KR101569213B1 - Compound having polydialkylpolysiloxane group perfluoropolyether group urethane group and methacryloyl group curable composition containing the same and cured film - Google Patents

Abstract

An object of the present invention is to provide a compound represented by the following formula (1) and a curable composition containing the same.

≪ Formula 1 >

[Formula (I) of the, R ¹ is an alkyl group having 1 to 3, R ² is a have also a divalent aliphatic group optionally substituted, alicyclic group or aromatic group, R ³ represents a single bond, methylene group or ethylene group, R ⁴ and R ⁵ is a methylene fluoride or a perfluoroalkylene group having 2 to 4 carbon atoms, R ⁷ is a group having at least one (meth) acryloyl group, R ⁸ is a group capable of having a substituent, p M is an integer of 10 to 100, n is an integer of 5 to 50, and p is 1 or 2,

A curable composition, a cured film, a polydialkylpolysiloxane group, a perfluoropolyether group, a urethane group, and a (meth) acryloyl group

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cured product comprising a compound having a poly (dialkylpolysiloxane group), a perfluoropolyether group, a urethane group and a (meth) acryloyl group, GROUP, CURABLE COMPOSITION CONTAINING THE SAME, AND CURED FILM}

The present invention relates to a compound having a polydialkylpolysiloxane group, a perfluoropolyether group, a urethane group and a (meth) acryloyl group, a curable composition containing the same, and a cured film.

BACKGROUND OF THE INVENTION [0002] In recent years, there has been a growing demand for plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, The present invention relates to a coating material for preventing scratches or contamination of various substrate surfaces such as glass, slate and the like, and a coating material for antireflection coating, There is a demand for a curable composition capable of forming an excellent cured film having both slip property, low curling property, adhesion property, transparency, chemical resistance and appearance of a coating film surface.

Various compositions have been proposed in order to satisfy such a demand. However, it has been proposed that a curable composition having excellent coating properties and having high hardness and scratch resistance when cured, excellent in transparency and excellent in antifouling property It is a reality that we have not gotten yet.

As a method for imparting antifouling property, for example, a curable composition comprising a polysiloxane having a (meth) acryloyl group is described in Patent Document 1 below, but there is room for further improvement from the viewpoint of oily marker removal .

The following Patent Document 2 discloses a composition for forming an antireflection film which can improve the slip property of the antireflection film surface, is soluble in a non-fluorine general-purpose solvent, and is easy to form a thin film. The composition for forming an antireflection film is a composition comprising a reactive surface modifier (I) and an antireflection film material (II), wherein the reactive surface modifier (I) is (A) a triisocyanate obtained by trimerizing a diisocyanate, (B-1) a perfluoropolyether having at least one active hydrogen, and (B-2) an active hydrogen-containing compound comprising at least two active hydrogen- And a monomer having a self-crosslinkable functional group. The addition of such a reactive surface modifier (I) improves the surface properties of the antireflection film, particularly the surface slip property (lowering of friction coefficient), surface hardness, abrasion resistance, chemical resistance, decontamination property, water repellency, oil repellency, , It is described that the modified surface properties can be imparted to the surface of the original coated film. The antireflection film material (II) combined with the reactive surface modifier (I) is for forming a low refractive index layer.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2005-36018

[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2006-37024

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a compound capable of imparting excellent transparency and antifouling property, particularly, oily marker removing property and scratch resistance to the obtained cured film.

It is also an object of the present invention to provide a curable composition for forming a hard coat layer having excellent transparency, scratch resistance and antifouling property, particularly excellent fingerprint removing property and fingerprint visibility.

In order to achieve the above object, the present inventors conducted intensive studies and found that a compound containing a polydialkylpolysiloxane group, a perfluoropolyether group, a urethane group and a (meth) acryloyl group has excellent transparency, , In particular, can remove the oil-based markers and provide scratch resistance.

The present inventors have also found that a curable composition containing (B) a compound having two or more polymerizable unsaturated groups is obtained by reacting (A) a polydialkylsiloxane group, a perfluoropolyether group, a urethane bond and a (meth) acryloyl group, , It is found that a cured film capable of satisfying the above-mentioned various characteristics can be obtained.

(A) a curable compound having a polysiloxane structure and a perfluoropolyether structure and (D) a (meth) acrylate having a perfluoropolyether structure, and (B) a curing compound having two or more polymerizable unsaturated groups in the molecule. It has been found that a cured film satisfying the above-mentioned various characteristics and having excellent fingerprint removing property and fingerprint visibility can be obtained by adding a curing compound containing a diol and a perfluoropolyether structure in combination .

That is, the present invention provides the following compounds and curable compositions.

1. A compound represented by the following formula (1).

Wherein R ¹ is independently an alkyl group having 1 to 3 carbon atoms, R ² is a divalent aliphatic group, alicyclic group or aromatic group which may have a substituent, R ³ is independently a single bond, a methylene group Or an ethylene group, R ⁴ and R ⁵ are each independently methylene fluoride or a perfluoroalkylene group having 2 to 4 carbon atoms, R ⁷ is a group having at least one (meth) acryloyl group, R ⁸ is a substituent M is an integer of 10 to 100, n is an integer of 5 to 50, and p is 1 or 2,

2. The compound according to the above 1, wherein R < ² > is a divalent aromatic group having a substituent.

3. The compound according to the above 1, wherein p is 1, and R < ⁸ >

Wherein R ²⁸ is a methyl group or an ethyl group, s is an integer of 0 to 2, and *

4. The compound according to the above 1, wherein p is 2, and R < ⁸ >

[Wherein R ⁶ represents an alkylene group having 2 to 10 carbon atoms and * represents a bonding site]

5. A composition comprising the following components (A) and (B):

(A) a compound represented by the formula (1) described in any one of the above 1 to 4

(B) a compound having two or more polymerizable unsaturated groups in the molecule other than the above (A)

≪ / RTI >

6. The curable composition according to the above 5, further comprising (C) particles mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium .

7. The curable composition according to 5 above, further comprising (D) a compound represented by the following formula (10).

R ¹⁶ -R ¹³ -R ¹⁴ O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -R ¹⁶

[R ¹³ are each a single bond, each independently, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently a fluorinated methylene or a carbon number of perfluoroalkyl of 2 to 4 groups, R ¹⁶ is a urethane bond and a (meth) An acryloyl group, and t is an integer of 5 to 50,

8. The curable composition as described in 5 above, wherein the amount of the compound (A) is in the range of 0.01 to 5% by weight based on 100% by weight of the total of the composition excluding the solvent.

9. The curable composition according to the above 6, wherein the component (C) is a particle surface-treated with an organic compound (Cb) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule.

10. The curable composition according to the above-mentioned 5, further comprising (E) a radical polymerization initiator.

11. The curable composition according to the above 5, further comprising (F) an organic solvent.

12. The curable composition as described in 5 above, which is used for forming a hard coating.

By adding the compound of the present invention to the curable composition, the resulting cured film can impart excellent transparency, antifouling property and scratch resistance. In addition, it may be possible to remove the marker.

According to the present invention, it is possible to produce a composition for hard coating excellent in transparency, scratch resistance and antifouling property. Further, it is possible to produce a composition for hard coating excellent in fingerprint removal property and fingerprint visibility.

Hereinafter, the present invention will be described in detail.

I. Compound (I)

The compound of the present invention has a structure represented by the following formula (1).

≪ Formula 1 >

In the general formula (1), R ¹ is independently an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

R ² is a divalent aliphatic group, alicyclic group or aromatic group which may have a substituent, preferably a divalent aromatic group which may have a substituent.

R ³ each independently represents a single bond, a methylene group or an ethylene group.

R ⁴ and R ⁵ are each independently methylene fluoride or perfluoroalkylene group having 2 to 4 carbon atoms, preferably methylene fluoride, perfluoroethylene group or perfluoropropylene group.

R ⁷ is a group having at least one (meth) acryloyl group, and preferably a hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) And a group excluding the hydroxyl group of tripentaerythritol (meth) acrylate.

R ⁸ is a p + 1 -valent organic group which may have a substituent or may contain a heteroatom, and p is 1 or 2.

When p is 1, R ⁸ preferably has a structure represented by the following formula.

In the formula, R ²⁸ represents a methyl group or an ethyl group, s represents an integer of 0 to 2, and * represents a bonding site.

R ⁸ is also preferably a group represented by the following formula.

In the formula, R ⁶ is an alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 4 to 7 carbon atoms, and * indicates a bonding site.

m is an integer of 10 to 100, preferably an integer of 10 to 80; When m is less than 10, sufficient scratch resistance may not be obtained when a coating film is formed, and when it is more than 100, there is a possibility that the solubility in a solvent is impaired.

n is an integer of 5 to 50, preferably an integer of 10 to 30. If n is less than 5, there is a possibility that a sufficient antifouling performance may not be obtained, and if it is more than 50, the solubility in a solvent may be impaired.

More specifically, it is preferable that the compound of the present invention has a structure represented by the following formulas (1-1) and (1-2).

Compound (1-1)

(1-1)

In the formula (1-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ²⁸ , m, n and s are as defined above, R ²² is a methyl group or an ethyl group, r is an integer of 0 to 2 to be.

R ²⁷ is a group having at least one (meth) acryloyl group, and preferably at least one of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) Or a group excluding a hydroxyl group of tripentaerythritol (meth) acrylate.

The compound (1-2)

(1-2)

In the formula (1-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , m and n are as defined above.

The molecular weight of the compound of the present invention is usually in the range of 2,500 to 10,000, preferably in the range of 2,500 to 9,000. Here, the molecular weight is measured by a gel permeation chromatography method.

The compound (1-1) or (1-2) of the present invention can be produced, for example, by the following production method.

(a) a step of reacting a diisocyanate represented by the following formula (4) with a polydialkylsiloxane monoalcohol represented by the following formula (3)

[Wherein R ² is as defined above]

[Wherein R ¹ and m are as defined above]

(b) reacting a perfluoropolyether diol represented by the following formula (2)

HO-R ³ -R ⁴ -O- (R ⁵ O) _n -R ⁴ -R ³ -OH

[Wherein R ³ , R ⁴ , R ⁵ and n are as defined above]

(c) reacting a diisocyanate compound or a triisocyanate compound (5), and

(d) reacting a (meth) acrylate represented by the following formula (6)

.

R ⁷ -OH

[Wherein R ⁷ is as defined above]

More specifically, the alcohol compound (3) having a polydialkylsiloxane group is diluted with a solvent such as methyl ethyl ketone or is mixed with the diisocyanate compound (4) in the absence of a solvent. After cooling to 10 to 20 占 폚 in a water bath, Lewis acid catalyst such as dibutyltin dilaurate is added and the mixture is stirred at 15 to 30 占 폚 for 1 to 3 hours. Thereafter, the mixture is cooled in a water bath at 10 to 20 占 폚, added with a methyl ethyl ketone solution of a diol compound (2) having perfluoropolyether or a solvent, and stirred at 40 to 65 占 폚 for 1 to 3 hours. The reactor is cooled to 10 to 20 DEG C in a water bath, and a diisocyanate compound or triisocyanate compound (5) is added thereto, followed by stirring at 15 to 30 DEG C for 1 to 3 hours. The mixture is cooled in a water bath at 10 to 20 占 폚, and the compound (6) having at least one (meth) acryloyl group and one hydroxyl group is mixed and reacted at 45 to 65 占 폚 for 3 to 6 hours.

Specific examples of the diisocyanate represented by Formula 4 include hexamethylene diisocyanate as the aliphatic diisocyanate, isophorone diisocyanate as the alicyclic diisocyanate, and aromatic diisocyanates such as methaphenylenediisocyanate Tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolylene diisocyanate, 1,4-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate and 2,7-naphthalene diisocyanate. And preferably an aromatic diisocyanate.

As polydialkylsiloxane monoalcohols represented by the above formula (3), known compounds can be used. Examples of commercially available polydialkylsiloxane monoalcohols include Siilaprene FM0411 (m = 10 to 15), FM0421 (m = 65 to 75) And the like.

The perfluoropolyether diol represented by the above-mentioned general formula (2) is not particularly limited as long as it is a compound having a hydroxyl group at both terminals of the perfluoropolyalkylene oxide. However, the terminal diol compound of perfluoropolyethylene oxide, A terminal diol compound of propylene oxide is preferred.

Examples of commercially available perfluoropolyether diols represented by the above formula (2) include Fluorolink D10H (manufactured by Sorvex Solexis) and the like.

When the isocyanate compound (5) used in the step (c) is a diisocyanate compound, the compound described in the above formula (4) can be mentioned. When the isocyanate compound (5) used in the step (c) is a triisocyanate compound, it is preferable to use 1,4,8-triisocyanate octane, triphenylmethane-4,4 ' 6-triisocyanate toluene, isocyanuric acid trisisocyanate hexyl, and the like.

Examples of the polyfunctional (meth) acrylate represented by the above formula (6) include pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. In addition, examples of the compound represented by the above formula (6) include (meth) acrylic acid and hydroxyethyl (meth) acrylate.

II. Curable composition

The curable composition of the present invention (hereinafter referred to as " composition of the present invention ") is a composition composed of the following components (A) to (G). Of these, (A) and (B) are essential components, and (C) to (G) are optional components that can be added as needed.

(A) the compound of the present invention represented by the above formula (1)

(Hereinafter referred to as a "compound containing a polyfunctional polymerizable unsaturated group") having two or more polymerizable unsaturated groups in the molecule (other than the above (A), (Cc) and (D)

(C) a compound selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium which may be combined with an organic compound (Cb) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule (Hereinafter referred to as " particles ") having an oxide of at least one element as a main component,

(D) a compound represented by the following formula (10)

≪ Formula 10 >

R ¹⁶ -R ¹³ -R ¹⁴ O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -R ¹⁶

R ¹⁴ and R ¹⁵ are each independently a methylene fluoride or a perfluoroalkylene group having 2 to 4 carbon atoms, and R ¹⁶ is a urethane bond or a urethane bond. In the formula, R ¹³ is independently a single bond, a methylene group or an ethylene group, And (meth) acryloyl groups, and t is an integer of 5 to 50,

(E) Radical polymerization initiator

(F) Organic solvents

(G) Additive

According to the composition of the present invention, a cured film excellent in transparency, scratch resistance and antifouling property can be produced.

In addition, the composition of the present invention provides a cured film having remarkably improved fingerprint removability and fingerprint visibility as well as scratch resistance (steel wool resistance) by blending the compound of component (D) having a specific structure.

When only the compound of the component (D) is added, the fingerprint removability is improved, but the fingerprint visibility and scratch resistance are lowered. When the components (A) and (D) are used in combination, the various properties, particularly scratch resistance, It is possible to provide a cured film improved in balance with good visibility at the same time.

Hereinafter, each component will be described.

(A) a compound represented by the formula (1)

Since the compound represented by the formula (1) (the compound of the present invention) has been described above, detailed description thereof is omitted here.

Component (A) is a compound having a polydialkylpolysiloxane group, a perfluoropolyether group, a urethane group and a (meth) acrylate group. By having these four kinds of groups at the same time, it is possible to provide a cured film excellent in compatibility with other components, low in haze, and excellent in transparency. In addition, by having a polydialkylpolysiloxane moiety, scratch resistance is improved and a cured film having excellent antifouling properties, particularly, removability of a solvent-based marker can be provided by having a perfluoropolyether group.

By containing the compound (A) in the composition of the present invention, a cured product having excellent transparency, scratch resistance and antifouling property can be produced.

By using the component (A) in combination with the component (D) to be described later, it is possible to provide excellent fingerprint removing properties and fingerprint visibility that can not be obtained when each of them is used alone.

The content of the compound (A) in the composition of the present invention is preferably in the range of 0.01 to 5% by weight, more preferably in the range of 0.1 to 1% by weight, based on 100% by weight of the total of the components excluding the solvent Do. If it is less than 0.01% by weight, the effect of addition may not be exhibited. If it exceeds 5% by weight, the hardness of the coating film may be damaged.

(B) a multifunctional polymerizable unsaturated group-containing compound

The multifunctional polymerizable unsaturated group-containing compound (B) used in the present invention is preferably used in order to enhance the film formability of the composition. The multifunctional polymerizable unsaturated group-containing compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include (meth) acrylic esters and vinyl compounds, ) Acrylic esters are preferred. In addition, the polyfunctional polymerizable unsaturated group-containing compound (B) in the present invention excludes the components (A) and (Cc) and (D) described below.

Examples of the (meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di Acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Ah Poly (meth) acrylates of ethylene oxide or propylene oxide adducts thereof in the hydroxyl groups thereof, oligo esters having two or more (meth) acryloyl groups in the molecule, hydroxyl group-containing (meth) (Meth) acrylates, oligoether (meth) acrylates and oligoepoxy (meth) acrylates. Of these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate and ditrimethylol propane tetra (meth) acrylate are preferable.

Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

Examples of commercially available products of such multifunctional polymerizable unsaturated group-containing compound (B) include ARONIX M-400, M-404, M-408, M-450, M-305 and M-309 manufactured by Toagosei Co., , M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M- -245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO- D-310, D-330, DPHA, and DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), TO-755, TO-756, TO-1343, TO-902, TO-904, TO- , DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR- -444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, 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- , TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, manufactured by Kyoeisha Chemical Co., And the like Lite Acrylate PE-4A, DPE-6A, DTMP-4A.

The compounding amount of the multifunctional polymerizable unsaturated group-containing compound (B) in the composition of the present invention is in the range of 20 to 99% by weight and in the range of 20 to 70% by weight when the total amount of the components excluding the solvent is 100% , And more preferably in the range of 25 to 60 wt%. When the component (B) is blended in the above range, a cured film having a high hardness can be obtained.

(C) Particles

The particles (C) used in the present invention are particles (oxide particles (Ca (O)) particles mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium ))to be. It is also preferable that the particles (reactive particles (Cc)) surface-treated with an organic compound (Cb) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule.

(1) Particles (Ca) containing an oxide as a main component

The oxide particles (Ca) used in the production of the reactive particles (Cc) are preferably selected from silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium in terms of transparency and color tone of the cured film of the curable composition And an oxide of at least one element selected from the group consisting of titanium oxide and titanium oxide.

Examples of the oxide particles Ca include particles such as silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, have. Among them, particles of silica, alumina, zirconia and antimony oxide are preferable from the viewpoint of hardness. These may be used alone or in combination of two or more. The oxide particles (Ca) are preferably used as powder-like or solvent-dispersed sols. When used as a solvent dispersion sol, an organic solvent is preferable as the dispersion medium from the viewpoint of compatibility with other components and dispersibility. 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; Esters such as ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, 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; And amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

The number average particle diameter of the oxide particles (Ca) can be appropriately selected according to the use of the cured film to be obtained, but is preferably 0.001 to 2 μm, more preferably 0.003 to 1 μm, and particularly preferably 0.005 to 0.5 μm . If the number average particle diameter exceeds 2 占 퐉, the transparency of a cured product tends to deteriorate or the surface state of the cured film tends to deteriorate. The number average particle diameter of the present invention refers to an average value of 20 particle diameters measured by observation with a transmission electron microscope. In addition, various surfactants and amines may be added to improve the dispersibility of the particles.

Examples of commodities commercially available as silicon oxide particles (for example, silica particles) include methanol silica sol, IPA-ST, MEK-ST, NBA-ST and XBA (trade name, manufactured by Nissan Chemical Industries, -ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50 and ST-OL. As the powdery silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 manufactured by Nippon Aerosil Co., Ltd., manufactured by Asahi Glass Co., Ltd. E220A and E220 manufactured by Nippon Silica Kagaku Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia K.K. and SG flakes manufactured by Nippon Itagaras Co., Ltd., and the like can be given.

As the alumina water dispersion, alumina sol-100, -200, -520, manufactured by Nissan Chemical Industries, Ltd., As the isopropanol dispersion product of alumina, AS-150I manufactured by Sumitomo Osaka Cement Co., Ltd .; As the toluene dispersion product of alumina, AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd.; As the toluene dispersion product of zirconia, HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd., Examples of the water content of zinc antimonate powder include Celanacs manufactured by Nissan Chemical Industries, Ltd.; Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide, and the like are available from Nanotech Co., Ltd .; As the water-dispersed sol of antimony doped tin oxide, SN-100D manufactured by Ishihara Sangyo Co., Ltd., As the ITO powder, a product of Mitsubishi Materials Corporation; As the cerium oxide aqueous dispersion, Nidral manufactured by Dakika Chemical Co., Ltd. can be mentioned.

The shape of the oxide particles Ca is spherical, hollow, porous, rod-like, plate-like, fibrous or irregular, and preferably spherical. The specific surface area (by BET specific surface area measurement method using nitrogen) of the oxide particles (Ca) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Ca) can be used in a state of being dispersed in a dry powder, water, or an organic solvent. For example, a dispersion of the particulate oxide particles known in the art as the solvent-dispersed sol of the oxide can be used directly. Particularly, in applications requiring excellent transparency to a cured product, it is preferable to use an organic solvent-dispersed sol of an oxide.

(2) Organic compound (Cb)

The organic compound (Cb) used in the present invention is not particularly limited as long as it is a compound having a polymerizable unsaturated group and a hydrolyzable silyl group. Examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group. The hydrolyzable silyl group reacts with water to form a silanol (Si-OH) group, and includes, for example, at least one methoxy group, ethoxy group, n-propoxy group, isopropoxy group, An alkoxy group, an aryloxy group, an acetoxy group, an amino group, and a halogen atom.

As the organic compound (Cb) used in the present invention, a commercially available product such as methacryloyloxypropyltrimethoxysilane may be used. For example, a compound described in International Publication WO97 / 12942 may be used.

(3) Production of reactive particles (Cc)

The organic compound (Cb) having a silanol group or a group capable of generating a silanol group by hydrolysis is mixed with the metal oxide particles (Ca) and hydrolyzed to bond them. The ratio of the organic polymer component in the resulting reactive particles (Cc), that is, the hydrolyzate and the condensate of the hydrolyzable silane is usually the weight value of% reduction in weight when the dry powder is completely burned in the air, And usually can be obtained by thermogravimetric analysis up to 800 ° C.

The bonding amount of the organic compound (Cb) to the oxide particles (Ca) is 100% by weight, preferably 0.01 to 40% by weight (the sum of the metal oxide particles (Ca) and the organic compound (Cb) %, More preferably 0.1 to 30 wt%, and particularly preferably 1 to 20 wt%. When the amount of the organic compound (Cb) to be reacted with the metal oxide particles (Ca) is within the above range, the dispersibility of the reactive particles (Cc) in the composition can be improved and the effect of increasing the transparency and scratch resistance of the resulting cured product You can expect.

In the composition of the present invention, the component (C) is an optional component, and the content of the particles (C) in the composition is either the particle (Ca) or the reactive particle (Cc) Is preferably 0 to 74% by weight, more preferably 20 to 74% by weight, and more preferably 40 to 70% by weight, based on 100% The particles (C) are components that can be arbitrarily blended, but when blended in the above range, it becomes easy to obtain a coating film having a high hardness.

The content of the particles (C) means a solid content, and when the particles (C) are used in the form of a solvent dispersion sol, the content thereof does not include the amount of the solvent.

(D) a compound represented by the formula (10)

The compound of the component (D) (hereafter also referred to as " compound (D) ") in the composition of the present invention includes a perfluoropolyether group, a urethane group and a (meth) Group. By having these groups at the same time, it is possible to provide a cured film excellent in compatibility with other components, low in haze, and excellent in transparency. In addition, by having a polydialkylpolysiloxane moiety, scratch resistance is improved and a cured film having excellent antifouling property, particularly, fingerprint removal property can be provided by having a perfluoropolyether group.

The composition of the present invention can produce a cured product that is excellent in transparency, scratch resistance and antifouling property, particularly, fingerprint removing property, obtained by containing the compound (D).

≪ Formula 10 >

R ¹⁶ -R ¹³ -R ¹⁴ O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -R ¹⁶

Formula of 10, R ¹³ represents a single bond, a methylene group or an ethylene odd and each independently, R ¹⁴ and R ¹⁵ are each independently a fluorinated methylene or perfluoroalkyl group having 2 to 4, R ¹⁶ is a urethane bond And (meth) acryloyl groups, and t is an integer of 5 to 50,

The molecular weight of the compound (D) used in the present invention is usually in the range of 2500 to 10,000 and preferably in the range of 2,500 to 9,000. Here, the molecular weight is measured by a gel permeation chromatography method.

The compound (D) may be a commercially available product or may be prepared by the following production method.

The method for producing the compound (D)

(i) reacting a perfluoropolyether diol represented by the following formula (24) with a diisocyanate compound or a triisocyanate compound, and (ii) reacting a hydroxyl group-containing (meth) acrylate compound.

HO-R ¹³ -R ¹⁴ -O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -OH

- represents a group of the formula 24, R ¹³ represents a single bond, each independently, a methylene group or ethylene, R ¹⁴ and R ¹⁵ each independently represents an alkylene group with fluoride, methylene, perfluoroalkyl having 2 to 4, t is from 5 to Lt; / RTI >

More specifically, the diol compound having perfluoropolyether is diluted with a solvent such as methyl ethyl ketone or mixed with an aromatic diisocyanate compound as a solvent. After cooling to 10 to 20 占 폚 in a water bath, Lewis acid catalyst such as dibutyltin dilaurate is added and the mixture is stirred at 15 to 30 占 폚 for 1 to 3 hours. Thereafter, the mixture is cooled in a water bath at 10 to 20 DEG C, and a compound having a (meth) acryloyl group and a hydroxyl group is mixed and reacted at 45 to 65 DEG C for 3 to 6 hours.

The perfluoropolyether diol represented by the above-mentioned general formula (24) is not particularly limited as far as it is a compound having a hydroxyl group at both terminals of the perfluoropolyalkylene oxide. However, examples of the perfluoropolyether diol include a terminal diol compound of perfluoropolyethylene oxide, A terminal diol compound of propylene oxide is preferred.

Examples of commercial products of the perfluoropolyether diols represented by the above formula (24) include Fluorolink D10H (manufactured by Sorvex Solexis) and the like.

As the diisocyanate compound or triisocyanate compound, the compound used as the component (A) may be used. Of these, aromatic diisocyanate compounds can be preferably used.

The compound having a (meth) acryloyl group and a hydroxyl group can be used as long as it is a compound containing a hydroxyl group and a (meth) acryloyl group. Since the compound (A) The compound having an acryloyl group and a hydroxyl group preferably has a plurality of (meth) acryloyl groups. Specific examples of the compound having a (meth) acryloyl group and a hydroxyl group include hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, , But pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate having three or more (meth) acryloyl groups are preferably used.

The content of the component (D) in the composition of the present invention is usually in the range of 0 to 5 wt%, preferably in the range of 0.01 to 5 wt%, when the total amount of the components excluding the solvent is 100 wt% And more preferably in the range of 0.1 to 1% by weight. By setting the content within the above range, it is possible to provide a cured film improved in balance of scratch resistance, fingerprint removal property, and fingerprint visibility at the same time.

The weight ratio of the compound (D) :( A) in the composition of the present invention is preferably in the range of 10: 1 to 1: 5. Outside of the above range, a synergistic effect obtained by the combined use of the compounds (A) and (D) may not be obtained.

(E) Radical polymerization initiator

The composition of the present invention preferably contains (E) a radical polymerization initiator.

Examples of such (E) radical polymerization initiators include compounds which generate thermally active radical species (thermal polymerization initiator) and compounds which generate active radical species by irradiation (light irradiation) (radiation (light) polymerization initiator) , And a radiation (light) polymerization initiator is preferable.

The radiation (light) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate radicals to initiate polymerization, and examples thereof include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2- chlorothioxanthone , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan- Non-1,4- (2-hydroxy 2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).

Examples of commercially available radiation polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, DauroCure 1116, 1173, Lucirin TPO manufactured by BASF, Ubecryl P36 manufactured by 8893UCB, and Ejecure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46 and KIP75 / B manufactured by Lambert TS.

The thermal polymerization initiator is not particularly limited as long as it is decomposed by heating to generate radicals to initiate polymerization. Examples thereof include peroxides and azo compounds. Specific examples thereof include benzoyl peroxide, t-butyl peroxybenzoate , Azobisisobutyronitrile, and the like.

In the composition of the present invention, the blending amount of the radical polymerization initiator (E) to be used is preferably within the range of 0.01 to 20 wt%, more preferably 0.1 to 10 wt%, based on 100 wt% By weight to 10% by weight. When the amount is less than 0.01% by weight, the hardness of a cured product may be insufficient, and when it is more than 20% by weight, the hardness of the coating film may be impaired.

(F) Organic solvents

The composition of the present invention may be diluted with an organic solvent to control the thickness of the coating film. For example, when used as an antireflection film or coating material, the viscosity is usually 0.1 to 50,000 mPa · sec / 25 ° C, 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; Esters such as ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, 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; And amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

The amount of the organic solvent (F) to be used in the composition of the present invention is preferably in the range of 50 to 10,000 parts by weight based on 100 parts by weight of the total of the components excluding the solvent. The blending amount of the solvent can be suitably determined in consideration of the coating film thickness, the viscosity of the composition, and the like.

(G) Additive

In addition to the above components, a radical polymerizing compound other than the component (B), an antioxidant, an ultraviolet absorber, a leveling agent and the like may be added to the composition of the present invention.

The composition of the present invention can be prepared by adding the components (A) to (G), respectively, and mixing them at room temperature or under heating conditions. Specifically, it can be produced by using a mixer such as a mixer, a kneader, a ball mill, or a three-axis roll. That is, in the case of mixing under heating conditions, it is preferable that the polymerization is carried out at a temperature lower than the decomposition initiation temperature of the polymerization initiator or polymerizable unsaturated group.

The composition of the present invention obtained as described above can be cured by heat and / or radiation (light).

III. Curing membrane

The cured film of the present invention can be obtained by coating the composition of the present invention on various substrates, for example, a plastic substrate and curing. Specifically, it can be obtained as a coated molded article by coating the composition, preferably drying the volatile component at 0 to 200 ° C, and then curing the composition with heat and / or radiation.

When heat is generated, for example, electric heaters, infrared lamps, hot air, etc. may be used as the heat source thereof. The preferred curing conditions in the case of heat are 20 to 150 캜, and are performed within a range of 10 seconds to 24 hours.

In the case of radiation (light), the source of the radiation is not particularly limited as long as the composition can be cured within a short period of time after coating, but ultraviolet rays and electron beams are preferable for reasons such as the availability of the apparatus. For example, a mercury lamp, a halide lamp, a laser or the like is used as a source of ultraviolet rays, and a system using thermal electrons generated from a tungsten filament commercially available as a source of electron beams. When ultraviolet rays or electron beams are used as the radiation, the irradiation amount of ultraviolet rays is preferably 0.01 to 10 J / cm ² , more preferably 0.1 to 2 J / cm ² . The irradiation condition of the electron beam is preferably 10 to 300 kV in acceleration voltage, 0.02 to 0.30 mA / cm ^{2 in} electron density, and 1 to 10 Mrad in electron beam irradiation.

The composition of the present invention is suitable for use as a coating material (hard coating) or an antireflection film, and examples of the substrate to be an antireflection or coating target include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin , Epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, and slate. The shape of these substrates may be a plate shape, a film shape, or a three-dimensional shaped product. The coating method may be a conventional coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, . The coating thickness of these coatings is usually from 0.1 to 400 μm, preferably from 0.5 to 200 μm after drying and curing.

The cured film obtained by curing the composition of the present invention has a high hardness and scratch resistance, and is particularly excellent in removability of a marker and removal of fingerprints, and a coating film (coating film) excellent in surface slipperiness (Scratches) on discs such as CD, DVD, and MO recording discs, plastic optical components, touch panels, film type liquid crystal devices, plastic containers, construction materials as building interior materials, wall materials, and artificial marble, A protective coating material for preventing or preventing contamination, or an antireflection film of a film type liquid crystal device, a touch panel, a plastic optical part, or the like.

IV. The laminate

The laminate of the present invention can be obtained by laminating a cured film obtained by curing the composition of the present invention on a transparent substrate. A preferable method of laminating the transparent substrate and the cured film is as described above. The laminate of the present invention is preferable as a surface protective film for various display devices because it has high transparency and hardness and is also excellent in antifouling property, in particular, fingerprint removability, fingerprint visibility, oily marker removability and sustainability.

<Examples>

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited at all by these examples. Unless otherwise stated, &quot;% &quot; represents weight%, and &quot; part &quot; represents a crown part.

Example 1

Synthesis of Compound 1

[In the formula, Me is a methyl group, n of R ⁵ are each independently methylene or ethylene fluoride perfluoro, is m = 10 to 15, n = 10 to 15;

Di-t-butyl-p-cresol (Yoshinox BHT, manufactured by Yoshitomi Pine Chemical Co., Ltd.) (0.024 g) and polydimethylsiloxane monool (manufactured by Mitsubishi Chemical Corporation) were placed in a reaction vessel equipped with a stirrer, (4.41 g), 2,4-tolylene diisocyanate (TOLDY-100, manufactured by Mitsui Chemicals, Inc., polyurethane), and methyl ethyl ketone (Maruzen Sekiyuu Oil Co., (29.72 g), and the mixture was cooled in a water bath. After adding dibutyltin dilaurate (CASTIN-D, manufactured by Kyodo Yakusho Co., Ltd.) (0.080 g) at 10 占 폚 ± 5 占 폚, the mixture was stirred at room temperature for 2 hours. Subsequently, the reaction mixture was cooled in a water bath, and thereto was added perfluoropolyether diol (Fluorolink D10H) (37.96 g) diluted with methyl ethyl ketone (37.96 g) And the mixture was heated for 2 hours. Thereafter, the reaction mixture was cooled in a water bath, and 2,4-tolylene diisocyanate (4.41 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by weight was added thereto, followed by stirring at room temperature for 2 hours. Subsequently, the reaction mixture was cooled in a water bath, and 27.92 g of dipentaerythritol penta / hexaacrylate (ARONIX M403, manufactured by Toagosei Co., Ltd.) diluted with methyl ethyl ketone to a solid concentration of 50 wt% The mixture was heated to 60 캜 and heated for 4 hours to obtain a methyl ethyl ketone solution (200 g) of the compound 1 represented by the structural formula.

IR charts, ¹ H NMR charts, and ¹³ C { ¹ H} NMR charts of the compound 1 thus obtained are shown in FIGS. 1 to 3, respectively.

Examples 2 to 9

In the same manner as in Example 1 except that the starting materials were used in the amounts shown in Table 1 below, the same procedures were repeated to obtain Compounds 2 to 9 having the structural formulas described later. In addition, except for Yoshinox BHT and CASTIN-D, methyl ethyl ketone was diluted to 50 wt% and added.

The compounds shown in Table 1 are as follows.

Yoshinox BHT: 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemicals Co., Ltd.)

Siilla plain FM0411: Polydimethylsiloxane monool (manufactured by Chisso Corporation)

Silica Plain FM0421: Polydimethylsiloxane monool (manufactured by Chisso Corporation)

TOLDY-100: 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals, Inc., polyurethane)

CASTIN-D: Dibutyltin dilaurate (manufactured by Kyodo Yakuhinha Co., Ltd.)

Fluorolink D10H: Perfluoropolyether diol (manufactured by Sorvex Solexis)

Sumidel N3300: Triisocyanate compound (Sumitacabaiel Urethane Co., Ltd.)

HMDI: hexamethylene diisocyanate (DURANATE HMDI, manufactured by Asahi Kasei Chemicals Co., Ltd.)

Aronix M403: dipentaerythritol penta / hexaacrylate (manufactured by Toagosei Co., Ltd.)

A-TMM-3LM-N: pentaerythritol triacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.)

HEA: hydroxyethyl acrylate (HEA, manufactured by Osaka Kyoe Kogyo Co., Ltd.)

Compound 2

M is from 65 to 75 and n is from 10 to 15, and R &lt; ⁵ &gt; is methylene or perfluoroethyl,

An IR chart, a ¹ H NMR chart, and a ¹³ C { ¹ H} NMR chart of Compound 2 are shown in FIGS. 4 to 6, respectively.

Compound 3

Wherein m is a methyl group, n R ⁵ are each independently methylene fluoride or perfluoroethylene, PETA is a group derived from pentaerythritol triacrylate, m = 10 to 15, n = 10 to 15, 15]

An IR chart, a ¹ H NMR chart, and a ¹³ C { ¹ H} NMR chart of Compound 3 are shown in FIGS. 7 to 9, respectively.

Compound 4

[In the formula, Me is a methyl group, n of R ⁵ include ethylene each independently fluoride, methylene or perfluoroalkyl with, DPPA is a group derived from dipentaerythritol pentaacrylate, m = 10 to 15, n = 10 To 15]

An IR chart, a ¹ H NMR chart, and a ¹³ C { ¹ H} NMR chart of Compound 4 are shown in FIGS. 10 to 12, respectively.

Compound 5

M is from 65 to 75, n is from 10 to 100, and R &lt; ⁵ &gt; is methylene or perfluoroethylene, PETA is a group derived from pentaerythritol triacrylate, 15]

An IR chart, a ¹ H NMR chart, and a ¹³ C { ¹ H} NMR chart of Compound 5 are shown in FIGS. 13 to 15, respectively.

Compound 6

M is from 65 to 75, n is from 10 to 10, and R &lt; ⁵ &gt; is methylene or perfluoroethylene, DPPA is a group derived from dipentaerythritol pentaacrylate, To 15]

An IR chart, a ¹ H NMR chart, and a ¹³ C { ¹ H} NMR chart of Compound 14 are shown in FIGS. 16 to 18, respectively.

Compound 7

Wherein n R ^{5 s} are each independently methylene fluoride or perfluoroethylene, HEA is a 2-acryloyloxyethyl group, m = 10 to 15, n = 10 to 15,

IR charts, ¹ H NMR charts, and ¹³ C { ¹ H} NMR charts of the obtained compound 7 are shown in FIGS. 19 to 21, respectively.

Compound 8

M is from 65 to 75 and n is from 10 to 15, and R &lt; ⁵ &gt; is methylene or perfluoroethyl,

Compound 9

[In the formula, Me is a methyl group, n of R ⁵ are each independently methylene or ethylene fluoride perfluoro, is m = 10 to 15, n = 10 to 15;

Synthesis Example 1

Synthesis of Compound D1 (Component (D))

Wherein R ⁵ is each independently methylene fluoride or perfluoroethylene and n is 6 to 10,

0.024 g of 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals Co., Ltd., Yoshinox BHT) and 0.024 g of perfluoropolyether diol (manufactured by Sorvex Solexis, , 8.58 g of 2,4-tolylene diisocyanate (TOLDY-100, manufactured by Mitsui Chemicals Polyurethanes, Inc.) and 45.58 g of methyl ethyl ketone (manufactured by Maruzen Sekiyu Kagaku Kabushiki Kaisha) were charged, Lt; / RTI &gt; 0.080 g of dibutyltin dilaurate (CASTIN-D, manufactured by Kyodo Yakushin Co., Ltd.) was added thereto, and then the mixture was heated to 60 캜 and heated for 1.5 hours. Subsequently, the reaction mixture was cooled in a water bath, and 54.42 g of dipentaerythritol pentaacrylate (ARONIX M403, manufactured by Toagosei Co., Ltd.) was diluted with methyl ethyl ketone to a solid content of 50% by weight. The reaction solution was heated to 60 DEG C and heated for 4 hours to obtain a compound D1 represented by the above formula.

Synthesis Example 3

Synthesis of compound D2 (component (D))

Wherein R ⁵ is each independently methylene fluoride or perfluoroethylene and n is 6 to 10,

0.024 g of 2,6-di-t-butyl-p-cresol (Yoshinox Fine Chemicals Co., Ltd., Yoshinox BHT) and 0.024 g of perfluoropolyether diol (manufactured by Sorvex Solexis, , 12.27 g of 2,4-tolylene diisocyanate (TOLDY-100, manufactured by Mitsui Chemicals, Inc.) and methyl ethyl ketone (manufactured by Maruzen Sekiyu Kagaku Kabushiki Kaisha) were placed in a separable flask, Lt; / RTI &gt; 0.080 g of dibutyltin dilaurate (CASTIN-D, manufactured by Kyodo Yakushin Co., Ltd.) was added thereto, and then the mixture was heated to 60 캜 and heated for 1.5 hours. Subsequently, the reaction mixture was cooled in a water bath, 34.84 g of tetramethylolmethane triacrylate (NK Ester A-TMM-3LM-N, manufactured by Shin Nakamura Chemical Co., Ltd.) was dissolved in methyl ethyl ketone at a solid content concentration of 50 wt% %. &Lt; / RTI &gt; The temperature was raised to 60 占 폚 and then heated for 4 hours. Thus, a compound D2 represented by the above chemical structural formula was obtained.

Production Example 1

Synthesis of organic compound (Cb)

222 parts of isophorone diisocyanate was added dropwise to a solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air at 50 DEG C over 1 hour while stirring, Followed by heating and stirring. To this was added NK Ester A-TMM-3LM-N (a mixture of 60 wt% of pentaerythritol triacrylate and 40 wt% of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., ) Was added dropwise at 30 占 폚 over 1 hour, followed by stirring at 60 占 폚 for 10 hours to obtain an organic compound (Cb) containing a polymerizable unsaturated group. The amount of residual isocyanate in the product was analyzed by FT-IR to be 0.1% or less, indicating that the reaction was almost quantitatively terminated. The infrared absorption spectrum of the product is such that the absorption peak at 2550 cm ^-1 characteristic of the mercapto group in the raw material and the absorption peak at 2260 cm ^-1 characteristic of the raw material isocyanate compound are lost and a new urethane bond and S (C═O) NH- And a peak at 1720 cm ^-1 characteristic of an acryloxy group were observed at the peak of 1,660 cm ^-1 characteristic of the acryl group and an acryloyl group having an acryloxy group as a polymerizable unsaturated group and -S (C═O) NH- and a urethane bond Indicating that a periodic alkoxysilane was formed. Thus, a total of 773 parts of the organic compound (Cb) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2

Preparation of reactive particles

(Solid content: 35% by weight, MEK-ST-L, number average particle diameter: 0.022 μm, manufactured by Nissan Chemical Industries, Ltd.), 2.98 parts (containing 2.32 parts of the organic compound (Cb) Ltd.), 0.12 parts of ion-exchanged water and 0.01 part of p-hydroxyphenyl monomethyl ether was stirred at 60 DEG C for 4 hours, and then 1.36 parts of methyl orthoformate was added and the mixture was stirred at the same temperature for 1 hour And the mixture was heated and stirred to obtain a reactive particle dispersion. The dispersion was weighed in an amount of 2 g on an aluminum plate, dried on a hot plate at 175 DEG C for 1 hour, weighed, and the solid content was determined to be 36.5%. Further, after 2 g of the dispersion was weighed in a magnetic crucible, the inorganic content in the solid content was determined from the inorganic residue after calcination for 1 hour in a muffle furnace at 750 캜 for 30 minutes on a hot plate at 80 캜 and found to be 95%.

&Lt; Preparation of curable composition >

Example 10

216.9 parts by weight (65.08 parts by weight as silica particles) of a silica particle dispersion (dispersion medium: methyl ethyl ketone, product name: MEK-ST-L, manufactured by Nissan Chemical Industries, Ltd.), dipentaerythritol hexaacrylate , 3 parts by weight of a photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.), 0.5 part by weight of the compound 3 synthesized in Example 3, and the solid content concentration (Methyl ethyl ketone: methyl isobutyl ketone = 3: 7) was added so that the amount of the solvent was 50%, and the mixture was stirred to obtain a curable composition.

Examples 11 to 25 and Comparative Examples 1 to 6

Each of the curable compositions was prepared in the same manner as in Example 10, except that the composition shown in Table 2 was used.

The abbreviations in the table indicate the following.

Compounds 1 to 9: Compounds of component (A) prepared in Examples 1 to 9

Dipentaerythritol hexaacrylate: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.

Pentaerythritol triacrylate: NK ester A-TMM-3LM-N manufactured by Shin Nakamura Chemical Co., Ltd.

Reactive particles: The reactive particle-modified colloidal silica prepared in Preparation Example 2

Compound D1: Compound (D) prepared in Synthesis Example 1

Compound D2: Compound (D) prepared in Synthesis Example 2

5101X: Fluorolink 5101X, manufactured by Sorvex Solexis

Irg.184: Photopolymerization initiator manufactured by Ciba Specialty Chemicals, Inc.

D10H: Perfluoropolyether diol represented by the formula (2), Fluorolink D10H, manufactured by Sorvex Solexis

Off tool DAC: urethane acrylate containing perfluoropolyether, manufactured by Daikin Kogyo Co., Ltd.

Sililla Plain FM0711: Polydimethylsiloxane-containing urethane acrylate, manufactured by Chisso Corporation

&Lt; Preparation of cured film &

Each of the curable compositions obtained in the above Examples and Comparative Examples was coated on a TAC film having a thickness of 80 mu m using a bar coater (12 mils). After drying at 80 DEG C for 2 minutes, each of the cured films was prepared by irradiating ultraviolet rays at a radiation intensity of 1.0 J / cm &lt; ² &gt; under air using a high-pressure mercury lamp.

&Lt; Evaluation of physical properties of cured film &

The haze, total light transmittance and contact angle of the obtained cured film were measured. In addition, the oil-based marker removability, steel wool resistance, and coating film appearance were evaluated. The results are shown in Table 1.

(1) Measurement of haze (%)

The haze (%) of the cured film was measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Shikiki Co., Ltd.).

(2) Measurement of total light transmittance (Tt;%)

The total light transmittance (%) of the cured film was measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Shikiki Co., Ltd.).

(3) Oil-based marker removal test

A milky marker (Zebra Kabushiki Kaisha, Mackie MO-120-MC-BK) was attached to the cured film and after 30 seconds, it was removed with a nonwoven fabric (trade name: Bencoat S-2, manufactured by Asahi Kasei). When completely removed, the oil-based marker was attached again, and the removal was repeated again. The number of times of removal was counted and evaluated according to the following evaluation criteria.

A: The number of times that the marker can be removed more than 10 times

B: Possible to remove the marker 5 to 10 times

C: Number of times that the oil-based marker can be removed 1 to 4 times

D: The number of times that the marker can be removed 0 times

(4) Scratch resistance (steel wool resistance)

A steel wool (BONSTAR No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a tensile rubfastness tester (AB-301, manufactured by Tester Sangyo KK), and the surface of the cured film was repeated 10 times with a load of 900 g The surface of the cured film was visually inspected for scratches and evaluated according to the following evaluation criteria.

A: The cured film is free from scratches.

B: A slight fine scratch is formed on the cured film.

C: Several scratches occur in the cured film.

D: A plurality of scratches are formed on the cured film.

E: Scratches occur on the entire surface of the cured film.

(5) Measurement of contact angle (°)

The contact angle of the cured film to water and hexadecane was measured in accordance with JIS 6768 using a contact angle meter Drop Master 500 manufactured by Kyowa Chemical Industry Co.,

(6) Fingerprint removal test

The back surface of the film was painted black, and a fingerprint was attached to the surface of the film. Thereafter, the fingerprints were removed with a tissue and evaluated according to the following evaluation criteria.

A: It is easily removed.

?: Removed.

B: Difficult to remove.

X: Not removed.

From the results shown in Table 2, it was found that the cured film obtained by curing the curable composition to which the compound of the present invention was added had excellent transparency, scratch resistance and antifouling property.

It was also found that the curable composition containing the compound of component (A) in the present invention has high transparency, excellent removability of oil-based markers and excellent resistance to steel wool.

In the comparative examples in which the compound of the component (A) was not compounded in the present invention, transparency was excellent, but it was found that compatibility between oil-based marker removal and scratch resistance was not possible.

It was also found that the curable composition containing the component (D) in addition to the component (A) of the present invention has high transparency, excellent scratch resistance (steel wool resistance), and excellent fingerprint removal properties.

&Lt; Industrial Availability >

The compound of the present invention is useful as a surface modifying agent for curing compositions for forming various hard coatings because it can impart excellent transparency, scratch resistance and antifouling property to the cured film obtained by curing the curable composition by adding it to the curable composition.

In particular, since the transparency of the cured film is not impaired, it is useful as an additive for a cured film intended for optical use.

The curable composition of the present invention is useful for producing a cured film excellent in transparency, scratch resistance and antifouling property.

The cured film of the present invention is particularly useful as a hard coating because of its excellent transparency, scratch resistance and antifouling property. Further, it is preferable for optical use because of its excellent transparency.

1 is an IR chart of Compound 1. Fig.

2 is a ¹ H NMR chart of Compound 1. Fig.

FIG. 3 is a ¹³ C { ¹ H} NMR chart of Compound 1. FIG.

4 is an IR chart of Compound 2. Fig.

5 is a ¹ H NMR chart of compound 2. Fig.

FIG. 6 is a ¹³ C { ¹ H} NMR chart of Compound 2. FIG.

7 is an IR chart of compound 3. Fig.

Fig. 8 is a ¹ H NMR chart of Compound 3. Fig.

9 is a ¹³ C { ¹ H} NMR chart of compound 3.

10 is an IR chart of Compound 4. Fig.

11 is a ¹ H NMR chart of compound 4.

FIG. 12 is a ¹³ C { ¹ H} NMR chart of Compound 4. FIG.

13 is an IR chart of Compound 5. Fig.

14 is a ¹ H NMR chart of compound 5.

FIG. 15 is a ¹³ C { ¹ H} NMR chart of Compound 5. FIG.

16 is an IR chart of Compound 6. Fig.

17 is a ¹ H NMR chart of compound 6.

18 is a ¹³ C { ¹ H} NMR chart of compound 6.

19 is an IR chart of Compound 7. Fig.

20 is a ¹ H NMR chart of Compound 7. Fig.

21 is a ¹³ C { ¹ H} NMR chart of compound 7.

Claims (12)

A compound represented by the following formula (1). &Lt; Formula 1 >

Wherein R ¹ is independently an alkyl group having 1 to 3 carbon atoms, R ² is a divalent aliphatic group, alicyclic group or aromatic group which may have a substituent, R ³ is independently a single bond, a methylene group Or an ethylene group, R ⁴ and R ⁵ are each independently methylene fluoride or a perfluoroalkylene group having 2 to 4 carbon atoms, R ⁷ is a group having at least one (meth) acryloyl group, R ⁸ is a substituent M is an integer of 10 to 100, n is an integer of 5 to 50, and p is 1 or 2, 2. The compound according to claim 1, wherein R &lt; ² &gt; is a divalent aromatic group having a substituent. 2. The compound according to claim 1, wherein p is 1 and R &lt; ⁸ &gt;

Wherein R ²⁸ is a methyl group or an ethyl group, s is an integer of 0 to 2, and * 2. The compound according to claim 1, wherein p is 2, and R &lt; ⁸ &gt;

[Wherein R ⁶ represents an alkylene group having 2 to 10 carbon atoms and * represents a bonding site] The following components (A) and (B): (A) a compound represented by the formula (1) described in any one of claims 1 to (B) a compound having two or more polymerizable unsaturated groups in the molecule other than the above (A) &Lt; / RTI &gt; The curable composition according to claim 5, further comprising (C) particles mainly composed of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium . The curable composition according to claim 5, further comprising (D) a compound represented by the following formula (10). &Lt; Formula 10 > R ¹⁶ -R ¹³ -R ¹⁴ O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -R ¹⁶ [R ¹³ are each a single bond, each independently, a methylene group or an ethylene group, R ¹⁴ and R ¹⁵ are each independently a fluorinated methylene or a carbon number of perfluoroalkyl of 2 to 4 groups, R ¹⁶ is a urethane bond and a (meth) An acryloyl group, and t is an integer of 5 to 50, The curable composition according to claim 5, wherein the compounding amount of the compound (A) is in the range of 0.01 to 5% by weight based on 100% by weight of the total of the composition excluding the solvent. The curable composition according to claim 6, wherein the component (C) is a particle surface-treated with an organic compound (Cb) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule. The curable composition according to claim 5, further comprising (E) a radical polymerization initiator. The curable composition according to claim 5, further comprising (F) an organic solvent. 6. The curable composition of claim 5, wherein the curable composition is for forming a hard coating.

Images