improved by improving the property, water repellency, oil repellency, solvent resistance, etc. can be imparted to the surface of the original coating film.

JP-A-2005-36018 JP 2006-37024 A

However, the conventional antireflection film-forming composition does not have sufficient abrasion resistance, and further improvements in scratch resistance and antifouling properties are necessary.
The present invention has been made in view of the above-mentioned problems, and provides a curable composition that provides a cured film having a low refractive index and not only excellent scratch resistance and antifouling properties but also excellent wear resistance at the same time. The purpose is to provide.

  In order to achieve the above object, the present inventors have intensively studied and improved the compound having a (meth) acryloyl group forming a matrix of the resulting cured film, a fluorine-containing compound and / or hardness for improving slipperiness. It is possible to achieve the above-mentioned object by blending a compound having a perfluoropolyether group and a dialkylsiloxane group in the molecule with a curable composition for forming a low refractive index layer containing hollow silica particles. The headline and the present invention were completed.

That is, the present invention provides the following curable composition for forming a low refractive index layer, a cured film and an antireflection film.
1. A curable composition for forming a low refractive index layer containing the following components (A) and (B). (A) Compound represented by the following general formula (A-1)
[In Formula (1), R < ¹¹ > is a C1-C3 alkyl group each independently, and R < ¹² > is the bivalent aliphatic group, alicyclic group, or aromatic which may have a substituent. R ¹³ is each independently a single bond, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently a methylene fluoride group or a C 2-4 perfluoroalkylene group, R ¹⁷ Is a group having a (meth) acryloyl group, R ¹⁸ is a p + 1 valent organic group which may contain a hetero atom, m is an integer of 10 to 100, and n is an integer of 5 to 50. , P is 1 or 2. ]
(B) A compound other than the above (A) having two or more ethylenically unsaturated groups and a fluorine content of 20% by mass or more. A curable composition for forming a low refractive index layer, comprising at least one selected from the group consisting of the following component (A), components (B) and (C), and component (D). (A) a compound represented by the following general formula (A-1),
[In Formula (1), R < ¹¹ > is a C1-C3 alkyl group each independently, and R < ¹² > is the bivalent aliphatic group, alicyclic group, or aromatic which may have a substituent. R ¹³ is independently a single bond, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently methylene fluoride or a C 2-4 perfluoroalkylene group, and R ¹⁷ is A group having a (meth) acryloyl group, R ¹⁸ is a p + 1 valent organic group which may contain a hetero atom, m is an integer of 10 to 100, and n is an integer of 5 to 50; p is 1 or 2. ]
(B) Compound other than (A) containing two or more ethylenically unsaturated groups and having a fluorine content of 20% by mass or more (C) Compound having two or more ethylenically unsaturated groups and containing no fluorine ( D) Silica particles having cavities3. The above (B) contains 2 or more ethylenically unsaturated groups, a polymer having a number average molecular weight measured by gel permeation chromatography of 5000 or more and a fluorine content of 30% by mass or more. Or the curable composition for low-refractive-index layer formation of 2. 4). The curable composition for forming a low refractive index layer according to any one of 1 to 3 above, wherein the amount of the component (A) is 1 to 10% by mass when the total amount of components excluding the solvent is 100% by mass. object. 5). The cured film formed by hardening | curing the curable composition for low-refractive-index layer formation in any one of said 1-4. 6). 6. An antireflection film comprising the cured film as described in 5 above as a low refractive index layer.

  The curable composition for forming a low refractive index layer of the present invention has a low refractive index, and can produce a cured film having not only excellent scratch resistance and antifouling properties but also excellent wear resistance at the same time. .

2 is an IR chart of Compound 1. 1 is a ¹ H NMR chart of Compound 1. 3 is a ¹³ C { ¹ H} NMR chart of Compound 1. FIG. 4 is an IR chart of Compound 2. 2 is a ¹ H NMR chart of Compound 2. 3 is a ¹³ C { ¹ H} NMR chart of Compound 2. 4 is an IR chart of Compound 3. 2 is a ¹ H NMR chart of Compound 3. 3 is a ¹³ C { ¹ H} NMR chart of Compound 3. 4 is an IR chart of Compound 4. ¹ is a ¹ H NMR chart of Compound 4. 10 is a ¹³ C { ¹ H} NMR chart of Compound 4. FIG. 5 is an IR chart of Compound 5. ¹ is a ¹ H NMR chart of Compound 5. 3 is a ¹³ C { ¹ H} NMR chart of Compound 5.

  Hereinafter, the curable composition for forming a low refractive index layer of the present invention and the cured film obtained by curing the same will be described in detail.

I. Curable composition for forming a low refractive index layer The curable composition for forming a low refractive index layer of the present invention (hereinafter referred to as the composition of the present invention) comprises (A) a perfluoropolyether group, a polydialkylsiloxane group, and 2 It contains a compound containing one or more (meth) acryloyl groups.
The composition for forming the low refractive index layer can be formed with silica particles having cavities and a curable component, or a curable component containing fluorine, or both.

Therefore, the composition of the present invention specifically has the following constitution (embodiment).
(1) Component (A) + (B) (corresponding to Examples 1 to 9, 11 to 15) (hereinafter referred to as embodiment (1))
(2) At least one selected from the group consisting of component (A) + component (B) and (C) + component (D) (corresponding to Examples 1 to 12) (hereinafter referred to as embodiment (2))
Each component is as follows.
(A) a compound containing a perfluoropolyether group, a polydialkylsiloxane group and two or more (meth) acryloyl groups (B) containing two or more ethylenically unsaturated groups and having a fluorine content of 20% by mass or more, Compound other than (A) (C) A compound containing two or more (meth) acryloyl groups and containing no fluorine (D) A silica particle having a cavity

The composition of the present invention may further contain the following components (E) to (H) depending on the purpose in addition to the components (A) to (D).
(E) Radical polymerization initiator (F) Organic solvent (G) Solid silica particle (H) additive Hereinafter, each component will be described. First, the component (A) which is a feature of the present invention will be described, and then the rest These components will be described sequentially.

(A) Compound containing perfluoropolyether group, polydialkylsiloxane group and two or more (meth) acryloyl groups Component (A) in the composition of the present invention comprises perfluoropolyether group, polydialkylsiloxane group and It is a compound having two or more (meth) acryloyl groups. By mix | blending a component (A), the abrasion resistance of a cured film obtained, antifouling property, and also abrasion resistance can be improved.

Component (A) is not particularly limited as long as it is a compound having a perfluoropolyether group, a polydialkylsiloxane group, and two or more (meth) acryloyl groups, but has a structure represented by the following general formula (1) It is preferable that

[In Formula (1), R < ¹¹ > is a C1-C3 alkyl group each independently, and R < ¹² > is the bivalent aliphatic group, alicyclic group, or aromatic which may have a substituent. R ¹³ is each independently a single bond, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently a methylene fluoride group or a C 2-4 perfluoroalkylene group, R ¹⁷ Is a group having a (meth) acryloyl group, R ¹⁸ is a trivalent organic group which may contain a hetero atom, m is an integer of 10 to 100, and n is an integer of 5 to 50. . ]

R ¹¹ is each independently an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.
m is an integer of 10 to 100, preferably an integer of 10 to 80. If m is smaller than 10, sufficient scratch resistance may not be obtained when a coating film is formed, and if it is larger than 100, solubility in a solvent may be impaired.
n is an integer of 5 to 50, preferably an integer of 10 to 30. If n is smaller than 5, sufficient antifouling performance may not be obtained, and if it is larger than 50, solubility in a solvent may be impaired.
R ¹³ is each independently a single bond, a methylene group or an ethylene group.
R ¹⁴ and R ¹⁵ are each independently a methylene fluoride group or a C 2-4 perfluoroalkylene group, preferably a perfluoroethylene group or a perfluoropropylene group.
R ¹⁷ is a group having a (meth) acryloyl group, preferably a group having two or more (meth) acryloyl groups, and more specifically, pentaerythritol tri (meth) acrylate, dipentaerythritol. It is a group derived from a structure in which a hydroxyl group is removed from penta (meth) acrylate or tripentaerythritol heptaacrylate.

p is 1 or 2. R ¹⁸ is a p + 1 valent organic group which may contain a hetero atom, and specifically, a group derived from a structure excluding an isocyanate group of a diisocyanate compound or a triisocyanate compound.

  The mass average molecular weight of the component (A) compound is usually in the range of 2,500 to 10,000, and preferably in the range of 2,500 to 9,000. Here, the molecular weight is measured by gel permeation chromatography.

The compound of component (A) can be produced, for example, through the following production steps (a) to (d).
(A) The following general formula (Aa)
[In Formula (Aa), R ¹ and m are as defined in Formula (1). And a diisocyanate compound OCN-R ¹² -NCO (Ab) shown below (Ab)
[In formula (Ab), R ¹² is as defined in formula (1). ]
And the step of reacting.
(B) The compound obtained in (a) above and the following general formula (Ac)
_{^{HO-R 13 -R 14 -O- (}} R 15 O) n -R 14 -R 13 -OH (Ac)
[In the formula (Ac), R ¹³ , R ¹⁴ , R ¹⁵ and n are as defined in the formula (1). ] The process with which perfluoropolyetherdiol shown by this is made to react.
(C) A step of reacting the compound obtained in (b) above with a diisocyanate compound (Ad1) or a triisocyanate compound (Ad2).
(D) When the compound to be reacted in (c) is a diisocyanate compound (Ad1), a hydroxyl group and two or more (meth) acryloyl such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate When the compound (De1) having a group is reacted in (c) above is a triisocyanate compound (Ad2), hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) A step of reacting a compound (Ae2) having a hydroxyl group and one or more (meth) acryloyl groups, such as acrylate.

  More specifically, the alcohol compound (Aa) having a polydimethylsiloxane group is diluted with a solvent such as methyl ethyl ketone, or mixed with the diisocyanate compound (Ab) without solvent. After cooling to 10 to 20 ° C. in a water bath, a Lewis acid catalyst such as dibutyltin dilaurate is added and stirred at 15 to 30 ° C. for 1 to 3 hours. Thereafter, the mixture is cooled to 10 to 20 ° C. in a water bath, added with a methyl ethyl ketone solution of the diol compound (Ac) having perfluoropolyether or without solvent, and stirred at 40 to 65 ° C. for 1 to 3 hours. The reactor is cooled to 10 to 20 ° C. in a water bath, a diisocyanate compound (Ad1) or a triisocyanate compound (Ad2) is added, and the mixture is stirred at 15 to 30 ° C. for 1 to 3 hours. Manufacture by cooling to 10 to 20 ° C. in a water bath, mixing a compound (Ae1) or (Ae2) having a (meth) acryloyl group and one hydroxyl group, and reacting at 45 to 65 ° C. for 3 to 6 hours. Can do.

  As the polydialkylsiloxane monoalcohol represented by the general formula (Aa), a known compound can be used. Examples of commercially available products include Silaplane FM0411 (m = 10 to 15), FM0421 (m = 65). -75) (made by Chisso Corporation) and the like.

  Examples of the diisocyanate compound represented by the general formula (Ab) or (Ad1) include hexamethylene diisocyanate as the aliphatic diisocyanate, and isophorone diisocyanate as the alicyclic diisocyanate. Includes tolylene diisocyanate, phenylene diisocyanate, and the like. Aromatic diisocyanates are preferred. (Ab) and (Ad1) may use the same compound or different compounds.

The perfluoropolyether diol represented by the general formula (Ac) is not particularly limited as long as it is a compound having hydroxyl groups at both ends of the perfluoropolyalkylene oxide, but the terminal diol compound of perfluoropolyethylene oxide, perfluoropolypropylene Oxide terminal diol compounds are preferred.
Examples of commercially available perfluoropolyether diols represented by the above general formula (Ac) include Fluorolink D10H, Fluorolink D10H (manufactured by Solvay Solexis) and the like.

  Examples of the triisocyanate compound (Ad2) include lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2,2,1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2,2,1) heptane, 3- (3 Isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2,2,1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2 , 2,1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2,2,1) heptane, 5- (2-isocyanatoethyl) -2 -Isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2,2,1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2 , 2, 1) heptane, triphenylmethane-4,4 ', 4 "-triisocyanate, 3,5 triisocyanate methylbenzene, tris (isocyanate alkyl) isocyanurate.

The compounding amount of the component (A) in the composition of the present invention is usually in the range of 1 to 10% by mass, preferably in the range of 3 to 7% by mass when the total of the components excluding the solvent is 100% by mass. Is within. If it is less than 1% by mass, the scratch resistance and antifouling property may be lowered, and if it exceeds 10% by mass, the wear resistance may be lowered.
In addition, when the silica particle which has a component (D) cavity is not mix | blended (equivalent to the said aspect (1)), the compounding quantity of a component (A) may be small.

(B) A compound other than (A), which contains two or more ethylenically unsaturated groups and has a fluorine content of 20% by mass or more. Component (B) in the composition of the present invention has a fluorine atom in the molecule. Thereby, a cured film can be made into a low refractive index and the antifouling property of the obtained cured film can be improved.
By having an ethylenically unsaturated group capable of radical polymerization in the molecule, it can be cross-linked with other radical polymerizable compounds in the composition, and a cured film having better scratch resistance can be obtained.
If the fluorine content in the component (B) is less than 20% by mass, the resulting cured film may have a high refractive index. The upper limit of the fluorine content is 70% by mass. When the fluorine content exceeds 70% by mass, the solubility in a solvent is lowered, and the applicability of the composition may be deteriorated. For this reason, the upper limit of the fluorine content is preferably 60% by mass or less.
Examples of the component (B) include (B-1) fluorine-containing (meth) acrylic esters and (B-2) an ethylenically unsaturated group-containing fluorine-containing polymer.

(B-1) Fluorine-containing (meth) acrylic esters Specific examples of the fluorine-containing (meth) acrylic esters (B-1) include perfluoro-1,6-hexanediol di (meth) acrylate, tri (meta) ) Acrylyl heptadecafluorononenyl pentaerythritol, octafluorooctane-1,6-di (meth) acrylate, octafluorooctanediol and 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1 , 1- (Bisacryloyloxymethyl) ethyl isocyanate and the like. These can be used alone or in combination of two or more.

(B-2) Ethylenically unsaturated group-containing fluorine-containing polymer The ethylenically unsaturated group-containing fluorine-containing polymer (B-2) is a polymer of a fluorine-based olefin. By the component (B-2), the composition of the present invention exhibits basic performance as a low refractive index material for an antireflection film.
Component (B-2) can be obtained, for example, by reacting a hydroxyl group-containing fluoropolymer with a compound having a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group. By adding the component (B-2), it can be co-crosslinked with the radically polymerizable (meth) acrylic compound, and the scratch resistance is improved.

(1) A compound containing a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group As a compound containing a group capable of reacting with a hydroxyl group and an ethylenically unsaturated group, the compound contains an ethylenically unsaturated group in the molecule. The compound is not particularly limited as long as it has a functional group capable of reacting with the hydroxyl group of the fluoropolymer.
Moreover, since the curable composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
Such compounds include (meth) acrylic acid, (meth) acryloyl chloride, anhydrous (meth) acrylic acid, 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1- One kind of (bisacryloyloxymethyl) ethyl isocyanate or a combination of two or more kinds may be mentioned.
In addition, as a commercial item of (meth) acrylate which has an isocyanate group, Showa Denko Co., Ltd. brand name Karenz MOI, AOI, BEI etc. are mentioned, for example.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate methyl) cyclohexane are preferred.

As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Organic Chemical Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product name Aronix M-215, M-233, M-305, M-400 and the like can be obtained.

(2) Hydroxyl group-containing fluoropolymer The hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A structural unit represented by the following formula (3).

[In 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)]

[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

[In 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]

(I) Structural unit (a)
In the above formula (1), examples of the fluoroalkyl group represented by R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples thereof include fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); Perfluoro (alkoxyalkyl vinyl ether) s such as perfluoro (propoxypropyl vinyl ether) These may be used alone or in combination of two or more.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and it is more preferable to use these in combination.

In addition, the content rate of a structural unit (a) is 20-70 mol% when the total amount of structural unit (a)-(c) in a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content rate is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material as intended by the present invention, This is because if the content exceeds 70 mol%, the solubility of the hydroxyl group-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 more preferably 25 to 65 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Ii) Structural unit (b)
In the formula (2), examples of the alkyl group represented by R ⁴ or R ⁵ include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and lauryl group. Examples of the group include a methoxycarbonyl group and an ethoxycarbonyl group.

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

In addition, the content rate of a structural unit (b) is 10-70 mol% when the total amount of the structural units (a)-(c) in a hydroxyl-containing fluoropolymer is 100 mol%. This is because if 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, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (b) is more preferably 20 to 60 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iii) Structural unit (c)
In the formula (3), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
Moreover, as a hydroxyl-containing vinyl monomer, in addition to the above, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene Glycol (meth) acrylate or the like can be used.

The content of the structural unit (c) is 5 to 70 mol% when the total amount of the structural units (a) to (c) in the hydroxyl group-containing fluoropolymer is 100 mol%. preferable. This is because if 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, if the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (c) is more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iv) Other Structural Units The hydroxyl group-containing fluoropolymer can be configured to include a polysiloxane structure, a structure derived from a monomer having an emulsifying action, or the like as long as the effects of the present invention are not impaired.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 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 lowered. 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 composition becomes high and thin film coating may be difficult.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

  The blending amount of the component (B) in the composition of the present invention of the above aspect (1) is preferably in the range of 5 to 80% by mass when the total of components excluding the solvent is 100% by mass. More preferably, it is in the range of 10 to 80% by mass. If it is less than 5% by mass, the refractive index may be high, and if it exceeds 80% by mass, the film strength may be lowered.

  In the composition of the present invention of the above aspect (2), when the component (B) is blended, the amount of the component (B) is 100% by mass when the total of the components excluding the solvent is 100% by mass. It is preferably in the range of 5 to 80% by mass, and more preferably in the range of 10 to 80% by mass. If it is less than 5% by mass, the refractive index may be high, and if it exceeds 80% by mass, the film strength may be lowered.

(C) Compound having two or more ethylenically unsaturated groups and not containing fluorine Component (C) Compound in the composition of the present invention (C) A compound containing two or more ethylenically unsaturated groups and containing no fluorine is obtained by curing. It is a component constituting the matrix in the film, and improves the film forming property, and gives a cured film having excellent scratch resistance and organic solvent resistance. The component (C) is an optional additive component in the composition of the present invention of the above aspect (1), and is one of the components selected from the group consisting of the components (B) and (C) in the above aspect (2). One.
Component (C) is not particularly limited as long as it is a compound having two or more ethylenically unsaturated groups and no fluorine, but is a polyfunctional (meth) acrylic ester having two or more (meth) acryloyl groups. It is preferable.

Polyfunctional (meth) acrylic esters include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) Isocyanurate di (meth) acrylate, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Pentae Thritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( Hydroxyl group-containing (meth) acrylates such as (meth) acrylate, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups, oligoesters having two or more (meth) acryloyl groups in the molecule ( Mention may be made of (meth) acrylates, oligoether (meth) acrylates, oligoepoxy (meth) acrylates and the like. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable.

  Examples of commercially available products of such polyfunctional (meth) acrylic esters include ARONIX M-400, M-404, M-408, M-450, M-305, M-309, manufactured by Toagosei Co., Ltd. M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M- 245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, KAYARAD D-310, D-330, DPHA, DPCA- manufactured by Nippon Kayaku Co., Ltd. 0, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR- 268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R- 526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., Ltd. Light acrylate PE-4A, DPE-6A, DTMP-4A, etc. can be mentioned.

  When the component (C) is blended in the composition of the present invention, the blending amount is any of the above-described embodiments (1) and (2), and the total amount of the components excluding the solvent is 100% by mass. In the range of 5 to 70% by mass, the range of 10 to 60% by mass is more preferable. If it is less than 5% by mass, the curability of the coating film may be insufficient, and if it exceeds 70% by mass, the refractive index becomes high.

(D) Silica particles having cavities Component (D) in the composition of the present invention is silica particles having cavities in particles such as hollow silica particles and porous silica particles. The refractive index of the cured film obtained when the silica particles have cavities can be kept low. As the component (D), hollow silica particles are preferable because of excellent scratch resistance. The component (D) is an essential component in the composition of the present invention of the above aspect (2), but is an optional additive component in the above aspect (1).
The number average particle diameter of the hollow silica particles is preferably in the range of 1 to 100 nm, and more preferably in the range of 5 to 80 nm. The particle size is measured with a transmission electron microscope. If it is less than 1 nm, the refractive index may be high, and if it exceeds 100 nm, the transparency of the cured film may be reduced.

  As the hollow silica particles, known particles can be used, and the shape thereof is not limited to spherical but may be indefinite. Further, colloidal silica having a solid content of 5 to 40% by mass is preferable. The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and 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 of two or more as a dispersion medium.

  Examples of commercially available hollow silica particles include ELCOM JX-1009SIV, ELCOM JX-1012SIV (manufactured by Catalysts and Chemicals), and the like.

Moreover, what carried out surface treatments, such as chemical modification, on the surface of a hollow silica particle can be used, for example, the hydrolyzable silicon compound which has one or more alkyl groups in a molecule | numerator, or its hydrolyzate Etc. can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane and the like having an OH group, bis (2-hydroxyethyl) -3aminotripropylmethoxysilane and the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane and the like having a thiocyanate group 3 As thiocyanate propyltrimethoxysilane and the like having an epoxy group (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like having a thiol group 3 -Mercaptopropyltrimethoxy Sisilane etc. can be mentioned. A preferred compound is 3-mercaptopropyltrimethoxysilane. It is also preferable to modify with a compound described in JP-A-9-100111.

  When component (D) is blended in the composition of the present invention (in any of the above embodiments (1) and (2)), the total amount of the components excluding the solvent is 100% by mass. Sometimes it is preferably in the range of 5 to 80% by mass, more preferably in the range of 5 to 70% by mass. If it is less than 5% by mass, the refractive index may be high, and if it exceeds 80% by mass, the film may be brittle. In addition, the quantity of the particle | grains of a component (D) means the amount of solid content, and when the particle | grains are used with the form of solvent dispersion | distribution sol, the quantity of a solvent is not included in the compounding quantity.

(E) Radical polymerization initiator Examples of the radical polymerization initiator (E) used in the present invention include a compound that thermally generates active radical species (thermal polymerization initiator), and an active radical upon irradiation with radiation (light). Commonly used compounds such as seed generating compounds (radiation (light) polymerization initiators) can be mentioned, and radiation (light) polymerization initiators are preferred.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane -1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether , Benzoy Ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) ) -2,4,4-trimethylpentylphosphie Oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like.

  Examples of commercially available radiation (photo) polymerization initiators include Irgacure 127, 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, and CG24 manufactured by Ciba Specialty Chemicals. -61, Darocur 1116, 1173, Lucylin TPO manufactured by BASF, Ubekrill P36 manufactured by 8893UCB, Ezacure KIP150, KIP65LT, KIP100F manufactured by Fratelli Lamberti, KT37, KT55, KTO46, KIP75 / B, and the like.

  The blending amount of the component (F) in the composition of the present invention is preferably in the range of 0.01 to 20% by mass when the total of the components excluding the solvent is 100% by mass. More preferably, it is in the range of -10 mass%. If it is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 20% by mass, the hardness of the coating film may be impaired.

(F) Organic solvent The composition of the present invention is usually diluted with an organic solvent to adjust the thickness of the coating film. For example, the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.

  Examples of the organic solvent (F) 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, ethyl lactate and γ-butyrolactone , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples include amides such as N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.

  The total amount of the organic solvent (F) in the composition of the present invention is preferably in the range of 50 to 10,000 parts by mass when the total of components excluding the solvent is 100 parts by mass. In addition, the organic solvent in the dispersion liquid of the silica particle (D) which has the said cavity, and the below-mentioned (G) solid silica particle can also be brought in in the composition of this invention. The blending amount of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the composition, etc. in consideration of the organic solvent derived from component (D) and / or (G).

(G) Solid silica particles In the composition of the present invention, together with the silica particles having the above (D) cavities (in the case of the above aspects (1) and (2)) or alone (in the case of the aspect (1)) (G) Solid silica particles may be blended. Although solid silica particles are inferior to solid silica particles in refractive index, they can impart scratch resistance to the resulting cured film.
As the solid silica particles, known ones can be used, and those having the same number average particle diameter as the silica particles having the above-mentioned (D) cavities are preferable. It may be a fixed form. Further, colloidal silica having a solid content of 5 to 40% by mass is preferable.

  Specific examples of commercially available solid silica particles include, for example, colloidal silica manufactured by Nissan Chemical Industries, Ltd. Trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-ST-S, MEK-ST- L, IPA-ZL, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL etc. are mentioned.

  (G) The solid silica particles may be surface-modified similarly to the (D) hollow silica particles.

  The blending amount of the component (G) in the composition of the present invention is preferably within the range of 5 to 80% by mass, and is preferably 5 to 70% by mass when the total of the components excluding the solvent is 100% by mass. It is more preferable to be within the range. If it is less than 5% by mass, the film hardness may be low, and if it exceeds 80% by mass, the film may be brittle. The amount of the component (G) particles means solid content, When used in the form of a solvent-dispersed sol, the blending amount does not include the amount of solvent.

(H) Additive In the composition of the present invention, inorganic particles other than silica particles, a photosensitizer, a thermal polymerization initiator, a polymerization inhibitor, and a polymerization initiation aid are within the range that does not impair the purpose and effect of the present invention. , Leveling agents, wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, pigments, dyes, slip agents, etc. .
In particular, the inorganic particles are effective for improving the coating strength, and when added, the number average particle size is preferably in the range of 1 to 100 nm, and spherical, beaded, amorphous particles can be used, and Porous and hollow particles having voids in the internal structure can also be used. As the inorganic particles that can be used, inorganic oxides or fluorides are preferable, and examples thereof include alumina, titania, zirconia, and magnesium fluoride. Moreover, the surface of these inorganic particles may be surface-modified with an arbitrary organic group, and by being modified with a (meth) acrylic group, compatibility with the curable composition is improved, and other properties at the time of curing It becomes possible to co-crosslink with the curable composition, and it is possible to improve the scratch resistance of the cured film.

  The thermal polymerization initiator is a compound that generates active species by heat, and examples thereof include a thermal radical generator that generates radicals as active species. Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert-butyl peroxide , Tert-butyl hydroperoxide, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. The combination of the above can be mentioned.

The curing conditions of the composition of the present invention are not particularly limited. For example, when active energy rays are used, it is preferable to set the irradiation light amount to a value within the range of 0.01 to 10 J / cm ^2. .
This is because when the irradiation light quantity is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the irradiation light quantity exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.

II. Cured film and antireflection film The cured film of the present invention is characterized by curing the composition of the present invention.
The cured film of the present invention has a low refractive index, is excellent in abrasion resistance and antifouling properties, and is also excellent in abrasion resistance, and is useful as a low refractive index layer which is the outermost layer of the antireflection film.

  The refractive index of the cured film of the present invention is usually 1.44 or less, preferably 1.40 or less, more preferably 1.38 or less.

  When the cured film of the present invention is used as the low refractive index layer of the antireflection film, the structure of the antireflection laminate, that is, the base material, the layer structure, the material of each layer, the production method, the film thickness, and the like are known. Therefore, detailed description is omitted here.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Synthesis Example 1: Synthesis of Compound 1
[Wherein, Me represents a methyl group, PETA represents a group derived from pentaerythritol triacrylate, m is 10 to 15, and n is 10 to 15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT) (0.024 g, 0.1 mmol), poly Dimethylsiloxane monool (manufactured by Chisso Corporation, Silaplane FM0411) (23.80 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100) (4.14 g, 23.8 mmol) and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) (27.94 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the mixture was stirred at room temperature for 1.5 to 2.0 hours. Next, the reaction mixture was cooled in a water bath, and methyl ethyl ketone (35.70 g) and perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) (35.70 g) were added thereto, and then the temperature was raised to 60 ° C. And heated at the same temperature for 2 hours. The reaction mixture was cooled in a water bath, and triisocyanate (Sumidule N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) (12.01 g, 23.8 mmol) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added thereto. And stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) (24.35 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added and the temperature was raised to 60 ° C. The mixture was heated and heated at the same temperature for 4 hours to obtain a methyl ethyl ketone solution of Compound 1 represented by the above structural formula (200 g).

The resulting IR chart of Compound ^1, 1 H NMR ^chart, showing the 13 ^C {1 H} NMR chart in FIGS 1-3.

Synthesis Example 2: Synthesis of Compound 2
[Wherein, Me represents a methyl group, DPPA represents a group derived from dipentaerythritol pentaacrylate, m is 10 to 15, and n is 10 to 15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT) (0.024 g, 0.1 mmol), poly Dimethylsiloxane monool (manufactured by Chisso Corporation, Silaplane FM0411) (18.57 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100) (3.23 g, 18.6 mmol) and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) (21.80 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the mixture was stirred at room temperature for 1.5 to 2.0 hours. Next, the reaction mixture was cooled in a water bath, and methyl ethyl ketone (27.86 g) and perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) (27.86 g) were added thereto, and the temperature was raised to 60 ° C. And heated at the same temperature for 2 hours. The reaction mixture was cooled in a water bath, and triisocyanate (Sumidule N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) (9.37 g, 18.6 mmol) diluted with methyl ethyl ketone to a solid concentration of 50% by mass was added thereto. And stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and dipentaerythritol penta / hexaacrylate (manufactured by Toagosei Co., Ltd .: Aronix M403) (40.97 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added thereto. The mixture was heated to 60 ° C. and heated at the same temperature for 4 hours to obtain a methyl ethyl ketone solution of compound 2 represented by the above structural formula (200 g).

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 2 are shown in FIGS.

Synthesis Example 3: Synthesis of Compound 3
[Wherein, Me represents a methyl group, PETA represents a group derived from pentaerythritol triacrylate, m is 65 to 75, and n is 10 to 15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT) (0.024 g, 0.1 mmol), poly Dimethylsiloxane monool (manufactured by Chisso Corporation, Silaplane FM0421) (60.96 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100) (2.12 g, 11.9 mmol) and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) (63.08 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the mixture was stirred at room temperature for 1.5 to 2.0 hours. Next, the reaction mixture was cooled in a water bath, and methyl ethyl ketone (18.29 g) and perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) (18.29 g) were added thereto, and the temperature was raised to 60 ° C. And heated at the same temperature for 2 hours. The reaction mixture was cooled in a water bath, and triisocyanate (Sumidule N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) (6.15 g, 12.2 mmol) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added thereto. And stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) (12.47 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added and the temperature was raised to 60 ° C. The mixture was heated and heated at the same temperature for 4 hours to obtain a methyl ethyl ketone solution of compound 3 represented by the above structural formula (200 g).

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained Compound 2 are shown in FIGS.

Synthesis Example 4: Synthesis of Compound 4
[Wherein, Me represents a methyl group, DPPA represents a group derived from dipentaerythritol pentaacrylate, m is 65 to 75, and n is 10 to 15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals, Yoshinox BHT) (0.024 g, 0.1 mmol), poly Dimethylsiloxane monool (manufactured by Chisso Corporation, Silaplane FM0421) (53.28 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100) (1.85 g, 10.6 mmol) and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) (55.13 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the mixture was stirred at room temperature for 1.5 to 2.0 hours. Next, the reaction mixture was cooled in a water bath, and methyl ethyl ketone (15.98 g) and perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) (15.98 g) were added thereto, and then the temperature was raised to 60 ° C. And heated at the same temperature for 2 hours. The reaction mixture was cooled in a water bath, and triisocyanate (Sumidule N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) (5.38 g, 10.7 mmol) diluted with methyl ethyl ketone to a solid concentration of 50% by mass was added thereto. And stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and dipentaerythritol penta / hexaacrylate (Aronix M403, manufactured by Toagosei Co., Ltd.) (23.51 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added thereto. The mixture was heated to 60 ° C. and heated at the same temperature for 4 hours to obtain a methyl ethyl ketone solution of compound 4 represented by the above structural formula (200 g).

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 4 are shown in FIGS.

Synthesis Example 5 Synthesis of Compound 5
[Wherein, m = 65 to 75, and n = 10 to 15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical, Yoshinox BHT) (0.024 g, 0.1 mmol), perfluoropoly Ether diol (manufactured by Solvay Solexis, Fluorolink D10H) (18.87 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethane, TOLDY-100) (4.38 g, 25.2 mmol) and methyl ethyl ketone (Maruzen) Petrochemical Co., Ltd.) (23.25 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and polydimethylsiloxane monoalcohol (Chisso Corp., Silaplane FM0421) (62.88 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by mass was added thereto using a dropping funnel. Added. This was heated up to 60 degreeC and heated for 2 hours. Next, dipentaerythritol pentaacrylate (manufactured by Toagosei Co., Ltd., Allotonics M403) (13.87 g) was added using a dropping funnel. This was heated to 60 ° C. and heated for 4 hours. Thus, a methyl ethyl ketone solution (200 g) of compound 2 represented by the above chemical structural formula was obtained.

An IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 2 are shown in FIGS.

Production Example 1 Production of Ethylenically Unsaturated Group-Containing Fluoropolymer Synthesis of Hydroxyl-Containing Fluoropolymer A stainless steel autoclave with an internal volume of 1.0 liter with a magnetic stirrer was sufficiently substituted with nitrogen gas, and then 600 g of ethyl acetate 138.5 g perfluoro (propyl vinyl ether), 37.5 g ethyl vinyl ether, 45.9 g hydroxyethyl vinyl ether, 1.5 g lauroyl peroxide, azo group-containing polydimethylsiloxane (VPS1001 (trade name), Wako Pure Chemical Industries, Ltd.) 9.0 g) and 45 g of a nonionic reactive emulsifier (ER-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), cooled to -50 ° C. with dry ice-methanol, and then again with nitrogen gas The oxygen inside was removed.

Next, 85.9 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 55 ° C. was 4.1 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 2.0 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 30.0%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 250 g of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer.

In a 1-liter separable flask equipped with a magnetic stirrer, a glass condenser and a thermometer, 50.0 g of the hydroxyl group-containing fluoropolymer obtained above and 2,6-di-t- 0.01 g of butylmethylphenol and 359 g of methyl isobutyl ketone (MIBK) were charged and stirred at 20 ° C. until the hydroxyl group-containing fluoropolymer 1 was dissolved in MIBK and the solution became transparent and uniform.
Next, 13.4 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 55. A MIBK solution of an ethylenically unsaturated group-containing fluoropolymer was obtained by maintaining the temperature at 65 ° C. and continuing stirring for 5 hours.
2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by mass.

Production Example 2:
Manufacture of specific organic compound (S1) (Silica particle surface modifier) In dry air, 60.0 parts of isophorone diisocyanate is stirred in a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate. While dropping at 50 ° C. over 1 hour, the mixture was stirred at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, it is pentaerythritol having a hydroxyl group that is involved in the reaction. (Only triacrylate.) After adding 202.0 parts dropwise at 30 ° C. over 1 hour, specific organic compound (S1) was obtained by heating and stirring at 60 ° C. for 3 hours.
In the infrared absorption spectrum of the product, the absorption peak at 2550 cm ⁻¹ characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm ⁻¹ characteristic for the isocyanate group disappear, and [−O—C (= O) -NH-] group and [-S-C (= O) -NH-] peak characteristic 1720 cm ^-1 to the carbonyl in the group the peak and acryloyl groups characteristic 1660 cm ^-1 - click is observed And a specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group is formed. Showed that.

Production Example 3:
Production of acrylic modified hollow silica particles 3.0 parts of the specific organic compound (S1) synthesized in Production Example 2, 137 parts of hollow silica particles (JX1009SIV, methyl isobutyl ketone sol, manufactured by Catalyst Chemical Industries) (solid content 30.1 parts) A mixture of 0.1 part of ion-exchanged water and 0.01 part of 0.05 mol / L dilute sulfuric acid was stirred at 80 ° C. for 3 hours, and then the particle dispersion D- was obtained using 1.4 parts of orthoformate methyl ester. 1 was obtained. It was 25 mass% when solid content of D-1 was calculated | required.
The average particle diameter of the silica-based particles was 50 nm. Here, the average particle diameter was measured with a transmission electron microscope.

<Manufacture of curable composition>
Example 1
100 g of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer produced in Production Example 1 (15 g as the solid content of component (B-2)), pentaerythritol triacrylate (PET-30, manufactured by Nippon Kayaku) ( Component (C)) 7 g, hollow silica particle MIBK sol (ELCOM JX1009SIV, produced by catalytic conversion) 200 g (50 g as the solid content of component (D)), triacryloylheptadecafluorononenyl pentaerythritol (LINC-3A, Manufactured by Kyoeisha Chemical Co., Ltd.) ((Component (B-1)) 20 g, as a photopolymerization initiator, 2-hydroxy-1- {4- [2- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} 2-methyl-propan-1-one (Irgacure 127, manufactured by Ciba Specialty Chemicals) (component (E)) 3 g, 3 g of Compound 1 (component (A)) synthesized in Synthesis Example 1 and 2117 g of MIBK were charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour to obtain a uniform curable composition. The solid content concentration determined by the method of Production Example 1 was 4.0% by mass.

Examples 2-16 and Comparative Examples 1-7
Each curable composition was obtained like Example 1 except having set it as the composition shown to the following Table 1-1 to 1-3.

<Production of cured film>
(1) Preparation of base material for curable composition coating On the TAC film (thickness 50 μm), the prepared composition for hard coat layer was applied with a wire bar coater to a film thickness of 6 μm. The film was dried at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 300 mJ / cm ² using a high-pressure mercury lamp in the air to prepare a curable composition coating substrate.

(2) Production of Low Refractive Index Material Each curable composition obtained in the above examples and comparative examples was hard coated on a curable composition coating substrate obtained above using a wire bar coater. The film was coated to a thickness of 0.1 μm and dried at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 600 mJ / cm ² using a high-pressure mercury lamp under a nitrogen stream to produce an antireflection film.

<Evaluation of physical properties of cured film>
Each cured film obtained above was measured or evaluated for refractive index, scratch resistance, abrasion resistance and antifouling property. The results are shown in Tables 1-1 to 1-3.

(1) Refractive index The back surface of the antireflection film is coated with black spray, and a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, manufactured by Hitachi, Ltd.) ), The reflectance was measured and evaluated from the substrate side in the wavelength range of 340 to 700 nm. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength is measured using the reflectance of the aluminum deposited film as a reference (100%), and from the reflectance of light at a wavelength of 550 nm, The refractive index was calculated.

(2) Scratch resistance (steel wool resistance)
The obtained cured film was attached with steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.). The surface was repeatedly rubbed 10 times under a load of 200 g, the presence or absence of scratches on the surface of the cured film was visually confirmed, and evaluated according to the following evaluation criteria. The results are shown in Tables 1-1 to 1-3.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or slight thin scratches are observed on the cured film.
Δ: Streaky scratches are observed on the entire surface of the cured film.
X: Peeling of the cured film occurs.

(3) Abrasion resistance (cloth)
The obtained cured film was attached with Bencot M-3 (manufactured by Asahi Kasei) to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded under the condition of a load of 500 g. By rubbing repeatedly, the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Tables 1-1 to 1-3.
A: The cured film is not damaged.
○: A slight color change is observed in the cured film.
Δ: A strong color change is observed in the cured film.
X: Scratches and peeling occur in the cured film.

(4) Abrasion resistance (isopropanol + cloth)
The obtained cured film was attached to a Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.) with Bencot M-3 (Asahi Kasei Co., Ltd.) impregnated with isopropanol. Scratching was repeated 50 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed and evaluated according to the following evaluation criteria. The results are shown in Tables 1-1 to 1-3.
A: The cured film is not damaged.
○: A slight color change is observed in the cured film.
Δ: A strong color change is observed in the cured film.
X: Scratches and peeling occur in the cured film.

(5) Antifouling (oil marker wiping)
About 0.25 cm ² (0.5 cm × 0.5 cm) of the surface of the obtained antireflection film is coated with an oil-based dye ink type marking pen (manufactured by Zebra Co., Ltd., trade name: McKee) without any gaps. After naturally drying for 30 seconds, the portion coated with the marker is wiped with a non-woven fabric (Bencot). Further, the same portion was coated with an oil marker, and wiping was repeated in the same manner until the oil ink could not be wiped off. The number of repetitions in which the oil-based ink could be wiped was counted and evaluated according to the following evaluation criteria. The results are shown in Tables 1-1 to 1-3.
◎: Can be wiped repeatedly 5 times or more ○: Can be wiped 3 to 4 times △: Can be wiped 1 to 2 times ×: Can not be wiped once

Each component in the above Tables 1-1 to 1-3 represents the following.
Pentaerythritol triacrylate: PET-30, Nippon Kayaku Co., Ltd.
Ethylenically unsaturated group-containing fluoropolymer: produced in Production Example 1 Fluorine acrylate: triacryloylheptadecafluorononenylpentaerythritol, product name: LINC-3A, Kyoeisha Chemical Co., Ltd.
Hollow silica particles: ELCOM JX-1009 SIV, Catalyst Chemical Industry Co., Ltd., average particle size 50 nm, those modified with acrylic in Production Example 3 Solid silica particles: MEK-ST-L, Nissan Chemical Co., Ltd., average particle size 40nm
Compound 1: synthesized in Synthesis Example 1 Compound 2: synthesized in Synthesis Example 2 Compound 3: synthesized in Synthesis Example 3 Compound 4: synthesized in Synthesis Example 4 Irgacure 127: manufactured by Ciba Specialty Chemicals
Silaplane FM0421: manufactured by Chisso Corporation, polydimethylsiloxane monool Sailorplane FM0721: manufactured by Chisso Corporation, methacryloxy group-containing polydimethylsiloxane TEGO Rad2500: manufactured by Tego Corporation, polyether alkyl group-containing silicone acrylate Optool DAC: manufactured by Daikin Corporation Perfluoropolyether group-containing urethane acrylate

From the results of Tables 1-1 to 1-3, from the curable compositions of Examples containing a compound having a perfluoropolyether group and a dialkylsiloxane group, any of scratch resistance, abrasion resistance, and antifouling property can be obtained. It can be seen that an excellent cured film can be obtained.
On the other hand, in the comparative example containing a conventional slip agent compound, the refractive index is the same as that of the example, but it is inferior in all of scratch resistance, abrasion resistance and antifouling property. In Comparative Example 5, a compound having no siloxane group and having a perfluoropolyether group (Optool DAC) and a compound having a polydimethylsiloxane monool (Silaplane FM0421) were blended. It can be seen that both the wear resistance and antifouling property are inferior to those of the examples.

According to the present invention, a cured film having a low refractive index, excellent scratch resistance (steel wool resistance), antifouling property (oil-based marker wiping property), and excellent wear resistance can be produced.
The cured film obtained by the present invention is useful as a low refractive index layer of an antireflection film.

Claims (6)

A curable composition for forming a low refractive index layer containing the following components (A) and (B).
(A) Compound represented by the following general formula (1)
[In Formula (1), R < ¹¹ > is a C1-C3 alkyl group each independently, and R < ¹² > is the bivalent aliphatic group, alicyclic group, or aromatic which may have a substituent. R ¹³ is each independently a single bond, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently a methylene fluoride group or a C 2-4 perfluoroalkylene group, R ¹⁷ Is a group having a (meth) acryloyl group, R ¹⁸ is a p + 1 valent organic group which may contain a hetero atom, m is an integer of 10 to 100, and n is an integer of 5 to 50. , P is 1 or 2. ]
(B) Compounds other than the above (A), containing two or more ethylenically unsaturated groups and having a fluorine content of 20% by mass or more A curable composition for forming a low refractive index layer, comprising at least one selected from the group consisting of the following component (A), components (B) and (C), and component (D).
(A) a compound represented by the following general formula (1),
[In Formula (1), R < ¹¹ > is a C1-C3 alkyl group each independently, and R < ¹² > is the bivalent aliphatic group, alicyclic group, or aromatic which may have a substituent. R ¹³ is independently a single bond, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently methylene fluoride or a C 2-4 perfluoroalkylene group, and R ¹⁷ is A group having a (meth) acryloyl group, R ¹⁸ is a p + 1 valent organic group which may contain a hetero atom, m is an integer of 10 to 100, and n is an integer of 5 to 50; p is 1 or 2. ]
(B) Compound other than (A) containing two or more ethylenically unsaturated groups and having a fluorine content of 20% by mass or more (C) Compound having two or more ethylenically unsaturated groups and containing no fluorine ( D) Silica particles having cavities   The (B) contains a polymer having two or more ethylenically unsaturated groups, a number average molecular weight measured by gel permeation chromatography of 5,000 or more, and a fluorine content of 30% by mass or more. 3. The curable composition for forming a low refractive index layer according to 1 or 2.   The amount of said component (A) is 1-10 mass% when the sum total of the component except a solvent is 100 mass%, The low refractive index layer formation of any one of Claims 1-3 Curable composition.   The cured film formed by hardening | curing the curable composition for low-refractive-index layer formation of any one of Claims 1-4. An antireflection film comprising the cured film according to claim 5 as a low refractive index layer.