KR101273731B1 - Curable composition, cured product, and laminate - Google Patents

Abstract

A curable composition comprising a curable composition and a cured product thereof, which can form a coating (film) having high hardness, small curling properties, and excellent bendability while having excellent coating properties, is provided. The present invention is based on the total amount of the composition excluding the solvent (A) 5 to 70% by weight of the metal oxide particles formed by combining an organic compound having a polymerizable unsaturated group, and (B) 20 to 50% by weight of the compound represented by the formula (1) It contains%, The curable composition characterized by the above-mentioned.

≪ Formula 1 >

In the formula, R _1, R ₂ and R ₃ are each independently a monovalent organic group, R ₁ to R ₃ and at least two of the _{^{-R 4 OCOCR 5 = CH 2,}} R 4 is a group of a carbon number of 2 to 8 It is a divalent organic group, R <^5> is a hydrogen atom or a methyl group.

Curable composition, hardened | cured material, laminated body, metal oxide particle, polyfunctional (meth) acrylate

Description

Curable Compositions, Cured Products and Laminates {CURABLE COMPOSITION, CURED PRODUCT, AND LAMINATE}

The present invention relates to a curable composition, a cured product of the curable composition, and a laminate. More specifically, the present invention provides plastics (eg, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS) with excellent coating properties. Resins, AS resins, norbornene resins), coatings with high hardness on the surface of substrates such as metal, wood, paper, glass, and slate, and excellent scratch resistance and adhesion to substrates and adjacent layers such as substrates or high refractive index layers. It relates to a curable composition capable of forming a (film), and a hard coat cured film having less curling and excellent flexibility and chemical resistance.

Recently, a protective coating material for preventing scratches or contamination of the surface of the substrate; Adhesives and sealants of substrates; As a binder of printing ink, a cured film having excellent coating properties and excellent hardness, flexibility, scratch resistance, abrasion resistance, low curling property (less curvature of the cured film), adhesiveness, transparency, chemical resistance, and appearance can be used. There is a demand for a curable composition that can be formed.

In the use of an antireflection film such as a film type liquid crystal element, a touch panel, or a plastic optical component, a curable composition capable of forming a cured film having a high refractive index is desired.

For example, a technique has been proposed in which particles obtained by modifying the surface of colloidal silica with methacryloxysilane and a composition containing an acrylate as a radiation (photo) -curable coating material have been proposed (Japanese Patent Publication (S)) 58-. 500251). This type of radiation curable composition has been widely used because of its excellent coating properties and the like, which is disclosed in, for example, Japanese Patent Laid-Open No. Hei 10-273595, No. 2000-143924, No. 2000-281863, and No. 2000-49077, 2001-89535, or 2001-200023.

<Problems to Solve Invention>

However, when the low refractive index film is applied onto the cured product of the above-mentioned composition and the resulting laminate is used as an antireflection film, although a constant improvement is seen in the antireflection effect, the balance of hardness, flexibility, and curling property is different. There is a need for further improved antireflective films that fit well.

The present invention has been accomplished in view of the above-described problems. Disclosure of Invention An object of the present invention is to provide a curable composition capable of forming a coating (film) having high hardness, flexibility, and low curling property on surfaces of various substrates with excellent coating properties, and a cured film for hard coating having excellent chemical resistance. will be.

<How to solve the problem>

According to the present invention, the following curable compositions, cured products and laminates are provided:

Based on the total amount of the composition excluding the solvent

(A) 5 to 70% by weight of metal oxide particles bonded to an organic compound containing a polymerizable unsaturated group; And (B) 20 to 50% by weight of a curable composition comprising a compound represented by the formula (1).

In the formula, R ^1, R ² and R ³ are independently a monovalent represents an organic group, and R ^1, R ^2, R ³ and at least two of the _{^{-R 4 OCOCR 5 = CH 2,}} R 4 is C 2 To bivalent organic group of 8 to 8, R ⁵ represents a hydrogen atom or a methyl group.

EFFECTS OF THE INVENTION [

According to the present invention, there is provided a curable composition having excellent coating properties and having a high hardness, a low curling property, and excellent curvature on the surface of a substrate, and a cured film comprising a cured product of the composition. can do.

BEST MODE FOR CARRYING OUT THE INVENTION [

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the curable composition of this invention, the hardened | cured material of a curable composition, and laminated body is demonstrated concretely.

I. Curable Compositions

The curable composition of the present invention comprises (A) 5 to 70% by weight of metal oxide particles to which an organic compound containing a polymerizable unsaturated group is bonded; And (B) 20 to 50% by weight of a compound comprising a structure represented by the following formula (1) (the amount of each component is based on the total amount of the composition excluding the solvent).

&Lt; Formula 1 >

In the above formula, R ¹ , R ² and R ³ independently represent a monovalent organic group, at least two of R ¹ to R ³ represent —R ⁴ OCOCR ⁵ ═CH ₂ , and R ⁴ represents an ethylene residue or a propylene residue. R <^5> represents a hydrogen atom or a methyl group, n represents the integer of 2-8.

Hereinafter, each component of the curable composition of this invention is demonstrated concretely.

1. Metal oxide particles (A) to which an organic compound having a polymerizable unsaturated group is bound

Component (A) used in the present invention is a particle produced by combining metal oxide particles (Aa) and an organic compound (Ab) having a polymerizable unsaturated group (hereinafter referred to as "reactive particles"). Components (Aa) and (Ab) can be bound by non-covalent bonds such as covalent bonds or physical adsorption.

(1) metal oxide particles (Aa)

The metal oxide particle (Aa) used for this invention is not specifically limited. In view of the hardness and colorlessness of the cured film of the resulting curable composition, the metal oxide particles (Aa) are metals of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It is preferable that it is an oxide particle.

Examples of the metal oxide particles (Aa) include silica particles, alumina particles, zirconia particles, titanium oxide particles, zinc oxide particles, germanium oxide particles, indium oxide particles, tin oxide particles, antimony-containing tin oxide (ATO) particles, Tin-containing indium oxide (ITO) particles, antimony oxide particles, cerium oxide particles, and the like. Among them, from the viewpoint of high hardness, silica particles, alumina particles, zirconia particles, and antimony oxide particles are preferable, and silica particles are particularly preferable. By using oxide particles of zirconium or titanium, a cured film having a high refractive index can be obtained. By using ATO particles or the like, conductivity can be provided to the cured film. These particles can be used alone or in combination of two or more thereof. The oxide particles (Aa) are preferably in the form of powder or dispersion. In the case of using the oxide particles (Aa) in the form of a dispersion, the dispersion medium is preferably an organic solvent in view of compatibility and dispersibility with other components. Examples of the 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, γ-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; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. In particular, 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 metal oxide particles (Aa) measured by electron microscopy is preferably 0.001 µm to 2 µm, more preferably 0.001 µm to 0.2 µm, particularly preferably 0.001 µm to 0.1 µm. When the number average particle diameter exceeds 2 µm, the transparency of the resulting cured product may be lowered, or the surface state of the resulting film may deteriorate. Various surfactants and amines can be added to improve the dispersibility of the particles.

Commercially available products of colloidal silica (silica particles) include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST- 20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL (made by Nissan Chemical Industries, Ltd.) etc. are mentioned. Commercially available products of powdered silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 (Nippon Aerosil Co., Limited (Nippon Aerosil) Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (manufactured by Asahi Glass Co., Ltd.), E220A, E220 (Nisbon silica) Industrial Co., Ltd. (manufactured by Nippon Silica Industrial Co., Ltd.), SYLYSIA 470 (manufactured by Fuji Silysia Chemical, Ltd.), SG Flake (Nippon Sheet) Glass Co., Ltd. (made by Nippon Sheet Glass Co., Ltd.), etc. are mentioned.

The water dispersion products of alumina include Alumina Sol-100, -200, -520 (made by Nissan Chemical Industries, Ltd.); The isopropanol dispersion of alumina is AS-150I (manufactured by Sumitomo Osaka Cement Co., Ltd.); Toluene dispersion of alumina is AS-150T (Sumitomo Osaka Cement Co., Ltd.); Toluene dispersions of zirconia are HXU-110JC (Sumitomo Osaka Cement Co., Ltd.); Water products of the zinc antimonate powder include Celnax (Nissan Chemical Industries, Ltd.); Solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide are commercially available from NanoTek (manufactured by C.I. Kasei Co., Ltd.); The water dispersion sol of antimony dope tin oxide is marketed as SN-100D (made by Ishihara Sangyo Kaisha, Ltd.); ITO powder is commercially available from Mitsubishi Materials Corporation; The cerium oxide aqueous dispersion is commercially available as Nedral (manufactured by Taki Chemical Co., Ltd.).

The shape of the metal oxide particles (Aa) may be spherical, hollow, porous, rod, plate, fibrous, or amorphous. The metal oxide particles (Aa) are preferably spherical. The specific surface area (measured by the BET method using nitrogen) of the metal oxide particles (Aa) is preferably 10 to 1000 m 2 / g, more preferably 100 to 500 m 2 / g. The metal oxide particles (Aa) can be used in the form of a dry powder or as a dispersion in water or an organic solvent. As the dispersion of the metal oxide particles (Aa), dispersions of fine metal oxide particles known in the art can be used. It is preferable to use the dispersion liquid of a metal oxide particle for the use which requires the outstanding transparency to the produced hardened | cured material.

(2) organic compound (Ab)

The organic compound (Ab) used for this invention is a compound which has a polymerizable unsaturated group. Preferably, the organic compound (Ab) further contains a group represented by the following formula (2). Preferably, the organic compound (Ab) is one of a [-OC (= O) -NH-] group and a [-OC (= S) -NH-] group and a [-SC (= O) -NH-] group. It contains the above. Preferably, an organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis.

In the formula, U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S.

(i) Polymerizable Unsaturated group

The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited. Preferable examples of the polymerizable unsaturated group include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group.

The polymerizable unsaturated group is a structural unit that causes addition polymerization in the presence of active radical species.

( ii ) As Formula 2 Displayed

The group [-UC (= V) -NH-] included in the organic compound and represented by the formula (2) is [-OC (= O) -NH-], [-OC (= S) -NH-], [- SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], or [-SC (= S) -NH-] to be. These groups can be used individually or in combination of 2 or more types. In particular, at least one of a [-0-C (= 0) -NH-] group, a [-OC (= S) -NH-] group, and a [-SC (= 0) -NH-] group in terms of thermal stability. It is preferable to use together.

The group [-UC (= V) -NH-] represented by the above formula (2) generates moderate cohesive force by hydrogen bonding between molecules, thereby providing excellent mechanical strength, adhesion to adjacent layers such as a substrate or a high refractive index layer, It is considered to provide a cured product having heat resistance and the like.

( iii ) Silanol group  Or by hydrolysis Silanol groups Forming machine

The organic compound (Ab) is preferably a compound having a silanol group in the molecule or a compound which forms a silanol group by hydrolysis. As a compound which forms such a silanol group, the compound which the alkoxy group, the aryloxy group, the acetoxy group, the amino group, the halogen atom, etc. couple | bonded with the silicon atom is mentioned. In particular, the compound which the alkoxy group or the aryloxy group couple | bonded with the silicon atom, especially the alkoxy silyl group containing compound or the aryloxy silyl group containing compound is preferable.

The silanol group formation site of the silanol group or the compound forming the silanol group is a structural unit bonded to the oxide particles (Aa) by condensation generated after condensation or hydrolysis.

( iv ) Preferred Embodiments

As a preferable example of an organic compound (Ab), the compound represented by following formula (3) is mentioned.

In formula (3), R ⁶ and R ⁷ individually represent a hydrogen atom or an alkyl or aryl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a phenyl group, or a xylyl group. Here j is an integer of 1-3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _{3 - j} Si-] include a trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, and dimethylmethoxy Silyl groups; and the like. Among these, trimethoxysilyl group or triethoxysilyl group is preferable.

R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a linear, branched or cyclic structure. Specific examples of such organic groups include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.

R ⁹ represents a divalent organic group selected from divalent organic groups having a molecular weight of 14 to 100,000, preferably 76 to 500. Specific examples of such organic groups include linear polyalkylene groups such as hexamethylene, octamethylene, and dodecamethylene; Alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; Divalent aromatic groups such as phenylene, naphthylene, biphenylene, and polyphenylene; And alkyl or aryl substitution products of these groups. These divalent organic groups may include atomic groups containing elements other than carbon atoms and hydrogen atoms, and may include polyether bonds, polyester bonds, polyamide bonds, and polycarbonate bonds.

R ¹⁰ represents a (k + 1) valent organic group, and is preferably selected from linear, branched, cyclic saturated hydrocarbon groups and unsaturated hydrocarbon groups.

Z represents a monovalent organic group containing in the molecule a polymerizable unsaturated group which causes an intermolecular crosslinking reaction in the presence of an active radical species. k is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, particularly preferably an integer of 1 to 5.

Specific examples of the compound represented by the formula (3) include compounds represented by the following formulas (4-1) and (4-2).

In the above formula, "Acryl" represents acryloyl group and "Me" represents a methyl group.

The organic compound (Ab) used for this invention can be synthesize | combined by the method disclosed by Unexamined-Japanese-Patent No. 9-100111, for example. Preferably, the organic compound (Ab) is reacted with mercaptopropyltrimethoxysilane and isophorone diisocyanate in the presence of dibutyltin dilaurate at 60 to 70 ° C. for several hours, and pentaerythritol triacrylate. Is added to the reaction product and further prepared by reacting the mixture at 60-70 ° C. for several hours.

(3) reactive particles (A)

The organic compound (Ab) having a silanol group or a group which forms a silanol group by hydrolysis is mixed with the metal oxide particles (Aa) and hydrolyzed to combine the metal oxide particles (Aa) and the organic compound (Ab). The amount of the organic polymer component (i.e., hydrolyzate and condensate of the hydrolyzable silane) in the produced reactive particles (A) is the amount of weight loss (%) when the dry powder is completely burned in air, for example air It can measure by thermal mass spectrometry from room temperature to 800 degreeC in the inside.

The amount of the organic compound (Ab) bonded to the oxide particles (Aa) is preferably 0.01% by weight or more, more preferably 100% by weight of the reactive particles (A) (the sum of the metal oxide particles (Aa) and the organic compound (Ab)). Preferably it is 0.1 weight% or more, Especially preferably, it is 1 weight% or more. When the amount of the organic compound (Ab) bonded to the metal oxide particles (Aa) is less than 0.01% by weight, the dispersibility of the reactive particles (A) in the composition is not sufficient, so that the resulting cured product has sufficient transparency and scratch resistance. You can't. The amount of the metal oxide particles (Aa) in the raw materials for the production of the reactive particles (A) is preferably 5 to 99% by weight, more preferably 10 to 98% by weight. The content of the oxide particles (Aa) in the reactive particles (A) is preferably 65 to 90% by weight.

The amount (content) of the reactive particles (A) in the curable composition is 100% by weight of the total composition excluding the organic solvent, preferably 5 to 70% by weight, more preferably 30 to 60% by weight, particularly preferably Is 40 to 60% by weight. If the amount is less than 5% by weight, the hardness of the cured product may be insufficient. When the amount exceeds 70% by weight, film formability may be inhibited. The amount of reactive particles (A) means solids. When the reactive particles (A) are used in the form of a dispersion, the amount of the reactive particles (A) does not include the amount of the dispersion medium.

2. Compound (B)

The compound (B) used for this invention is a compound represented by following formula (1).

&Lt; Formula 1 >

In said formula, R <^1> , R <^2> and R <^3> represent a monovalent organic group independently, Two or more of R <^1> , R <^2> and R <^3> is -R <^4> OCOCR < ⁵ > CH <_2> , R <^4> is C2-C 8 is a divalent organic group, preferably an organic group having 2 to 4 carbon atoms, particularly preferably -CH ₂ CH _2- , and R ⁵ represents a hydrogen atom or a methyl group.

Compound (B) reduces the warpage of the cured film obtained by curing the composition of the present invention and imparts flexibility to the cured film.

Specific examples of the compound (B) that can be used in the present invention include bis ((meth) acryloxymethyl) hydroxymethyl isocyanurate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, tris ( (Meth) acryloxymethyl) isocyanurate, tris ((meth) acryloxyethyl) isocyanurate, caprolactone modified tris ((meth) acryloxyethyl) isocyanurate, etc. are mentioned. Of these, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate and tris ((meth) acryloxyethyl) isocyanurate are preferable.

Commercially available products which can be suitably used as the compound (B) include M-215, M-315, and M-325 (above, manufactured by Toagosei Co., Ltd.), TEICA (above, Daiichi Kogyo Co., Ltd.) Seiyaku Co., Ltd. (made by Daiichi Kogyo Seiyaku Co., Ltd.), TAIC, TMAIC (above, Nippon Kasei Chemical Co., Ltd.), etc. are mentioned. These compounds may be used alone or in combination of two or more.

The amount of the compound (B) used in the present invention is 100% by weight of the total amount of the composition excluding the organic solvent, preferably 20 to 50% by weight, more preferably 30 to 40% by weight. If the amount is less than 20% by weight, the resulting cured film can be curled. When the amount exceeds 50% by weight, the hardness of the cured film may be insufficient.

The compound (B) is preferably at least 40% by weight, more preferably at least 50% by weight, particularly preferably at least 60% by weight with respect to 100% by weight of all (meth) acrylate components other than component (A) in the composition. to be. When the content of component (B) is at least 40% by weight, the warpage of the resulting cured film can be effectively reduced. The total (meth) acrylate component other than component (A) herein refers to the (meth) acrylate component included in all of the soluble components except component (A) which is insoluble particles. Specifically, the total (meth) acrylate component refers to component (B) and the total amount of components (C) and (D) (components (C) and (D) are described below).

3. Urethane ( Mat ) Acrylate  (C)

The composition of this invention may contain (C) urethane (meth) acrylate as needed. Preferably, compound (C) is used to improve the flexibility of the resulting cured film.

Urethane (meth) acrylate (C) is not specifically limited. Basically, urethane (meth) acrylate (C) is obtained by making (a) polyisocyanate compound and (b) hydroxy group containing (meth) acrylate monomer react. The urethane (meth) acrylate has another oligomer as a main chain, and the (meth) acrylate may be bonded thereto through a urethane bond.

The urethane (meth) acrylate has two or more (meth) acryloyl groups, preferably four or more, and more preferably six or more. Such urethane (meth) acrylates generally have a structure in which a hydroxyl group-containing (meth) acrylate monomer (b) is bonded to each isocyanate group of the polyisocyanate compound (a) having 2 to 6 isocyanate groups.

Urethane (meth) acrylate represented by the following formula (5) does not significantly affect the hardness of the cured film can improve the bendability and curling resistance.

In the above formula, "Acryl" represents an acryloyl group.

Urethane (meth) acrylate (C) used by this invention may be synthesize | combined, and a commercial item may be used. Urethane (meth) acrylate (C) is manufactured as follows.

A vessel equipped with a stirrer is charged with a polyisocyanurate compound and dibutyltin dilaurate (0.001 equivalent to 1 equivalent of isocyanurate group). Thereafter, the reaction solution is cooled to 10 ° C to 15 ° C while stirring. A small amount of the (meth) acrylate compound containing a hydroxyl group is added while maintaining the reaction solution at about 50 ° C or lower. After the addition of the hydroxyl group-containing (meth) acrylate compound, the temperature of the reaction solution was raised to 65 ° C and stirred for 1 hour. The reaction solution is subjected to FT-IR measurement to terminate the reaction when the residual isocyanurate content is 0.2% by weight or less. The polyisocyanurate compound and the hydroxy group-containing (meth) acrylate monomer are used so that the hydroxy group of the (meth) acrylate monomer containing a hydroxy group is 1.0 to 2 equivalents to 1 equivalent of the isocyanurate group of the polyisocyanurate compound. do.

As a commercial item of a urethane (meth) acrylate (C), Beamset 102, 502H, 505A-6, 510, 550B, 551B, 575 manufactured by Arakawa Chemical Industries, Ltd. , 575CB, EM-90, EM92, Photomer 6008 and 6210, manufactured by SAN NOPCO, Ltd., Shin-Nakamura Chemical Co., Ltd. NK OLIGO U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, and U-6H, Doagosei Co., Ltd.). , Aronix M-1100, M-1200, M-1210, M-1310, M-1600, and M-1960, Kyoeisha Chemical Co., Ltd. AH-600, AT606, and UA-306H, Nippon Kayaku Co., Ltd., manufactured by Kayarad UX-2201, UX-2301 , UX-3204, UX-3301, UX-4101, UX-6101, and UX-7101, Nippon Synthetic Chemical Industries UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, and UV-2010B, Negami Chemical Industrial Co., manufactured by Nippon Synthetic Chemical Industry Co., Ltd. , Artresin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN manufactured by Negami Chemical Industrial Co., Ltd. -3320HC, UN-3320HS, H-61, and HDP-M20, Ebecryl 6700, 204, 205, 220, 254, 1259, manufactured by Daicel UBC Co Ltd. 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301 and the like. Among these, U-6HA is preferable as the urethane (meth) acrylate having three or more (meth) acrylate groups.

The amount of the compound (C) used in the present invention is 100% by weight of the total amount of the composition excluding the organic solvent, preferably 5 to 20% by weight, more preferably 5 to 10% by weight. If the amount exceeds 20% by weight, the hardness of the resulting cured film may be insufficient.

4. Multifunctional  ( Mat ) Acrylate  Compound (D)

The composition of this invention may contain (D) polyfunctional (meth) acrylate as needed. The polyfunctional (meth) acrylate compound (D) is a (meth) acrylate monomer containing two or more polymerizable unsaturated groups in a molecule, and is a component other than components (A), (B) and (C). The polyfunctional (meth) acrylate compound is suitably used to improve the curability and hardness of the resulting cured film. As used herein, the expression "multifunctional" means a (meth) acrylate compound containing two or more (meth) acryloyl groups in a molecule. In view of film forming property and hardness, a trifunctional or higher (meth) acrylate compound is preferable, and a tetrafunctional or higher (meth) acrylate compound is more preferable.

Preferable examples of the polyfunctional (meth) acrylate compound (D) include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.

A polyfunctional (meth) acrylate compound (D) can also be synthesize | combined and can use a commercial item. Multifunctional (meth) acrylates are prepared as described below.

Polyfunctional (meth) acrylate compounds are commercially available as Kayarrad DPHA (Nipbon Kayaku Co., Ltd.) and the like.

The amount of the compound (D) used in the present invention is 100% by weight of the total amount of the composition excluding the organic solvent, preferably 5 to 20% by weight, more preferably 10 to 20% by weight. When the amount is more than 20% by weight, the flexibility and curling resistance of the resulting cured film may be insufficient. If the amount is less than 10% by weight, the cured film may exhibit insufficient hardness.

5. Radical  Polymerization Initiator (E)

The composition of this invention can contain (E) radical polymerization initiator as needed.

As an example of a radical polymerization initiator (E), the compound (thermal polymerization initiator) which generate | occur | produces an active radical species thermally, and the compound (radiation (photo) polymerization initiator) which generate | occur | produce an active radical species at the time of radiation (light) irradiation are mentioned. .

The radiation (photo) polymerization initiator is not particularly limited as long as it decomposes upon irradiation with light to generate radicals to initiate polymerization. Examples of radiation (photo) polymerization initiators include acetophenone, acetophenonebenzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-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-2-methyl-1-phenylpropane- 1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethok Benzoyl) -2,4,4- trimethylpentyl phosphine comprises a pin oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), and the like.

As a commercial item of a radiation (photo) polymerization initiator, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, and Darocur 1116, 1173 (manufactured by Ciba Specialty Chemicals Inc.), Lucirin TPO (manufactured by BASF), Ebecryl P36 (manufactured by UCB), Esacure KIP150, KIP65LT , KIP100F, KT37, KT55, KTO46, KIP75 / B (manufactured by Lamberti) and the like.

The radical polymerization initiator (E) used as an optional component in the present invention is 100% by weight of the total composition excluding the organic solvent, preferably in an amount of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight. Used. If the amount is less than 0.01% by weight, the resulting cured product may exhibit insufficient hardness. When the amount exceeds 20% by weight, the inside (lower layer) of the cured product may not be cured.

When hardening the composition of this invention, it can use combining a photoinitiator and a thermal polymerization initiator as needed.

Examples of preferred thermal polymerization initiators include peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butylperoxybenzoate, azobisisobutyronitrile and the like.

6. Organic Solvents (F)

The composition of the present invention may be diluted with an organic solvent (F) to control the thickness of the coating formed using the composition. When using a composition as an antireflection film or coating material, the viscosity of the composition is usually 0.1 to 50,000 mPa sec / 25 ° C, preferably 0.5 to 10,000 mPa sec / 25 ° C.

The organic solvent (F) is not particularly limited. However, since the crystallinity of the compound used as the component (B) is high, it is preferable to use the high boiling point solvent because the composition of the present invention can be uniformly coated. Specific 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, γ-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, xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned. Among them, high boiling point solvents such as methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, toluene, and xylene are preferred.

The amount of the organic solvent (F) in the composition of the present invention is usually 30 to 80% by weight of the total amount of the composition, preferably 40 to 60% by weight. When the amount of the organic solvent (F) is in the range of 30 to 80% by weight, the composition is excellent in coatability.

7. Other Ingredients

Curable compositions of the present invention are photosensitizers, polymerization inhibitors, polymerization aids, leveling agents, wettability modifiers, surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents within a range that does not impair the effects of the present invention. , Inorganic fillers, pigments, dyes and the like.

8. Preparation of Composition

The composition of the present invention is prepared as follows.

A reaction vessel equipped with a stirrer is filled with a reactive particle dispersion, a radiation (photo) polymerization initiator, a polyfunctional (meth) acrylate, and a urethane (meth) acrylate. The mixture is stirred at 35 ° C. to 45 ° C. for 2 hours to obtain a composition of the present invention.

When the solvent is replaced with a solvent (B) different from the solvent (A) used for the reactive particle dispersion, 1.3 times the solvent (B) is also added to the mixture relative to the amount of the solvent (A) of the reactive particle dispersion, so that the mixture is the same. Stir under conditions. Thereafter, the composition solution is concentrated using a rotary evaporator under reduced pressure to the weight before adding the solvent (B) to obtain the composition of the present invention.

9. Application of Composition (Coating)

The composition of this invention is suitable for the use of an antireflection film and a coating material. Examples of the substrate on which the composition is applied include plastics (for example, polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, Norbor) Nene resin), metal, wood, paper, glass, a slate, etc. are mentioned. The shape of the substrate may be a plate, film, or three-dimensional molded body. Coating methods include conventional coating methods such as dipping, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating and the like. The thickness of the coating formed using this coating method is usually 0.1 to 400 mu m, preferably 1 to 200 mu m, after drying and curing.

10. Curing of the composition

The composition of the present invention can be cured by heat and / or radiation (light). When applying heat to cure the composition, the heat source may be an electric heater, an infrared lamp, hot air, or the like. When curing the composition by radiation (light), the source is not particularly limited as long as it can cure the composition in a short time after application. As an example of an infrared ray source, a lamp, a resistance heating plate, a laser, etc. are mentioned. Examples of the source of visible light include daylight, lamps, fluorescent lamps, lasers, and the like. As an example of the ultraviolet light source, a mercury lamp, a halide lamp, a laser, etc. are mentioned. Further examples of the source of electron beams include systems using hot electrons generated from commercially available tungsten filaments, cold cathode systems applying high voltage pulses through metal to generate electron beams, and collision of ionized gaseous molecules with metal electrodes. The secondary electronic system using the secondary electron which generate | occur | produces by is mentioned. In addition, examples of the sources of alpha rays, beta rays, and gamma rays include fission materials such as Co ⁶⁰ . As a source of the α-rays, a vacuum tube or the like which causes the accelerated electrons to collide with the anode can be used. Radiation can be used individually or in combination of 2 or more types. In the latter case, two or more types of radiation may be irradiated simultaneously or at regular intervals.

The curing reaction of the composition of the present invention can be carried out under anaerobic conditions such as in air or a nitrogen atmosphere. Even when the composition of the present invention is cured under anaerobic conditions, the resulting cured product has excellent scratch resistance.

II . Cured product

The cured product of the present invention can be obtained by applying a curable composition to various substrates such as a plastic substrate and curing the applied composition. Specifically, after the composition was applied to the substrate, the volatile components were preferably dried at a temperature of 0 to 200 ° C, and cured by curing the composition with heat and / or radiation to obtain a coating molded product. When the composition is cured by heat treatment, the composition is preferably cured at 20 to 150 ° C. for 10 seconds to 24 hours. In the case of curing by radiation treatment, it is preferable to use ultraviolet rays or electron beams. In such a case, the irradiation light amount of the ultraviolet ray is preferably 0.01 to 10 J / cm 2, more preferably 0.1 to 2 J / cm 2. The irradiation of the electron beam is preferably treated with a pressurized voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mA / cm 2, and an irradiation amount of 1 to 10 Mrad.

The cured product of the present invention has a high hardness, a small curling property, excellent flexibility, and can form a coating (film) excellent in scratch resistance and adhesion to an adjacent layer such as a substrate or a high refractive index layer. Cargo is especially suitable as an antireflection film, such as a film type liquid crystal element, a touch panel, a plastic optical component.

III . Laminate

Moreover, this invention relates to the laminated body containing hardened | cured material.

The cured product of the present invention is usually laminated on a substrate as a hard coating layer. A laminate preferable as an antireflection film can be formed on a cured film (hard coating layer) by laminating a high refractive index layer and a low refractive index layer. The antireflective film may further include layers other than these layers. For example, a combination of a high refractive index layer and a low refractive index layer can be provided to form a wide band anti-reflection layer having relatively uniform reflectance characteristics for light in a wide wavelength range. Alternatively, an antistatic layer can be provided.

There is no restriction | limiting in particular as a base material. In the case of using a laminate as an antireflection film, plastic (for example, polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS Resin, norbornene resin), etc. are mentioned as a base material.

As an example of the high refractive index film used for the laminated body of this invention, the film whose refractive index is 1.65-2.20 like the coating material cured film containing metal oxide particles, such as a zirconia particle, is mentioned.

Examples of the low refractive index film used in the present invention include a film having a refractive index of 1.38 to 1.45, such as a metal oxide film or a fluorine-based coating material cured film containing magnesium fluoride or silicon dioxide.

As a method of forming a low refractive index film on the high refractive index cured film obtained by hardening | curing a curable composition, when forming a metal oxide film, vacuum vapor deposition, sputtering, etc. are mentioned. When forming a fluorine-type coating material cured film, the method similar to the coating (coating) method of a composition is mentioned.

By laminating a high refractive index cured film and a low refractive index film on a substrate, reflection of light on the surface of the substrate can be effectively prevented.

Since the laminate of the present invention has high hardness, small curling property, excellent bendability, low reflectance, and excellent chemical resistance, the laminate can prevent reflection of film type liquid crystal elements, touch panels, plastic optical parts, and the like. It is especially suitably used as a film.

Hereinafter, an Example is shown and this invention is demonstrated further more concretely. However, the scope of the present invention is not limited to the description of the following examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

Manufacturing example  One: Polymerizable Unsaturated groups  Preparation of Organic Compound (Ab) Containing

To the solution of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate were added dropwise at 50 ° C for 1 hour with stirring. Stir at 70 ° C. for 3 hours. Contains NK ester A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd .; 60 wt% pentaerythritol triacrylate and 40 wt% pentaerythritol tetraacrylate; pentaeryte having a hydroxy group Only itol triacrylate was involved in the reaction) 549 parts were added dropwise at 30 ° C. for 1 hour, and then the mixture was heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) having a polymerizable unsaturated group. The residual isocyanate content in the product was analyzed by FT-IR and found to be 0.1% or less. This indicated that the reaction was almost quantitatively terminated. In the infrared absorption spectrum of the product, the absorption peak of the 2550 kaiser characteristic of the mercapto group in the raw material and the absorption peak of the 2260 kaiser characteristic of the raw isocyanate compound are lost, and the 1660 characteristic of the urethane bond and the S (C═O) NH-group The peak of Kaiser and the peak of 1720 Kaiser characteristic of the acryloyl group were observed. It was shown that an acryloxy group, -S (C = 0) NH-, and a urethane bond as an acryloxy group-modified alkoxysilane as a polymerizable unsaturated group were produced. The reaction yielded compounds represented by Formulas 4-1 and 4-2. 220 parts of pentaerythritol tetraacrylate not involved in the reaction were contained.

Manufacturing example  2: urethane ( Mat ) Acrylate  Preparation of (C-2)

A vessel equipped with a stirrer was charged with a solution of 18.8 parts of isophorone diisocyanate and 0.2 parts of dibutyltin dilaurate. 93 parts of NK ester A-TMM-3LM-N (manufactured by Shinnakamura Chemical Co., Limited; only pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) was added dropwise at 10 ° C. in 1 hour, and then the mixture was 60 ° C. After stirring for 6 hours to obtain a reaction solution.

In the same manner as in Preparation Example 1, the residual isocyanate content in the reaction solution was measured by FT-IR, and the result was 0.1 wt% or less. This indicated that the reaction was almost quantitatively completed. It was confirmed that the urethane bond and the acryloyl group (polymerizable unsaturated group) were contained in the molecule.

The reaction yielded 75 parts of a compound represented by formula (5). In addition, 37 parts of pentaerythritol tetraacrylate not involved in the reaction were contained.

Manufacturing example  3: Preparation of Silica Particle Dispersion

(i) Preparation of Colloidal Silica Dispersed in Methanol

Water-disperse colloidal silica (Snowtex-O manufactured by Nissan Chemical Industries, Limited; solid content: 20% by weight, pH: 2.7, specific surface area measured by BET method: 226 m 2 / g, Silanol concentration on silica particles as determined by methyl red adsorption: 4.1 x 10 ^-5 mol / g, metal content in solvent as determined by atomic absorption method: Na; 4.6 ppm, Ca; 0.013 ppm, K; 0.011 ppm) 30 kg Was charged to the tank. The colloidal silica was heated to 50 ° C. and the ultrafiltration membrane module (manufactured by Tri Tec Corporation) and the alumina ultrafiltration membrane (NGK Insulators, NGK Insulators, at a circulation rate of 50 liters / minute and a pressure of 1 kg / cm 2) &Quot; Ceramic UF Element &quot;, specification: 4 mm phi, 19 holes, length 1 m, fractional molecular weight = 150,000, membrane area = 0.24 m 2). After 30 minutes, 10 kg of filtrate was discharged to obtain a residue having a solid content of 30% by weight. The average permeation flow rate (unit area of the ultrafiltration membrane, membrane permeation weight per unit time) before concentration was 90 kg / m 2 / hour. After concentration, the average permeate flow rate was 55 kg / m 2 / hour. The number average particle diameter before and after concentration measured by the dynamic light scattering method was 11 nm.

After 14 kg of methanol was added, the mixture was concentrated using the ultrafiltration membrane module and the ultrafiltration membrane at 50 ° C., a circulation flow rate of 50 liters / minute, and a pressure of 1 kg / cm 2, and 14 kg of the filtrate was discharged. The above steps were repeated six times, and the colo dispersed in methanol having a solid content of 30% by weight, a water content measured by the Karl Fisher method, 1.5% by weight, and a number average particle diameter of 11 nm measured by the dynamic light scattering method. 20 kg of silica was prepared this month. The average permeation flow rate of six times was 60 kg / m 2 / hour, and the time required was 6 hours. The specific surface area measured by the BET method of the colloidal silica dispersed in obtained methanol was 237 m <2> / g. Silane concentration of olgi of the silica particles determined by methyl red adsorption method was 3.5 × 10 ^- was ⁵ mol / g.

(ii) Preparation of Hydrophobic Colloidal Silica Dispersed in Methyl Ethyl Ketone

To 20 kg of colloidal silica dispersed in methanol prepared in Preparation Example 1, 0.6 kg of trimethyl methoxysilane (manufactured by Toray-Dow Corning Silicone Co., Ltd.) was added. The mixture was stirred with heating at 60 ° C. for 3 hours. The number average particle diameter measured by the dynamic light scattering method was 11 nm, which was the same value as before stirring. The specific surface area measured by the BET method of hydrophobic colloidal silica dispersed in the obtained methanol was 240 m 2 / g. Silanol group concentration on the silica particles determined by a methyl red adsorption method was 2.1 × 10 ^- was ⁵ mol / g.

After addition of 14 kg of methyl ethyl ketone, the mixture was concentrated using the ultrafiltration membrane module and the ultrafiltration membrane at 50 ° C., a circulation flow rate of 50 liters / minute, and a pressure of 1 kg / cm 2, to discharge 14 kg of filtrate. . This step was repeated five times, the solid content was 30% by weight, the amount of water measured by Karl Fischer method, 0.3% by weight, the methanol content measured by gas chromatography (GC) was 3.2% by weight, and measured by dynamic light scattering method. 20 kg of hydrophobic colloidal silica (silica particle dispersion) dispersed in methyl ethyl ketone having a number average particle diameter of 11 nm were prepared. The average permeation flow rate of five times was 70 kg / m 2 / hour, and the time required was 4 hours. The specific surface area measured by the BET method of the colloidal silica dispersed in the obtained methyl ethyl ketone was 230 m 2 / g. Silane concentration of olgi on the silica particles determined by a methyl red adsorption method was 1.8 × 10 ^- was ⁵ mol / g. The metal content in the solvent of the hydrophobic colloidal silica dispersed in methyl ethyl ketone measured by atomic absorption method was very small, 0.05 ppm Na, 0.001 ppm Ca, K.

Manufacturing example  4: Preparation of Reactive Silica Particle Dispersion (A-1)

2.32 parts of organic compounds (Ab) containing a polymerizable unsaturated group prepared in Production Example 1, 89.90 parts of silica particle dispersion (Aa) (silica concentration: 32%) prepared in Production Example 3, 0.12 parts of ion-exchanged water, and p A liquid mixture of 0.01 part of hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 4 hours. After adding 1.36 parts of methyl orthoformate, the mixture was stirred at the same temperature for 1 hour to obtain reactive particles (dispersion (A-1)). 2 g of the dispersion (A-1) was weighed into an aluminum dish and dried for 1 hour on a hot plate at 175 ° C. The dry matter was weighed to obtain a solid content, which was 30.7%. 2 g of the dispersion (A-1) was weighed into a magnetic crucible, pre-dried for 30 minutes on a hot plate at 80 ° C, and calcined for 1 hour in a muffle at 750 ° C. The inorganic content in the solid was measured from the resulting inorganic residue, and the inorganic content was 90%.

Example  One

(1) Preparation of Curable Composition

176.74 parts of reactive silica particle dispersion (A-1) prepared in Production Example 4 (54.26 parts as reactive particles (A), 48.6 parts of silica particles (Aa) and 5.67 parts by mass of organic compound (Ab) bonded to silica particles) ), 31.28 parts of tris (acryloxyethyl) isocyanurate (B-1), 6.05 parts of urethane acrylate (C-2) prepared in Production Example 2 represented by the formula (5), (D-2) pentaeryte 4.64 parts of lithol tetraacrylate, 2.36 parts of 1-hydroxycyclohexyl phenyl ketone (E-1), and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 ( E-2) 1.41 parts and 159.22 parts of methyl isobutyl ketone (MIBK) were stirred at 40 degreeC for 2 hours, and the uniform solution was obtained. The resulting solution was concentrated using a rotary evaporator under reduced pressure until the amount of the solution was 222.48 parts, thereby substituting the solvent with MIBK principal to obtain a uniform composition solution. Pentaerythritol tetraacrylate (D-2) is derived from pentaerythritol tetraacrylate in organic compounds (Ab) and urethane (meth) acrylates (C-2). It was 45% when the solid content of this composition was calculated | required.

(2) antireflection film Of the laminate  Produce

The composition obtained in (1) was apply | coated so that the thickness might be 20 micrometers after drying using a bar coater on the base material. The composition was dried in a hot air dryer at 100 ° C. for 1 minute, and then irradiated with a light amount of 300 mJ / cm 2 using a conveyor mercury lamp to obtain a cured film. Flexibility and curling properties were evaluated using the resulting cured film. The results are shown in Table 1 below. In the same manner as described above, a cured film having a thickness of 31 μm was formed after drying using a bar coater on the slide, and the resulting cured film was subjected to the universal hardness test.

A slide having a thickness of 1 mm as a substrate was used for the universal hardness test, and a triacetyl cellulose (TAC) film having a thickness of 81 μm as the substrate was used for evaluation of flexibility and curling.

Example  2 to 4 and Comparative example  1 and 2

A composition was prepared in the same manner as in Example 1 except for using the composition shown in Table 1.

Evaluation of Cured Film

The cured film evaluation method is shown below. The evaluation results are shown in Table 1.

Flexibility, semi-culling property, and universal hardness in the cured films obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured or evaluated according to the method shown below.

(One) Curling property

The cured film formed on the triacetyl cellulose film (15 × 15 cm) was cut into 10 × 10 cm squares and stored for 1 hour at room temperature 25 ° C. and humidity 50%. The thickness of the cured film was measured using a thickness gauge, and a cured film having a film thickness of 20 ± 2 μm was used for curling test. In the curling test, the cured film was placed on a glass plate, and the rise of each corner of the cured film and the glass plate was measured with a ruler. The four corner injuries were taken as curling values.

Evaluation 5: 0 mm to 5 mm

Evaluation 4: 6 mm to 10 mm

Evaluation 3: 11 mm to 15 mm

Evaluation 2: 16 mm to 20 mm

Evaluation 1: 21 mm or more

(2) flexibility

The 10 x 10 cm cured film obtained by the method described in the above (1) was cut into strips having a width of 1 cm, and the strip film was used for the flexibility test. The strip-like film was slowly wound around the cylinders of different diameters and slowly returned. The minimum diameter at which cracking did not occur was taken as the flexibility value.

Evaluation 3: 1 mm to 5 mm

Evaluation 2: 6 mm to 10 mm

Evaluation 1: 11 mm or more

(3) universal hardness

The thickness of the cured film formed on the slide by the method described in (1) was measured using a DEK-TAK tester (WIN-HCU manufactured by Fischer Ltd.). The universal hardness test was performed at the portion where the film thickness was 31 ± 2 μm. In the measurement of the universal hardness test, a load of 300 mN / cm 2 was applied to the film over 60 seconds, then the load was maintained for 5 seconds and the load was reduced over 60 seconds. Vickers squeezers were used as squeezers.

Evaluation 4: universal hardness 370 mN / mm2 or more

Evaluation 3: Universal Hardness 351 mN / mm 2 to 370 mN / mm 2

Evaluation 2: Universal Hardness 331 mN / mm 2 to 350 mN / mm 2

Evaluation 1: Universal Hardness 300 mN / mm 2 to 330 mN / mm 2

Amount (% by weight) Example Comparative example One 2 3 4 One 2 Composition Component (A) A-1 54.26 42.31 42.31 54.26 42.31 30.37 Component (B) B-1 31.28 22.44 33.66 23.46 18.85 58.40 Component (C) C-1 11.22 11.22 7.82 11.22 C-2 6.05 4.72 4.72 6.05 4.72 3.37 Component (D) D-1 11.22 14.81 D-2 4.64 3.62 3.62 4.64 3.62 2.58 Component (E) E-1 2.36 2.79 2.79 2.36 2.79 3.30 E-2 1.41 1.68 1.68 1.41 1.68 1.98 system 100.00 100.00 100.00 100.00 100.00 100.00 (B) / [(B) + (C) + (D)] (%) 78.08 43.39 65.08 58.56 36.45 92.24 Ingredient (F)
Organic solvent MEK 12.25 122.48 122.48 122.48 122.48 12.25 MIBK 110.23 110.23 Curing film Curing atmosphere air air air air air air Thickness of Cured Film (μm) 20 20 20 20 20 20 Universal hardness 4 4 3 3 3 One Curling property 5 5 5 5 4 5 Flexibility 2 2 3 One One 3

In Table 1, the quantity of reactive silica particle (A-1) shows the fine powder dry weight (excluding organic solvent).

The abbreviated content of Table 1 is shown below.

A-1: Reactive Silica Particles Obtained in Production Example 4

B-1: tris (acryloxyethyl) isocyanurate (Toagosei Co., Ltd. make)

C-1: U-6HA (Shin-Nakamura Chemical Co., Ltd.)

C-2: Compound represented by Formula 5 prepared in Preparation Example 2

D-1: dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)

D-2: pentaerythritol tetraacrylate (from NK ester A-TMM-3LM-N manufactured by Shinnakamura Chemical Co., Ltd.)

E-1: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals Inc.)

E-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (irgacure 907; manufactured by Ciba Specialty Chemicals Inc.)

MEK: Methyl Ethyl Ketone

MIBK: Methyl Isobutyl Ketone

From the results of Table 1, it can be seen that the cured product of the curable resin composition of the present invention exhibits curling property, flexibility, and hardness in a balanced manner.

As described above, since the curable composition and the cured product of the present invention have high hardness, low curling property and excellent flexibility, they are used as plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, and building interior materials. Protective coatings for preventing scratches or contamination of floors, walls and artificial marble; Anti-reflection films for film type liquid crystal elements, touch panels, or plastic optical components; Adhesives or sealing materials for various substrates; It may be suitable for use as a binder for printing inks and the like. In particular, the cured composition and the cured product can be suitably used as antireflection films.

Claims (10)

Based on the total amount of the composition excluding the solvent (A) 5 to 60% by weight of metal oxide particles bonded with an organic compound containing a group causing addition polymerization in the presence of an active radical species, (B) bis ((meth) acryloxymethyl) hydroxymethyl isocyanurate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, tris ((meth) acryloxymethyl) isocyanurate 20 to 50% by weight of a compound which is tris ((meth) acryloxyethyl) isocyanurate or caprolactone modified tris ((meth) acryloxyethyl) isocyanurate, (C) 5 to 20% by weight of urethane (meth) acrylate, (D) 5 to 20% by weight of a (meth) acrylate monomer compound comprising at least two groups which cause addition polymerization in the presence of active radical species in addition to components (A), (B) and (C), (E) 0.01 to 20% by weight radical polymerization initiator  Including, The organic compound in the particles of component (A) comprises a group of formula (2) in addition to the group causing addition polymerization in the presence of active radical species, <Formula 2>

(Wherein U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S) The organic compound in the particle | grains of the said component (A) is a compound which has a silanol group in a molecule | numerator, or a compound which forms a silanol group by hydrolysis. Curable composition. The curable composition according to claim 1, wherein component (B) is tris ((meth) acryloxyethyl) isocyanurate. The curable composition according to claim 1, wherein component (D) contains dipentaerythritol hexaacrylate. The curable composition of claim 1 comprising the component (B) in an amount of at least 40% by weight of 100% by weight of the total (meth) acrylate component, excluding component (A) in the composition. The cured film manufactured by hardening | curing the curable composition of any one of Claims 1-4. A laminate comprising the cured film of claim 5. delete delete delete delete