JP5141596B2 - Compound having polydialkylpolysiloxane group, perfluoropolyether group, urethane group and (meth) acryloyl group, curable composition and cured film containing the same - Google Patents

Description

  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 compound, and a cured film.

  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 oil marker wiping. 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. The antireflection film material (II) combined with the reactive surface modifier (I) is for forming a low refractive index layer.

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

This invention is made | formed in view of the above-mentioned problem, and provides the compound which can provide the transparency which was excellent in the cured film obtained, antifouling property, especially oil-based marker wiping property, and abrasion resistance. Objective.
Furthermore, an object of the present invention is to provide a curable composition for forming a hard coat layer having excellent transparency, scratch resistance and antifouling property, particularly excellent fingerprint wiping property and fingerprint visibility. To do.

  In order to achieve the above object, the present inventors have intensively studied, and according to a compound containing a polydialkylpolysiloxane group, a perfluoropolyether group, a urethane group and a (meth) acryloyl group, the obtained cured film can be obtained. It has been found that excellent transparency, antifouling properties, particularly oily marker wiping properties, and scratch resistance can be imparted.

  Furthermore, the present inventors added (B) a curable composition containing a compound having two or more polymerizable unsaturated groups to (A) a polydialkylsiloxane group, a perfluoropolyether group, a urethane bond and ( It has been found that by adding a compound containing a (meth) acryloyl group, a cured film that can satisfy the above properties can be obtained.

  In addition, the present inventors have (B) a curable composition containing a compound having two or more polymerizable unsaturated groups in the molecule, (A) a curing having a polysiloxane structure and a perfluoropolyether structure. By adding a combination of an organic compound, a (D) (meth) acryloyl group and a curable compound containing a perfluoropolyether structure, the above properties are satisfied, and excellent fingerprint wiping and fingerprint visibility. The present invention was completed by finding that a cured film having the above can be obtained.

That is, this invention provides the following compound and curable composition.
1. A compound represented by the following general formula (1).
[In Formula (1), R ¹ is each independently an alkyl group having 1 to 3 carbon atoms, and R ² is a divalent aliphatic group, alicyclic group or aromatic group which may have a substituent. R ³ is each independently a single bond, a methylene group or an ethylene group, R ⁴ and R ⁵ are each independently methylene fluoride or a C 2-4 perfluoroalkylene group, and R ⁷ is It is a group having one or more (meth) acryloyl groups, R ⁸ is a p + 1 valent organic group which may have a substituent and may contain a hetero atom, and m is an integer of 10 to 100 N is an integer of 5 to 50, and p is 1 or 2. ]
2. ^2. The compound according to 1 above, wherein R ² is a divalent aromatic group having a substituent.
3. 3. The compound according to 1 or 2 above, wherein p is 1 and R ⁸ is represented by the following formula.
[Wherein R ²⁸ represents a methyl group or an ethyl group, s represents an integer of 0 to 2, and * represents a binding site. ]
4). 3. The compound according to 1 or 2 above, wherein p is 2 and R ⁸ is represented by the following general formula.
[Wherein R ⁶ represents an alkylene group having 2 to 10 carbon atoms, and * represents a bonding site. ]
5). The compound according to any one of the above 1 to 3, wherein R ⁷ is represented by the following general formula.
[In formula, Ac represents a (meth) acryloyl group, q is 0-2, * represents a coupling | bond part. ]
6). The following components (A) and (B):
(A) The compound represented by the general formula (1) according to any one of the above 1 to 5 (B) containing a compound having two or more polymerizable unsaturated groups in the molecule other than the above (A) Curable composition.
7). (C) further comprising (C) particles containing as a main component an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Curable composition.
8). Furthermore, (D) The curable composition of said 6 or 7 containing the compound represented by following General formula (10).
R < ¹⁶ > -R < ¹³ > -R < ¹⁴ > O- (R < ¹⁵ > O) _t- R < ¹⁴ > -R < ¹³ > -R < ¹⁶ > (10)
[R ¹³ is each 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 ¹⁶ is a urethane bond. It is a group having at least one (meth) acryloyl group, and t is an integer of 5 to 50. ]
9. The curing according to any one of 6 to 8 above, wherein the compounding amount of the compound (A) is in the range of 0.01 to 5% by weight when the total composition excluding the solvent is 100% by weight. Sex composition.
10. The curable composition according to any one of 7 to 9 above, 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. .
11. Further (E) The curable composition in any one of said 6-10 containing a radical polymerization initiator.
12 Furthermore, (F) The curable composition in any one of said 6-11 containing an organic solvent.
13. The curable composition according to any one of 6 to 12, which is used for forming a hard coat.
14 The cured film formed by hardening | curing the curable composition in any one of said 6-13.

  By adding the compound of the present invention to a curable composition, it is possible to impart excellent transparency, antifouling property, and scratch resistance to the resulting cured film. Furthermore, oily marker wiping property can be imparted.

  According to the present invention, it is possible to produce a hard coat composition having excellent transparency, scratch resistance and antifouling properties. Furthermore, it is possible to produce a hard coat composition having excellent fingerprint wiping properties and fingerprint visibility.

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. 4 is an IR chart of Compound 6. ¹ is a ¹ H NMR chart of Compound 6. 10 is a ¹³ C { ¹ H} NMR chart of Compound 6. 7 is an IR chart of Compound 7. ¹ is a ¹ H NMR chart of Compound 7. 10 is a ¹³ C { ¹ H} NMR chart of Compound 7.

Hereinafter, the present invention will be described in detail.
I. Compound represented by general formula (1) The compound of the present invention has a structure represented by the following general formula (1).

In formula (1), each R ¹ is independently an alkyl group having 1 to 3 carbon atoms, and is 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 is each independently a single bond, a methylene group or an ethylene group.
R ⁴ and R ⁵ are each independently methylene fluoride or a C 2-4 perfluoroalkylene group, preferably a methylene fluoride, a perfluoroethylene group, or a perfluoropropylene group.

R ⁷ is a group having one or more (meth) acryloyl groups, and is preferably hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate or tripentaerythritol hepta ( It is a group excluding the hydroxyl group of (meth) acrylate.

R ⁷ is also preferably a group represented by the following general formula.
In the formula, Ac represents a (meth) acryloyl group, q is 0 to 2, and * represents a binding site.

R ⁸ is a p + 1 valent organic group which may have a substituent and may contain a hetero atom, 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 binding site.

R ⁸ is also preferably a group represented by the following general 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 * represents a bonding site.

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.

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

Compound (1-1)
In 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, and r is It is an integer of 0-2.
R ²⁷ is a group having one or more (meth) acryloyl groups, preferably hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate or tripentaerythritol hepta ( It is a group excluding the hydroxyl group of (meth) acrylate.

Compound (1-2)
In 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, and preferably in the range of 2,500 to 9,000. Here, the molecular weight is measured by gel permeation chromatography.

The compound (1-1) or (1-2) of the present invention can be produced, for example, by the following production method.
(A) The following general formula (4)
^OCN-R 2 -NCO (4)
[In the formula (4), R ² is as defined above. And the following general formula (3)
[In the formula (3), R ¹ and m are as defined above. A step of reacting a polydialkylsiloxane monoalcohol represented by the formula:
(B) The following general formula (2)
_{^{HO-R 3 -R 4 -O- (}} R 5 O) n -R 4 -R 3 -OH (2)
[In the formula (2), R ³ , R ⁴ , R ⁵ and n are as defined above. A step of reacting a perfluoropolyether diol represented by the formula:
(C) a step of reacting the diisocyanate compound or triisocyanate compound (5), and (d) the following general formula (6)
R ⁷ -OH (6)
[In the formula (6), R ⁷ is as defined above. The process of making the (meth) acrylate shown by this react.

  More specifically, the alcohol compound (3) having a polydialkylsiloxane group is diluted with a solvent such as methyl ethyl ketone, or mixed with the diisocyanate compound (4) 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 in a methyl ethyl ketone solution of the diol compound (2) having perfluoropolyether or without solvent, and stirred at 40 to 65 ° C. for 1 to 3 hours. The reactor is cooled to 10-20 ° C. in a water bath, a diisocyanate compound or a triisocyanate compound (5) is added, and the mixture is stirred at 15-30 ° C. for 1-3 hours. It cools to 10-20 degreeC with a water bath, the compound (6) which has a 1 or more (meth) acryloyl group and one hydroxyl group is mixed, and it is made to react at 45-65 degreeC for 3 to 6 hours.

  Specific examples of the diisocyanate represented by the general formula (4) include hexamethylene diisocyanate and the like as the aliphatic diisocyanate, isophorone diisocyanate and the like as the alicyclic diisocyanate, Phenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate Examples include 2,6-naphthalene diisocyanate and 2,7-naphthalene diisocyanate. Aromatic diisocyanates are preferred.

  A known compound can be used as the polydialkylsiloxane monoalcohol represented by the general formula (3). Examples of commercially available products include Silaplane FM0411 (m = 10 to 15), FM0421 (m = 65). -75) (made by Chisso Corporation) and the like.

The perfluoropolyether diol represented by the general formula (2) 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 general formula (2) include Fluorolink D10H (manufactured by Solvay Solexis).

  When the isocyanate compound (5) used at the said process (c) is a diisocyanate compound, the compound demonstrated by the said General formula (4) is mentioned. When the isocyanate compound (5) used in the step (c) is a triisocyanate compound, 1,4,8-triisocyanate octane, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 2,4 , 6-triisocyanatotoluene, isocyanuric acid trisisocyanatohexyl and the like.

  Examples of the polyfunctional (meth) acrylate represented by the general formula (6) include pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate. In addition, (meth) acrylic acid, hydroxyethyl (meth) acrylate, etc. are mentioned as a compound shown by the said General formula (6).

II. Curable composition The curable composition of this invention (henceforth "the composition of this invention") is a composition comprised by the following component (A)-(G). Among these, (A) and (B) are essential components, and (C) to (G) are optional components that can be added as necessary.

(A) The compound (B) of the present invention represented by the general formula (1) (other than (A), (Cc) and (D) below) has two or more polymerizable unsaturated groups in the molecule. Compound (hereinafter referred to as “polyfunctional polymerizable unsaturated group-containing compound”)
(C) silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, which may be bonded to an organic compound (Cb) having a polymerizable unsaturated group and hydrolyzable silyl group in the molecule; Particles whose main component is an oxide of at least one element selected from the group consisting of cerium (hereinafter referred to as “particles”)
(D) Compound represented by the following general formula (10): R ¹⁶ -R ¹³ -R ¹⁴ O- (R ¹⁵ O) _t -R ¹⁴ -R ¹³ -R ¹⁶ (10)
[In Formula (10), R ¹³ is each 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, R ¹⁶ is a group having at least one urethane bond and one (meth) acryloyl group, and t is an integer of 5 to 50. ]
(E) radical polymerization initiator (F) organic solvent (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 has not only scratch resistance (steel wool resistance) but also particularly high fingerprint wiping property and fingerprint visibility by blending the component (D) compound having a specific structure. Gives an improved cured film.
When only the compound of component (D) is added, the fingerprint wiping property is improved, but the fingerprint visibility and scratch resistance are reduced, but by using components (A) and (D) in combination, Thus, a cured film having improved properties in particular, such as scratch resistance, fingerprint wiping property and fingerprint visibility can be provided in a balanced manner.

  Hereinafter, each component will be described.

(A) Compound represented by general formula (1) Since the compound represented by general formula (1) (the compound of the present invention) has been described above, details thereof are 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 types of groups at the same time, a cured film having excellent compatibility with other components, low haze, and excellent transparency can be provided. Furthermore, by having a polydialkylpolysiloxane part, the scratch resistance is improved, and at the same time, by having a perfluoropolyether group, a cured film excellent in antifouling property, particularly oily marker wiping property, can be obtained. Can be given.
By containing the compound (A), the composition of the present invention can produce a cured product having excellent transparency, scratch resistance and antifouling properties.
By using the component (A) in combination with the component (D) described later, excellent fingerprint wiping properties and fingerprint visibility that cannot be obtained when each component is used alone can be provided.

  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 when the total amount of the components excluding the solvent is 100% by weight. More preferably, it is in the range of 1 to 1% by weight. 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 impaired.

(B) Polyfunctional polymerizable unsaturated group-containing compound The polyfunctional polymerizable unsaturated group-containing compound (B) used in the present invention is suitably used for enhancing the film-forming property of the composition. The polyfunctional polymerizable unsaturated group-containing compound (B) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule. For example, (meth) acrylic esters, vinyl compounds (Meth) acrylic esters are preferred. In addition, the polyfunctional polymerizable unsaturated group containing compound (B) in this invention shall exclude the above-mentioned (A) and below-mentioned (Cc) and (D) component.

  (Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Hydroxyl-containing (meth) such as ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate Acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates And oligoepoxy (meth) acrylates. 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 vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  As a commercial item of such a polyfunctional polymerizable unsaturated group containing compound (B), Toagosei Co., Ltd. Aronix M-400, M-404, M-408, M-450, M-305, M-309, 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, Nippon Kayaku Co., Ltd. KAYARAD D-310, D-330, DPHA, DPC -20, 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, Kyoeisha Chemical Co., Ltd. ) Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like.

  The compounding quantity of the polyfunctional polymerizable unsaturated group containing compound (B) in the composition of this invention exists in the range of 20-99 weight% when the sum total of the component except a solvent is 100 weight%, and is 20-20. It is preferably within the range of 70% by weight, and more preferably within the range of 25-60% by weight. When the component (B) is blended in the above range, a cured film having high hardness can be obtained.

(C) Particle The particle (C) used in the present invention is 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. (Oxide particles (Ca)). Moreover, it is also preferable that it is the particle | grains (reactive particle (Cc)) surface-treated with the organic compound (Cb) which has a polymerizable unsaturated group and a hydrolyzable silyl group in a molecule | numerator.

(1) Particles mainly composed of oxide (Ca)
The oxide particles (Ca) used for the production of the reactive particles (Cc) are silicon, aluminum, zirconium, titanium, zinc, germanium, indium from the viewpoints of transparency and hue of the cured film of the resulting curable composition. , Particles mainly composed of an oxide of at least one element selected from the group consisting of tin, antimony and cerium.

  Examples of these oxide particles (Ca) include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can be mentioned. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more. Furthermore, the oxide particles (Ca) are preferably used as a powder or solvent-dispersed sol. When used as a solvent-dispersed sol, the dispersion medium is preferably an organic solvent 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; 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 thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the oxide particles (Ca) may be appropriately selected according to the use of the obtained cured film, but is preferably 0.001 μm to 2 μm, more preferably 0.003 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm is particularly preferable. When the number average particle diameter exceeds 2 μm, the transparency when cured is lowered or the surface state when cured is deteriorated. 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. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Commercially available products as silicon oxide particles (for example, silica particles) include, for example, colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA- manufactured by Nissan Chemical Industries, Ltd. ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Moreover, as an aqueous dispersion product of alumina, Nissan Chemical Industries, Ltd. alumina sol-100, -200, -520; As an alumina isopropanol dispersion product, Sumitomo Osaka Cement Co., Ltd. AS-150I; AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; Nissan Chemical Industries, Ltd. as an aqueous dispersion of zinc antimonate powder ) Cellax: Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powders and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; Antimony-doped tin oxide water dispersion sol is Ishihara Sangyo ( SN-100D, manufactured by Mitsubishi Materials Corp .; cerium oxide The dispersion can be exemplified Taki Chemical Co., Ltd. Nidoraru like.

The oxide particles (Ca) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of the oxide particles (Ca) (by the BET specific surface area measurement method using nitrogen) 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 dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, the use of an organic solvent-dispersed sol of an oxide is preferable in applications where the cured product requires excellent transparency.

(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 is a group that reacts with water to produce a silanol (Si-OH) group. For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. A group, an alkoxy group such as an n-butoxy group, an aryloxy group, an acetoxy group, an amino group, or a halogen atom is bonded.

  As the organic compound (Cb) used in the present invention, commercially available products such as methacryloyloxypropyltrimethoxysilane can be used, for example, compounds described in International Publication No. WO97 / 12942 can also be used. .

(3) Preparation of reactive particles (Cc) An organic compound (Cb) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with metal oxide particles (Ca), hydrolyzed, and the two are combined. . The ratio of the organic polymer component, that is, the hydrolyzable silane hydrolyzate and condensate in the resulting reactive particles (Cc) is usually the weight loss% when the dry powder is completely burned in air. The constant value can be obtained, for example, by thermogravimetric analysis from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Cb) bound to the oxide particles (Ca) is preferably 100% by weight of the reactive particles (Cc) (the total of the metal oxide particles (Ca) and the organic compound (Cb)), It is 0.01 to 40 weight%, More preferably, it is 0.1 to 30 weight%, Most preferably, it is 1 to 20 weight%. By setting the amount of the organic compound (Cb) to be reacted with the metal oxide particles (Ca) within the above range, the dispersibility of the reactive particles (Cc) in the composition can be improved, and the cured product obtained can be obtained. The effect of improving transparency and scratch resistance can be expected.

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 both the particles (Ca) and the reactive particles (Cc). When the total of components excluding the solvent is 100% by weight, it is 0 to 74% by weight, preferably 20 to 74% by weight, and preferably 40 to 70% by weight. More preferred. The particles (C) are components that can be blended arbitrarily, but by blending in the above range, it becomes easy to obtain a coating film with high hardness.
In addition, content of particle | grains (C) means solid content, and when particle | grains (C) are used with the form of solvent dispersion | distribution sol, the quantity of a solvent is not included in the content.

(D) Compound represented by general formula (10) The compound of component (D) in the composition of the present invention (hereinafter sometimes referred to as “compound (D)”) is represented by the following general formula (10). It is a compound having a perfluoropolyether group, a urethane group and a (meth) acrylate group. By having these groups simultaneously, a cured film having excellent compatibility with other components, low haze, and excellent transparency can be provided. Further, by having a polydialkylpolysiloxane portion, the scratch resistance is improved, and at the same time, by having a perfluoropolyether group, a cured film having excellent antifouling property, particularly fingerprint wiping property is provided. be able to.
By containing this compound (D), the composition of the present invention can produce a cured product having excellent transparency, scratch resistance and antifouling properties, particularly excellent fingerprint wiping properties.

R < ¹⁶ > -R < ¹³ > -R < ¹⁴ > O- (R < ¹⁵ > O) _t- R < ¹⁴ > -R < ¹³ > -R < ¹⁶ > (10)
[In Formula (10), R ¹³ is each 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, R ¹⁶ is a group having at least one urethane bond and one (meth) acryloyl group, 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 gel permeation chromatography.

Compound (D) may be a commercially available product, or can be produced by the following production method.
The production method of compound (D) is as follows:
(I) The following general formula (24)
HO-R < ¹³ > -R < ¹⁴ > -O- (R < ¹⁵ > O) _t- R < ¹⁴ > -R < ¹³ > -OH (24)
Wherein ^{(24), R 13} are each independently a single bond, a methylene group, or ethylene ^{group, R 14} and ^{R 15} are each independently methylene fluoride, represents a perfluoroalkylene group having 2 to 4 carbon atoms , T is an integer of 5-50. And a step of reacting a diisocyanate compound or a triisocyanate compound, and (ii) a step of reacting a hydroxyl group-containing (meth) acrylate compound.

  More specifically, a diol compound having perfluoropolyether is diluted with a solvent such as methyl ethyl ketone or mixed with an aromatic diisocyanate compound 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. Then, it cools to 10-20 degreeC with a water bath, the compound which has a (meth) acryloyl group and one hydroxyl group is mixed, and it is made to react at 45-65 degreeC for 3 to 6 hours.

The perfluoropolyether diol represented by the general formula (24) is not particularly limited as long as it is a compound having a hydroxyl group at both ends of the perfluoropolyalkylene oxide. Oxide terminal diol compounds are preferred.
Moreover, Fluorolink D10H (made by Solvay Solexis) etc. are mentioned as an example of the commercial item of the perfluoro polyether diol shown by the said General formula (24).

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

  As the compound having the (meth) acryloyl group and one hydroxyl group, any compound containing a hydroxyl group and a (meth) acryloyl group can be used, but the compound (A) is expected to be unevenly distributed on the surface. Therefore, the compound having a (meth) acryloyl group and one hydroxyl group preferably has a plurality of (meth) acryloyl groups. Specific examples of the compound having a (meth) acryloyl group and one hydroxyl group include hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate having three or more 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% by weight and 0.01 to 5% by weight when the total amount of the components excluding the solvent is 100% by weight. % Is preferably within 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 in which scratch resistance, fingerprint wiping property, and fingerprint visibility are simultaneously improved in a well-balanced manner.

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

(E) Radical polymerization initiator It is preferable to mix | blend (E) radical polymerization initiator with the composition of this invention.
Examples of such (E) radical polymerization initiator include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation (radiation (light ) Polymerization initiators) and the like can be mentioned, and radiation (photo) 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, 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, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -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-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1- Methyl vinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61 , Darocur 1116, 1173, BASF's Lucillin TPO, 8893UCB's Ubekrill P36, Lamberti's Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

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

  In the composition of the present invention, the blending amount of the (E) radical polymerization initiator used as necessary is in the range of 0.01 to 20% by weight when the total of the components excluding the solvent is 100% by weight. The content is preferably within the range, and more preferably within the range of 0.1 to 10% by weight. If it is less than 0.01% by weight, the hardness of the cured product may be insufficient, and if it exceeds 20% by weight, the hardness of the coating film may be impaired.

(F) Organic solvent The composition of the present invention can be used after being diluted with an organic solvent in order 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.

  The amount of the organic solvent (F) used as necessary in the composition of the present invention is within the range of 50 to 10,000 parts by weight when the total of components excluding the solvent is 100 parts by weight. Is preferred. The blending amount of the solvent can be appropriately determined in consideration of the coating film thickness, the viscosity of the composition, and the like.

(G) Additive In addition to the above components, the composition of the present invention may contain a radical polymerizable compound other than the component (B), an antioxidant, an ultraviolet absorber, a leveling agent, and the like as necessary. .

  The composition of the present invention can be prepared by adding the above components (A) to (G) and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start 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. Cured film The cured film of the present invention can be obtained by coating the composition of the present invention on various substrates, for example, plastic substrates, and curing them. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it can be obtained as a coated molded body by performing a curing treatment with heat and / or radiation.
When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours.

In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating, but for reasons such as the availability of equipment, ultraviolet rays, electrons Lines are preferred. For example, a mercury lamp, a halide lamp, a laser, or the like can be used as the ultraviolet ray source, and a thermoelectron generated from a commercially available tungsten filament can be used as the electron beam source. When ultraviolet rays or electron beams are used as the radiation, the preferred irradiation light quantity of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, preferable irradiation conditions of the electron beam are an acceleration voltage of 10 to 300 kV, an electron density of 0.02 to 0.30 mA / cm ² , and an electron beam irradiation amount of 1 to 10 Mrad.

  The composition of the present invention is suitable for use as a coating material (hard coat) or an antireflection film. Examples of the base material to be subjected to antireflection or coating include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin). , Epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. These substrates may be in the form of a plate, film or three-dimensional molded body, and the coating method may be a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush. A paint etc. can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 0.5 to 200 μm after drying and curing.

  A cured film obtained by curing the composition of the present invention has high hardness and scratch resistance, and is particularly excellent in oil marker wiping property and fingerprint wiping property. Recording film such as CD, DVD, MO, etc., plastic optical parts, touch panel, film type liquid crystal element, plastic container, flooring as a building interior material, wall material, It is particularly preferably used as a protective coating material for preventing scratches (scratching) such as artificial marble or preventing contamination, or an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components, and the like.

IV. Laminated body The laminated body of this invention can be obtained by laminating | stacking the cured film formed by hardening | curing the said composition of this invention on a transparent base material. A suitable transparent substrate and a laminated method of the cured film are as described above. The laminate of the present invention has high transparency and hardness, and is excellent in antifouling properties, particularly fingerprint wiping property and fingerprint visibility, oily marker wiping property and its sustainability. It is suitable as a surface protective film.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” represents wt%, and “part” represents part by weight.

Example 1
Synthesis of compound 1
[In the above formula, Me is a methyl group, and n R ^5s are each independently methylene fluoride or perfluoroethylene, and m = 10-15 and n = 10-15. ]

  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), polydimethylsiloxane monool (Manufactured by Chisso Corporation, Silaplane FM0411) (25.31 g), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100) (4.41 g) and methyl ethyl ketone (manufactured by Maruzen Petrochemical Co., Ltd.) ( 29.72 g) was added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) (0.080 g) at 10 ° C. ± 5 ° C., the mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and after adding perfluoropolyether diol (Solvisolexis, Fluorolink D10H) (37.96 g) diluted with methyl ethyl ketone (37.96 g) to 60 ° C. The temperature was raised and heated for 2 hours. Thereafter, the reaction mixture was cooled in a water bath, 2,4-tolylene diisocyanate (4.41 g) diluted with methyl ethyl ketone to a solid concentration of 50% by weight was added thereto, and the mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was cooled in a water bath, and dipentaerythritol penta / hexaacrylate (Tonya Gosei Co., Ltd .: Aronix M403) (27.92 g) diluted with methyl ethyl ketone to a solid content concentration of 50% by weight was added thereto, The mixture was heated to 60 ° C. and heated for 4 hours to obtain a methyl ethyl ketone solution (200 g) of compound 1 represented by the above structural formula.

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

Examples 2-9
In Example 1, the same operation was performed except having made each raw material the compound and addition amount which are shown in following Table 1, and obtained the compounds 2-9 which have a structural formula mentioned later. In addition, except Yoshinox BHT and CASTIN-D, it diluted to 50 weight% with methyl ethyl ketone and injected | thrown-in.

The compounds described in Table 1 are as follows.
Yoshinox BHT: 2,6-di-t-butyl-p-cresol (manufactured by Yoshitomi Fine Chemicals)
Silaplane FM0411: Polydimethylsiloxane monool (manufactured by Chisso Corporation)
Silaplane FM0421: Polydimethylsiloxane monool (manufactured by Chisso Corporation)
TORDY-100: 2,4-tolylene diisocyanate (Mitsui Chemical Polyurethane)
CASTIN-D: Dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd.)
Fluorolink D10H: Perfluoropolyether diol (manufactured by Solvay Solexis)
Sumidur N3300: Triisocyanate compound (manufactured by Sumika Bayer Urethane Co., Ltd.)
HMDI: Hexamethylene diisocyanate (Duranate HMDI Asahi Kasei Chemicals Corporation)
Aronix M403: Dipentaerythritol penta / hexaacrylate (manufactured by Toa Gosei Co., Ltd.)
A-TMM-3LM-N: Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
HEA: Hydroxyethyl acrylate (HEA, Osaka Organic Industry Co., Ltd.)

Compound 2
[In the formulas, Me is a methyl radical, n pieces is ^{R 5} methylene fluoride are each independently or a perfluoroalkyl ethylene, m = 65 to 75, a n = 10 to 15. ]

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

Compound 3
[In the above formula, Me is a methyl group, n R ^5s are each independently methylene fluoride or perfluoroethylene, PETA is a group derived from pentaerythritol triacrylate, m = 10 to 15, n = 10-15. ]

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of Compound 3 are shown in FIGS.

Compound 4
[In the above formula, Me is a methyl group, n R ^5s are each independently methylene fluoride or perfluoroethylene, DPPA is a group derived from dipentaerythritol pentaacrylate, m = 10 to 15, n = 10-15. ]

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

Compound 5
[In the formulas, Me is a methyl radical, n pieces is ^{R 5} methylene fluoride or perfluoro ethylene independently, PETA is a group derived from pentaerythritol triacrylate, m = 65~75, n = 10-15. ]

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of Compound 5 are shown in FIGS.

Compound 6
[In the formulas, Me is a methyl radical, n pieces is ^{R 5} methylene fluoride or perfluoro ethylene independently, DPPA is a group derived from dipentaerythritol pentaacrylate, m = 65~75, n = 10-15. ]

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of Compound 14 are shown in FIGS.

Compound 7
[In the above formula, n R ^{5 s} are each independently methylene fluoride or perfluoroethylene, HEA is a 2-acryloyloxyethyl group, and m = 10-15 and n = 10-15. ]

An IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 7 are shown in FIGS.

Compound 8
[In the formulas, Me is a methyl radical, n pieces is ^{R 5} methylene fluoride are each independently or a perfluoroalkyl ethylene, m = 65 to 75, a n = 10 to 15. ]

Compound 9
[In the above formula, Me is a methyl group, and n R ^5s are each independently methylene fluoride or perfluoroethylene, and m = 10-15 and n = 10-15. ]

Synthesis example 1
Synthesis of Compound D1 (Component (D))
[Wherein R ⁵ is each independently methylene fluoride or perfluoroethylene, and n = 6-10. ]

  In a three-necked flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical, Yoshinox BHT), perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) 37.00 g, 2,4-tolylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., TOLDY-100) 8.58 g and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) 45.58 g were charged and cooled in a water bath. Then, 0.080 g of dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) was added, and then the temperature was raised to 60 ° C. 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 ° 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 = 6-10. ]

  In a three-necked flask equipped with a stirrer, 0.024 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical, Yoshinox BHT), perfluoropolyether diol (manufactured by Solvay Solexis, Fluorolink D10H) 52.89 g, 12.4-tolylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., TOLDY-100) 12.27 g and methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) were charged and cooled in a water bath. Then, 0.080 g of dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) was added, and then the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and 34.84 g of tetramethylolmethane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-TMM-3LM-N) was added to the solid content concentration of 50% by weight with methyl ethyl ketone. Diluted material was added. The temperature was raised to 60 ° C. and 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) In dry air, 222 parts of isophorone diisocyanate was added dropwise to a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate at 50 ° C. with stirring for 1 hour, and then 70 ° C. And stirred for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Among them, the one involved in the reaction is pentaerythritol having a hydroxyl group. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Cb) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, a total of 773 parts of organic compound (Cb) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2
Production of Reactive Particles 2.98 parts of composition produced in Production Example 1 (including 2.32 parts of organic compound (Cb)), silica particle dispersion (Ca) (solid content: 35% by weight, MEK-ST-) L, number average particle size 0.022 μm, manufactured by Nissan Chemical Industries, Ltd.) 89.90 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts, After stirring for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 36.5%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 95%.

<Manufacture of curable composition>
Example 10
Silica particle dispersion (dispersion medium: methyl ethyl ketone, manufactured by Nissan Chemical Co., Ltd .: product name MEK-ST-L) 216.9 parts by weight (65.08 parts by weight as silica particles), dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) Company: KAYARAD DPHA) 31.42 parts by weight and photoinitiator (Ciba Specialty Chemicals Co., Ltd .: Irgacure 184) 3 parts by weight were mixed, and 0.5 parts by weight of compound 3 synthesized in Example 3 was added. A solvent (methyl ethyl ketone: methyl isobutyl ketone = 3: 7) was added so that the solid content concentration was 50%, and the mixture was stirred to obtain a curable composition.

Examples 11-25, Comparative Examples 1-6
Each curable composition was produced in the same manner as in Example 10 except that the compositions shown in Tables 2-1 and 2-2 were used.

Abbreviations in the table indicate the following.
Compound 1-9: Compound of component (A) produced in Examples 1-9 Dipentaerythritol hexaacrylate: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
Pentaerythritol triacrylate: Shin Nakamura Chemical Co., Ltd. NK ester A-TMM-3LM-N
Reactive particles: Reactive group-modified colloidal silica produced in Production Example 2 Compound D1: Compound of component (D) produced in Synthesis Example 1 Compound D2: Compound of component (D) produced in Synthesis Example 2 5101X: Fluorolink 5101X Irg., Manufactured by Solvay Solexis, Inc. 184: Photopolymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd. D10H: Perfluoropolyether diol represented by the general formula (2), Fluorolink D10H, manufactured by Solvay Solexis, Inc. OPTOOL DAC: Perfluoropolyether-containing urethane acrylate, Daikin Industries Silaplane FM0711: Urethane acrylate containing polydimethylsiloxane, manufactured by Chisso Corporation

<Manufacture of cured film>
Each curable composition obtained in the above Examples and Comparative Examples was coated on a TAC film having a thickness of 80 μm using a bar coater (12 mil). After drying at 80 ° C. for 2 minutes, each cured film was prepared by photocuring by irradiating with ultraviolet rays at an intensity of 1.0 J / cm ^{2 in} air using a high-pressure mercury lamp.

<Evaluation of physical properties of cured film>
The haze, total light transmittance, and contact angle of the obtained cured film were measured. Moreover, oil-based marker wiping property, 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 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7105.

(2) Measurement of total light transmittance (Tt;%) The total light transmittance (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). .

(3) Oil marker wiping test An oil marker (Zebra Co., Ltd., McKee MO-120-MC-BK) was attached to the cured film, and after 30 seconds, wiped with a non-woven fabric (Asahi Kasei brand name: Bencott S-2). It was. When it was completely wiped off, an oily marker was attached again, and wiping was repeated again. The number of possible wipings was counted and evaluated according to the following evaluation criteria.
A: Oil marker wiping possible 10 times or more B: Oil marker wiping possible 5-10 times C: Oil marker wiping possible 1 to 4 times D: Oil marker wiping possible 0 times

(4) Scratch resistance (steel wool resistance)
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is loaded 10 times with a load of 900 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.
A: The cured film is not damaged.
B: Slight fine scratches are generated on the cured film.
C: Several scratches are generated on the cured film.
D: Many scratches are generated 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 with respect to water and hexadecane was measured according to JIS 6768 using a contact angle meter Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd.

(6) Fingerprint wiping property test The back surface of the film was hit black, and the fingerprint was attached to the film surface. Thereafter, the fingerprint was wiped off with a tissue and evaluated according to the following evaluation criteria.
(Double-circle): It can wipe off easily.
○: Can be wiped off.
Δ: It is difficult to wipe off.
X: Cannot be wiped off.

From the results in Table 2, it can be seen that the cured film obtained by curing the curable composition to which the compound of the present invention is added is excellent in transparency, scratch resistance and antifouling property.
Furthermore, it turns out that the curable composition with which the compound of the component (A) in this invention was mix | blended has high transparency, and is excellent in both oil-based marker wiping off property and steel wool resistance.
In the comparative example in which the compound of the component (A) in the present invention is not blended, it is understood that although the transparency is excellent, the oil marker wiping property and the scratch resistance cannot be compatible.
Moreover, the curable composition which mix | blended the component (D) in addition to the component (A) in this invention is not only highly transparent and excellent in scratch resistance (steel wool resistance), but also in the wipeability of fingerprints. It turns out that it is excellent.

The compound of the present invention can impart excellent transparency, scratch resistance and antifouling property to a cured film obtained by curing the curable composition by adding it to the curable composition. It is useful as a surface modifier such as a curable composition for forming a coat.
In particular, since the transparency of the cured film is not impaired, it is useful as an additive for a cured film for optical applications.

The curable composition of the present invention is useful for producing a cured film excellent in transparency, scratch resistance and antifouling property.
Since the cured film of the present invention is excellent in transparency, scratch resistance and antifouling property, it is particularly useful as a hard coat. Moreover, since it is excellent in transparency, it is suitable for optical applications.

Claims (14)

A compound represented by the following general formula (1).
[In Formula (1), R ¹ is each independently an alkyl group having 1 to 3 carbon atoms, and R ² is a divalent aliphatic group, alicyclic group or aromatic group which may have a substituent. R ³ is each independently a single bond, a methylene group or an ethylene group, R ⁴ and R ⁵ are each independently methylene fluoride or a C 2-4 perfluoroalkylene group, and R ⁷ is It is a group having one or more (meth) acryloyl groups, R ⁸ is a p + 1 valent organic group which may have a substituent and may contain a hetero atom, and m is an integer of 10 to 100 N is an integer of 5 to 50, and p is 1 or 2. ] The compound according to claim 1, wherein R ² is a divalent aromatic group having a substituent. The compound according to claim 1, wherein the p is 1 and the R ⁸ is represented by the following formula.
[Wherein R ²⁸ represents a methyl group or an ethyl group, s represents an integer of 0 to 2, and * represents a binding site. ] The compound according to claim 1 or 2, wherein the p is 2, and the R ⁸ is represented by the following general formula.
[Wherein R ⁶ represents an alkylene group having 2 to 10 carbon atoms, and * represents a bonding site. ] The compound according to any one of claims 1 to 4, wherein R ⁷ is represented by the following general formula.
[In formula, Ac represents a (meth) acryloyl group, q is 0-2, * represents a coupling | bond part. ] The following components (A) and (B):
(A) Compound represented by general formula (1) according to any one of claims 1 to 5 (B) Compound having two or more polymerizable unsaturated groups in the molecule other than (A) above A curable composition containing   Furthermore, (C) The particle | grains which have as a main component the oxide of the at least 1 element chosen from the group which consists of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium are contained. Curable composition. The curable composition according to claim 6 or 7, further comprising (D) a compound represented by the following general formula (10).
R < ¹⁶ > -R < ¹³ > -R < ¹⁴ > O- (R < ¹⁵ > O) _t- R < ¹⁴ > -R < ¹³ > -R < ¹⁶ > (10)
[R ¹³ is each 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 ¹⁶ is a urethane bond. It is a group having at least one (meth) acryloyl group, and t is an integer of 5 to 50. ]   The amount of the compound (A) is in the range of 0.01 to 5% by weight when the total composition excluding the solvent is 100% by weight. The curable composition as described.   The said (C) component is the particle | grains surface-treated with the organic compound (Cb) which has a polymerizable unsaturated group and a hydrolyzable silyl group in a molecule | numerator, The hardening of any one of Claims 7-9 Sex composition.   Furthermore, the curable composition of any one of Claims 6-10 containing (E) radical polymerization initiator.   Furthermore, the curable composition of any one of Claims 6-11 containing the organic solvent (F).   It is an object for hard-coat formation, The curable composition of any one of Claims 6-12. The cured film formed by hardening | curing the curable composition of any one of Claims 6-13.