KR20050018647A - Curable composition, cured product, and laminate - Google Patents

Abstract

The present invention is prepared by combining (A) an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and an organic compound comprising a polymerizable group Particles;

(B) a compound having a melamine group but no polymerizable unsaturated group; And

The curable composition containing the compound which has two or more polymerizable groups in molecules other than (C) component (B), and the hardened | cured product and laminated body which have low reflectance and excellent chemical-resistance.

Description

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

The present invention relates to curable compositions and cured products and laminates thereof. In particular, the present invention exhibits excellent applicability, and is suitable for plastics (polycarbonates, polymethyl methacrylates, polystyrenes, polyesters, polyolefins, epoxy resins, melamine resins, triacetyl cellulose resins, ABS). Resins, AS resins, norbornene resins, etc.), low hardness layers on the surfaces of various substrates such as metals, wood, paper, glass, and slate, as well as high hardness, high refractive index, good scratch resistance It relates to a curable composition capable of forming a coating (film) having scratch resistance, scratch resistance and excellent adhesion. The present invention also relates to a cured product made of the curable composition and to a laminate having low reflectance and excellent chemical resistance. The curable compositions, cured products, and laminates of the present invention are, for example, made of plastic optical components, touch panels, film-like liquid crystal devices, plastic containers, flooring, walls and artificial marble (used as interior finishing materials for construction). Protective coatings to prevent scratches or contamination; Antireflection films for film type liquid crystal elements, touch panels, and plastic optical components; Adhesives or sealing agents of various substrates; It can be preferably used as an excipient for printing ink and the like. Curable compositions, cured products, and laminates may be particularly suitable as antireflection films.

In recent years, curable compositions exhibiting excellent coating properties and capable of forming cured films excellent in hardness, abrasion resistance, abrasion resistance, low curling property, adhesion, transparency, chemical resistance, and appearance of coating film surfaces have been developed. It is required as a protective coating material for preventing scratches or contamination, as an adhesive or sealant for various substrates, or as an excipient for printing ink.

In addition to the above requirements for curable compositions used as antireflection films for film liquid crystal devices, touch panels, or plastic optical parts, the ability to form cured films of high refractive index is required.

Various compositions have been proposed to satisfy the above needs. However, curable compositions which satisfy the following properties (1) to (3) have not yet been developed: (1) curable compositions having good coatability; (2) a cured film made of the composition having high hardness, high refractive index, excellent scratch resistance, and excellent adhesion to a film and a substrate having a low refractive index; (3) A laminate comprising a cured film having low reflectance and excellent chemical resistance and a film of low refractive index applied thereon.

For example, Japanese Patent Publication No. 2215/1987 proposes the use of a composition containing particles of colloidal silica and an acrylate whose surface has been modified by methacrylooxysilane for a radiation (photo) curable coating material. Radiation curable compositions of this kind are frequently used in recent years because of their excellent coatability and the like.

However, although the laminate formed by applying a low refractive index film to the cured product of the composition exhibited an improved antireflection effect as an antireflection film, the chemical resistance of the laminate was inadequate.

Problems solved by the present invention

The present invention has been made in view of the above problems. It is an object of the present invention to cure a curable composition and a material having a low refractive index and a curable composition capable of forming a coating (film) which exhibits excellent coatability and has high hardness, high refractive index, good scratch resistance and good adhesion to a substrate. To provide a product and a laminate having low reflectance and excellent chemical resistance.

Means to solve the problem

As a result of extensive research for achieving the above object, the present inventors (A) particles produced by combining the oxide particles of a specific element with an organic compound containing a polymerizable group; (B) a compound having a melamine group but no polymerizable unsaturated group; And (C) a curable composition comprising a compound having two or more polymerizable groups in a molecule other than component (B), has been found to be a product which satisfies all these properties.

The curable compositions of the invention and their cured products and laminates will be described in more detail below.

I. Curable composition

The curable composition is (A) an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium (hereinafter referred to as "oxide particles (Aa)"). And particles prepared by combining an organic compound comprising a polymerizable group (hereinafter referred to as "organic compound (Ab)") (hereinafter referred to as "reactive particles (A)" or "component (A)"), (B) a melamine compound having no polymerizable unsaturated group (hereinafter referred to as "compound (B)" or "component (B)") and a compound having two or more polymerizable unsaturated groups in the molecule (C) (hereinafter "compound" (C) "or" component (C) ".

Preferably, the curable composition of the present invention contains a polymerizable group of compounds (A), (B) and (C) which is a polymerizable unsaturated group.

Each component of the curable composition of the present invention will be described in more detail below.

1. Reactive Particles (A)

Reactive particles (A) used in the present invention are polymerizable with oxide particles (Aa) of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It is manufactured by combining the group-containing organic compound (Ab) (the organic compound preferably contains a group represented by the following formula (1)).

(In Formula 1, U represents NH, O (oxygen atom) or S (sulfur atom); V represents O or S).

(1) Oxide Particles (Aa)

In order to obtain a colorless curing coating from the curable composition, the oxide particles (Aa) used in the present invention are one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. It is preferable that it is the oxide particle of the above element.

Examples of the oxide particles (Aa) include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium-tin oxide (ITO), antimony oxide and cerium oxide. Among the above, particles of silica, alumina, zirconia and antimony oxide are preferable from the viewpoint of high hardness. The compounds may be used alone or in combination of two or more thereof. The oxide particles (Aa) are preferably in the form of powder or a solvent dispersion sol. In the case where the oxide particles are in the form of a solvent dispersing sol, the organic solvent is preferably a dispersion medium 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 and 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 and N-methylpyrrolidone. Among the above, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

The number average particle diameter of the oxide particles (Aa) may be 0.001 μm to 2 μm, preferably 0.001 μm to 0.2 μm, and more preferably 0.001 μm to 0.1 μm. When the number average particle diameter exceeds 2 mu m, the transparency of the cured product and the surface conditions of the film tend to be impaired. In addition, various surfactants and amines may be added to improve the dispersibility of the particles.

Among the silicon dioxide particles, examples of commercially available products of silica particles include the trade name Methanol Silica Sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP. And colloidal silicas such as ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL (all manufactured by Nissan Chemical Industries, Ltd.). As the powder silica, trade names AEROSIL 130, AEROSIL 300, AEROSIL 380, AEROSIL TT600 and AEROSIL OX50 (manufactured by Japan Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (Asahi Glass Co. , Ltd.), E220A, E220 (manufactured by Nippon Silica Industrial Co., Ltd.), SYLYSIA470 (manufactured by Fuji Silycia Chemical Co., Ltd.), and SG flake (SG Flake) (manufactured by Nippon Sheet Glass Co., Ltd.) Products may be provided.

Commercially available products of the aqueous dispersion of alumina include Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 (manufactured by Nissan Chemical Industries, Ltd.); Isopropanol dispersion of alumina includes AS-150l (manufactured by Sumitomo Osaka Cement Co., Ltd.); Toluene dispersion of alumina includes AS-150T (manufactured by Sumitomo Osaka Cement Co., Ltd.); Toluene dispersions of zirconia include HXU-110JC (manufactured by Sumitomo Osaka Cement Co., Ltd.); Aqueous dispersions of zinc antimonate powder include Celnax (manufactured by Nissan Chemical Industries, Ltd.); Powders and solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide include Nano Tek (manufactured by CI Kasei Co., Ltd.); Aqueous dispersion solos of antimony dope-tin oxides include SN-100D (manufactured by Ishihara Sangyo Kaisha, Ltd.); ITO powder includes products made by Mitsubishi Material Co., Ltd .; An aqueous dispersion of cerium oxide is Needral (manufactured by Taki Chemical Co., Ltd.).

The oxide particle (Aa) has a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, or an irregular shape, and a spherical shape is preferable. The specific surface area (measured by the BET method using nitrogen) of an oxide particle (Aa) becomes like this. Preferably it is 10-1000 m <2> / g, More preferably, it is 100-500 m <2> / g. Oxide particles (Aa) that can be used herein may be used in the form of a dry powder, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art can be used as the solvent dispersion sol for the oxide. In particular, it is preferable to use the solvent dispersion sol of an oxide in the use which requires the outstanding transparency for a hardened | cured product.

(2) organic compound (Ab)

The organic compound (Ab) used in the present invention is a compound having a polymerizable unsaturated group in a molecule, preferably a specific organic compound containing the group [-U-C (= V) -NH-] represented by the formula (1). Further, the organic compound (Ab) is represented by a group represented by [-OC (= O) -NH-] and represented by [-OC (= S) -NH-] and [-SC (= O) -NH-]. It is preferred to include at least one of the groups. It is preferable that an organic compound (Ab) has a silanol group in a molecule | numerator, or forms a silanol group by hydrolysis.

1) polymerizable unsaturated groups

There is no particular restriction on the preferable polymerizable unsaturated group contained in the organic compound (Ab). Acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group and acrylamide group can be provided as a preferable example.

The said polymerizable unsaturated group is a structural unit for performing addition polymerization by an active radical.

2) a group represented by formula (1)

There are six kinds of groups [-UC (= V) -NH-] of the formula (1) included in certain organic compounds, in particular, [-OC (= O) -NH-], [-OC (= S)- NH-], [-SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-] and [-SC (= S ) -NH-]. The groups may be used alone or in combination of two or more thereof. Among them, one or more of a group [-OC (= O) -NH-] and a group [-OC (= S) -NH-] and [-SC (= O) -NH-] is used in combination. It is preferable to ensure excellent thermal stability.

The group [-UC-(= V) -NH-] of Formula 1 generates a moderate adhesive force by hydrogen bonding in a molecule to produce a cured product having properties such as excellent mechanical strength, excellent adhesion to a substrate, and excellent heat resistance. to provide.

3) silanol groups or groups that produce silanol groups by hydrolysis

The organic compound (Ab) is a compound having a silanol group (hereinafter referred to as a "silanol group-containing compound") or a compound which generates a silanol group by hydrolysis (hereinafter referred to as "silanol group-generating compound"). desirable. The silanol group-generating compound may be provided with a compound having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, etc. on a silicon atom, a compound comprising an alkoxy group or an aryloxy group on a silicon atom, In particular, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.

The silanol group-generating site of the silanol group or silanol group-generating compound is a structural unit that is bonded to the oxide particles (Aa) by a condensation reaction generated following condensation reaction or hydrolysis.

4) Preferred Embodiments

Compounds represented by the following formula (4) may be provided as specific preferred examples of the organic compound (Ab):

(In Formula 4, R ³ and R ⁴ are each a hydrogen atom or an alkyl or aryl group having 1-8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, or 6-12 carbons. An aryl group having atoms, for example a phenyl group or a xylyl group; R ⁵ is a divalent organic group having 1 to 12 carbon atoms and has an aliphatic structure (straight, branched or cyclic) or aromatic structure R ⁶ is a divalent organic group having a molecular weight of 14 to 10,000, preferably 76 to 500; R ⁷ is a (q + 1) valence organic group, straight, branched or cyclic, saturated or unsaturated hydrocarbons; Preferably selected from the group consisting of groups; R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ contain heteroatoms such as O, N, S, P; Z undergoes intermolecular crosslinking reaction in the presence of an active radical Monovalent organic having a polymerizable unsaturated group in the molecule to be produced And; q is 1 to 20, more preferably from 1 to 10, and most preferably an integer of 1 to 5; p is an integer of 1-3)

Examples of groups represented by [(R ³ O) _p R ⁴ _3-p Si-] include trimethoxy silyl, triethoxy silyl, triphenoxy silyl, methyldimethoxy silyl and dimethylmethoxy sil There is a diary. Among the groups, trimethoxysilyl group, triethoxysilyl group and the like are most preferred.

Examples of the organic group (Z) include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group and acrylamide group.

The organic compound (Ab) used in the present invention can be synthesized using the method disclosed in Japanese Patent Application Laid-Open No. 100111/1997.

The proportion of the organic compound (Ab) bonded to the oxide particles (Aa) is preferably 0.01 weight based on 100% by weight of the reactive particles (A) (total weight of the oxide particles (Aa) and the organic compound (Ab)). At least%, more preferably at least 0.1% by weight and particularly preferably at least 1% by weight. If the ratio is less than 0.01% by weight, the dispersibility of the reactive particles (A) in the composition may be inadequate, thereby impairing the transparency and scratch resistance of the obtained cured product. In the production of the reactive particles (A), the proportion of the oxide particles (Aa) in the raw material is preferably 5-99% by weight and more preferably 10-98% by weight.

The proportion (content) of reactive particles (A) to be blended in the composition is preferably 5-90 based on 100% by weight of the composition (total weight of reactive particles (A), compounds (B) and (C)). Weight percent and more preferably 65-85 weight percent. If the ratio is less than 5% by weight, a product with a high refractive index cannot be obtained. When the said ratio is 90 weight% or more, film-forming property is inadequate.

The content of oxide particles (Aa) constituting the reactive particles (A) in the composition is preferably 65-90% by weight.

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

2. Compound (B)

The compound (B) used for this invention is a melamine compound which does not have a polymerizable unsaturated group. It is preferable that compound (B) is a compound represented by following formula (2):

(In Formula 2, X represents a hydrogen atom or an organic group having 1-20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1-10 carbon atoms; Y represents a hydrogen atom or 1-20, respectively. Organic group having 3 carbon atoms, preferably a hydrogen atom, an alkyl group having 1-10 carbon atoms, or a monovalent organic group represented by the following general formula (3): n is an integer of 1 to 20)

(In the above formula (3), X each represents a hydrogen atom or an organic group having 1-20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1-10 carbon atoms).

The organic group or alkyl group may be linear, branched, cyclic, substituted or unsubstituted.

Compound (B) is suitably used to increase the refractive index of the cured product and to improve the chemical resistance of the laminate.

Examples of the organic group having 1-20 carbon atoms represented by X and Y in the formulas (2) and (3) include straight or branched chain alkyl groups such as methyl group, ethyl group, n-propyl group and isopropyl group; Aromatic groups such as phenyl, tolyl, xylyl and naphthyl groups. Among the above, lower alkyl groups having 1-5 carbon atoms are preferred.

X in formulas (2) and (3) is preferably a methyl group, isobutyl group, sec-butyl group and tert-butyl group.

Substituent (X) in formula (2) is preferably a methyl group, giving the advantage that an improved curability can be obtained.

In the formula (2), Y is preferably a methyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an organic group represented by the formula (3).

Commercially available products of compound (B) include Cymel 238, XV805, XM2819, Simel 303 (manufactured by Mitsui-Cytec, Ltd.), Nikalac E-1201 (Sanwa Chemical Co., Ltd.). 1) and the like may be provided.

The number average molecular weight of the compound (B) used in the present invention is preferably 300 to 20,000. The number average molecular weight of the compound (B) is more preferably 300 to 5,000. If the number average molecular weight is less than 500, the chemical resistance of the obtained laminate may be insufficient. When a number average molecular weight exceeds 20,000, coatability may be inadequate.

Compound (B) can be used in combination of 2 or more types. When compound (B) is a compound represented by the formula (2), two or more compounds (where X, Y or n are different) may be used in combination.

In particular, it is preferable that at least 25 mol% of the substituents (X and Y) in the formula (2) is an isobutyl group. If the content of isobutyl group is 25 mol% or more, the scratch resistance of the cured product is increased.

More preferably, the isobutyl group is 40 mol% or more.

The amount of compound (B) used in the present invention is preferably 0.01-50% by weight, and more preferably, based on 100% by weight of the composition (reactive particles (A), compounds (B) and compounds (C) in total). Is 1-40% by weight. If the amount is less than 0.01% by weight, the chemical resistance of the laminate may be insufficient. If the amount exceeds 50% by weight, the hardness of the cured product may be insufficient.

3. Compound (C)

It is preferable that the compound (C) used by this invention is a compound which has 2 or more polymerizable unsaturated groups in molecules other than a compound (B). Compound (C) is suitably used to increase the film formability of the composition. There is no particular limitation on the compound (C) within the range of the compound having two or more polymerizable groups in the molecule, but (meth) acrylic esters, vinyl compounds and the like can be provided as examples. Among these, (meth) acrylic ester is preferable.

The following compounds can be given as special examples of the compound (C) used in the present invention.

Examples of (meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol 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, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and bis (2-hydroxyethyl) isocia Late di (meth) acrylates, poly (meth) acrylates of ethylene oxide or propylene oxide adducts to the starting alcohols of the (meth) acrylates, oligoester (meth) acrylates, oligoether (meth) acrylics Olefins, oligourethane (meth) acrylates, and oligoepoxy (meth) acrylates having two or more (meth) acryloyl groups in the molecule. Among the above, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate are preferable.

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

Examples of commercially available products of compound (C) include Aronix M-400, 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 (manufactured by Toagosei Co., Ltd.); KAYARAD D-310, D-330, DPHA, DPCA-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 (manufactured by Nippon Kayaku Co., Ltd.); Light Acrylate PE-4A, DPE-6A, DTMP-4A (manufactured by Kyoeisha Chemical Co., Ltd.).

The proportion of compound (C) used in the present invention is preferably 10-80% by weight, more than 100% by weight of the composition (total weight of reactive particles (A), compound (B) and compound (C)) Preferably 20-75% by weight. If the ratio is less than 10% by weight or more than 80% by weight, hardened products having a high hardness cannot be obtained.

In addition, the compound which has one polymerizable unsaturated group in a molecule | numerator can be added to the composition of this invention other than compound (C) as needed.

4. Acid Generator

In addition to the reactive particles (A), compounds (B) and (C), (D) acid generators (hereinafter referred to as "acid generators (D)") may be added to the composition of the present invention as needed. Can be.

Examples of acid generators (D) may be provided with compounds which generate cations by thermal (light) irradiation and thermally generate cations known in the art.

Examples of thermally generating cations include aliphatic sulfonic acids, aliphatic sulfonates, aliphatic carboxylic acids, aliphatic carboxylates, aromatic carboxylic acids, aromatic carboxylates, alkylbenzene sulfonic acids, alkylbenzene sulfonates, phosphates, metal salts, and the like. Can be provided.

The compounds may be used alone or in combination of two or more thereof.

Preferred examples of the compound which generates a cation by irradiation may be an onium salt having a structure represented by the following formula (5).

The onium salt is represented by the following Chemical Formula 5, and is a compound that generates Lewis acid when exposed to light.

[In Formula 5, the cation is an onium ion; W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or -N = N; R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are organic groups which may be the same or different; d, e, f and g are each an integer of 0 to 3, provided that (d + e + f + g) is equal to the valence of W; M is a metal or metalloid constituting the central atom of the halide complex [MT _{j + k} ], such as B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V , Cr, Mn and Co; Y is a halogen atom such as F, Cl and Br; j is the effective charge of the halide complex ion; k is the valence]

Specific examples of the anion [MT _{j + k]} in the formula (5) are tetrafluoroborate (BF ₄ ^-), hexafluorophosphate (PF ₆ ^-), antimonate hexafluorophosphate (SbF ₆ ^-), are hexafluoro Cenate (AsF ₆ ⁻ ) and hexachloroantimonate (SbCl ₆ ⁻ ) may be provided.

In addition, onium salts having anions of the structural formula [MT _k (OH) ⁻ ] may also be used. Further, perchlorate ion (ClO ₄ ^-), methanesulfonic acid ion trifluoroacetate (CF ₃ SO ₃ ^-), sulfonate ion fluoro (FSO ₃ ^-), toluenesulfonic acid ion, trinitrotoluene sulfonic acid anion, and trinitrotoluene sulfonic Onium salts with other anions such as phonic acid anions can be used.

Among the onium salts, aromatic onium salts are particularly effective as acid generators (D). Particularly preferred onium salts include aromatic halonium salts disclosed in Japanese Patent Application Laid-Open Nos. 151996/1975 and 158680/1975; Group VIA aromatic onium salts disclosed in Japanese Patent Application Laid-Open Nos. 151997/1975, 30899/1977, 55420/1981, and 125105/1980; Group VA aromatic onium salts disclosed in Japanese Patent Application Laid-Open No. 158698/1975; Oxosulfonium salts disclosed in Japanese Patent Application Laid-Open Nos. 8428/1981, 149402/1981, and 192429/1982; Aromatic diazonium salts disclosed in Japanese Patent Application Laid-Open No. 1740/1974 and thiopyryllium salts disclosed in US Pat. No. 4,139,655. And iron / allen complex initiator, aluminum complex / photodecomposition silicon compound type initiator, etc. can be provided as an example.

The onium salt may be used alone or in combination of two or more thereof.

Examples of commercially available products suitably used as acid generators (D) include Catalyst 4050 (manufactured by Mitsui-Cytec, Ltd.), UVI-6950, UVI-6970, UVI-6974, and UVI-6990 (Union Carbide Corp.). Adekaoptomer SP-150, SP-151, SP-170, SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (Ciba Specialty Chemicals Co.) ., Ltd.), CI-2481, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (Sartomer Co., Ltd.) Problem), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (manufactured by Nippon Kayaku Co., Ltd.) and the like may be provided. Among them, UVI-6970, UVI-6974, UVI-6990, Adekaoptomer SP-150, SP-170, SP-171, CD-1012 and MPI-103 are particularly suitable for expressing excellent surface curability in the curable composition. desirable.

The amount of acid generator (D) optionally used in the composition of the present invention is 0.01-20 weight based on 100 parts by weight of the composition (total weight of reactive particles (A), compound (B) and compound (C)) Parts, more preferably 0.1-10 parts by weight. If the amount is less than 0.01 part by weight, the film formability may be insufficient. If the amount is 20 parts by weight or more, a cured product having a high hardness cannot be obtained.

5. Radical polymerization initiator (E)

Reactive particles (A), compounds (B) and compounds (C), as well as (E) radical polymerization initiators (hereinafter referred to as "radical polymerization initiators (E)") may be added as necessary to the compositions of the present invention. Can be.

Examples of radical polymerization initiators (E) include compounds which generate thermally active radicals (thermal polymerization initiators) and compounds which generate active radicals by radiation (light) irradiation (radiation (photo) polymerization initiators). Can be.

There is no particular limitation on the radiation (photo) polymerization initiator as long as it decomposes by irradiation to generate radicals to initiate polymerization. Examples of the initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, xanthone, fluorenone, benzaldehyde, flu Orene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzo Phosphorus ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 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-trimethylbenzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-t There is methyl pentyl phosphine oxide and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).

Examples of commercially available products of radiation (photo) polymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116 , 1173 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO (manufactured by BASF), Ubecryl P36 (manufactured by UCB), Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55 , KTO46, KIP75 / B (manufactured by Lamberti) and the like can be provided.

The amount of radical polymerization initiator (E) optionally used in the present invention is preferably 0.01-20 based on 100 parts by weight of the composition (total weight of reactive particles (A), compound (B) and compound (C)). Parts by weight, more preferably 0.1-10 parts by weight. If the amount is less than 0.01 part by weight, the hardness of the cured product may be insufficient. If the amount is 20 parts by weight or more, the inner layer may remain uncured during the curing operation.

When curing the composition of the present invention, a photo-polymerization initiator and a heat-polymerization initiator may be used in combination as necessary.

Preferred examples of thermal-polymerization initiators may be provided with peroxides, azo compounds and the like. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile and the like.

6. Other Ingredients

Curable compositions of the present invention include additives such as photosensitizers, polymerization inhibitors, polymerization aids, leveling agents, wetting improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes, and the like. It can be included within the range that the effect of is not impaired.

7. Application of Composition

The composition of the present invention can be suitably used as an antireflection film or coating material. Examples of substrates to which the composition can be applied include plastics (polycarbonates, polymethacrylates, polystyrenes, polyesters, polyolefins, epoxy resins, melamine resins, triacetyl cellulose resins, ABS resins, AS resins and norbornene resins). ), Metal, wood, paper, glass, slate and the like can be provided. The said base material is plate shape, a film shape, or a three-dimensional molded object. Conventional coating methods such as dip coating method, spray coating method, flow coating method, shower coating method, roll coating method and brush coating method are the coating methods. Can be used. The film thickness after drying and curing is usually 0.1-400 μm, preferably 1-200 μm.

To adjust the film thickness, the compositions of the present invention can be used diluted with a solvent. For example, when used as an antireflective film or coating, the viscosity of the composition is usually 0.1-50,000 mPa · s / 25 ° C., preferably 0.5-10,000 mPa · s / 25 ° C.

8. Curing method of the composition

The composition of the present invention is cured by heat and / or radiation (light). In the case of curing the composition by heat, an electric heater, an infrared lamp, hot air, or the like may be provided as the heat source. When curing the composition using radiation (light), there is no particular limitation on the radiation source within the range in which the composition can be cured in a short time after coating. Examples of infrared sources may be provided with lamps, heat-resistant plates, lasers and the like. Examples of visible light sources may be daylight, lamps, fluorescent lamps, lasers and the like. Examples of ultraviolet sources may be mercury lamps, halogen lamps, lasers and the like. Examples of electron beam sources include systems using hot electrons made from commercially available tungsten filaments, cold cathode methods for generating electron beams by passing high voltage pulses through the metal, and ionized gaseous molecules and metals. There is a secondary electron method using secondary electrons generated by collision with an electrode. Fissionable substances such as Co ⁶⁰ may be provided as a source of α-ray, β-ray and γ-ray. For γ-rays, a vacuum tube or the like may be used to collide the accelerated electrons with the anode. The radiation may be used alone or in combination of two or more thereof. In the latter case, two or more radiations may be used simultaneously or at specific time intervals.

II. Cured Product

The cured product of the present invention can be obtained by applying a curable composition to various substrates such as plastic substrates and curing the composition. In particular, the cured product may be coated by coating the composition on a substrate, removing volatile components from the composition by drying at 0-200 ° C., and curing the composition using heat and / or radiation. body). Curing with heat is preferably carried out at 20-150 ° C. for 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. The dose of ultraviolet light is preferably 0.01-10 J / cm 2, more preferably 0.1-2 J / cm 2. The electron beam is preferably irradiated with an electron density of 0.02-0.30 mA / cm 2 at a pressurized voltage of 10-300 KV and an irradiation light amount of 1-10 Mrad.

Since the cured product of the present invention has a high hardness and a high refractive index and can form a coating (film) exhibiting not only a low refractive index layer but also excellent scratch resistance and good adhesion to a substrate, the cured product is particularly a film type liquid crystal device. It is especially suitable as an antireflection film for touch panels or plastic optical parts.

III. Laminate

The laminate of the present invention is formed by laminating a cured film produced by curing a curable composition on a substrate and then laminating a film of low refractive index on the cured film. The laminate is particularly suitable as an antireflection film.

There is no particular limitation on the substrate used in the present invention. When used as an antireflection film, as a plastic (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.) The prepared substrate can be provided as an example.

Examples of the low refractive index film used in the present invention may be a film made of a metal oxide such as magnesium fluoride and silicon dioxide, a cured film of a fluorine-type coating material having a refractive index of 1.38-1.45, and the like.

Other films may be present between the high refractive index cured film and the low refractive index film or between the substrate and the high refractive index cured film. For example, a hard coat layer or an antireflection layer may be provided between the substrate and the high refractive index cured film.

Vacuum deposition and sputtering are suitable methods for forming a low refractive index metal oxide film on a high refractive index cured film made by curing the curable composition. The same methods can be used to apply the fluorine-type coating to the cured film.

The reflection of light from the substrate surface can be effectively prevented by applying the composition of the present invention onto the substrate, applying the heat or radiation to the composition to cure the composition, and applying a low refractive index film onto the cured film.

The laminate of the present invention is particularly suitable as an antireflection film for film type liquid crystal elements, touch panels or plastic optical parts due to its low reflectance and excellent chemical resistance.

The invention will be explained in more detail by way of examples, which are not to be considered as limiting the invention. In the following examples, "parts" and "%" mean "parts by weight" and "wt% (wt%)", respectively, unless otherwise specified.

In the present invention, "solid content" means the content of components excluding volatile components such as solvents from the dispersion, in particular "solid content" is obtained by drying the composition for 1 hour on a hot plate at 175 ℃ Refers to the content of water (non-volatile components).

Preparation Example 1 Preparation of Oxide Particles (Aa)

300 parts of spherical zirconia fine particles (manufactured by Sumitomo Osaka Cement Co., Ltd., number average primary particle diameter: 0.01 μm) were added to 700 parts of methyl ethyl ketone (MEK), and dispersed for 168 hours using glass beads. . The glass beads were removed to give 950 parts of methyl ethyl ketone zirconia sol (Aa). 2 g of the dispersion sol was weighed in an aluminum dish and dried for 1 hour on a 120 ° C. hot plate. The dried product was weighed and had a solids content of 30%. As a result of observing the solid under an electron microscope, the minor axis average particle diameter was 15 nm, the major axis average particle diameter was 20 nm, and the aspect ratio was 1.3.

Preparation Example 2 Preparation of Organic Compound (Ab) Having a Polymerizable Unsaturation Group

To 0.6 parts of mercaptopropyltrimethoxysilane and 0.2 parts of dibutyltin dilaurate in a vessel equipped with a stirrer, 20.6 parts of isophorone diisocyanate were added dropwise in dry air at 50 ° C. The mixture was stirred at 60 ° C. for 3 hours.

After 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. for 1 hour, the mixture was stirred at 60 ° C. for 3 hours to obtain a reaction solution.

The residual isocyanate content in the reaction product (organic compound having a polymerizable unsaturated group) in the reaction solution was analyzed by FT-IR and found to be 0.1 wt% or less. This indicates that each reaction was almost quantitatively completed. The organic compound had a thiurethane bond, a urethane bond, an alkoxysilyl group, and an acryloyl group (polymerizable unsaturated group) in the molecule.

Preparation Example 3 Preparation of Reactive Zirconia Fine Powder Sol (A-1)

5.2 parts of organic compound (Ab) having a polymerizable unsaturated group prepared in Preparation Example 2, 237 parts of methyl ethyl ketone zirconia sol (Aa) prepared in Preparation Example 1 (zirconia content: 30%), 0.1 parts of ion-exchanged water, and p A mixture of 0.03 parts of hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 3 hours. After addition of 1.0 part of methyl orthoformate, the mixture was stirred at the same temperature for 1 hour to obtain reactive particles (dispersion (A-1)). 2 g of dispersion (A-1) were weighed in an aluminum dish and dried for 1 hour on a 120 ° C. hot plate. The dried product was weighed to confirm that the solids content was 31%. 2 g of the dispersion (A-1) was weighed in a magnetic crucible, pre-dried for 30 minutes on a hot plate at 80 ° C., and calcined for 1 hour in a muffle furnace at 750 ° C. The inorganic content in the solid content was measured from the obtained inorganic residue to confirm that the inorganic content was 93%.

Preparation Example 4 Preparation of Reactive Silica Fine Powder Sol (A-2)

8.7 parts of organic compound (Ab) which has a polymerizable unsaturated group manufactured in the preparation example 2, silica particle sol (methyl ethyl ketone silica sol, MEK-ST by Nissan Chemical Industries, Ltd., number average particle diameter: 0.022 micrometer, silica content : 30%) A mixture of 91.3 parts (27 parts as silica particles) and 0.1 parts of ion-exchanged water was stirred at 60 ° C. for 3 hours. After addition of 1.4 parts of methyl orthoformate, the mixture was stirred at 60 ° C. for 1 hour to give reactive particles (dispersion (A-2)). 2 g of dispersion (A-2) was weighed on an aluminum dish and dried for 1 hour on a hot plate at 175 ° C. The dried product was weighed to confirm that the solids content was 35%.

Example 1

164.6 parts of reactive zirconia fine powder sol (A-1) prepared in Preparation Example 3 (reactive zirconia: 51.0 parts), dipentaerythritol pentacrylate (C-1) ("Gayarad from Nippon Kayaku Co., Ltd.") DPHA-2C ") 35.8 parts, 113.6 parts of methyl isobutyl ketone (abbreviated as MIBK) were mixed in a UV shielding vessel. Using a rotary evaporator until the solids content was 65.5% The mixture was condensed Melamine compound (B-1) ("Cymel 238" from Mitsui-Cytec, Ltd., mixed alkylated melamine; in formula (2), n = 1.8, X and hydrogen or an alkyl group of Y After adding 6.2 parts of 40 mol% isobutyl group and the remaining 60 mol% is methyl group, Catalyst 4050 (D-1) (manufactured by Mitsui-Cytec, Ltd., isopropyl alcohol solution, solid content: 55% by weight) ) 4.0 parts, 1-hydroxycyclohexyl phenyl ketone (E-1) 1.9 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 ( E-2) 1.1 parts and 51.2 parts of MIBK were added to the condensed product, and then the mixture was stirred for 2 hours at 30 ° C. to obtain a composition of homogeneous solution of the composition measured in the same manner as in Preparation Example 3. Solid content was 50%.

Example 2-5

The composition of Example 2-5 was obtained in the same manner as in Example 1 except for changing the composition as described in Table 1.

Example 6

The composition of Example 6 is melamine acrylate (C-2) 3.1 which is a melamine compound ("Nikalac MX-302" manufactured by Sanwa Chemical Co., Ltd.) having a polymerizable unsaturated group instead of a part of the melamine compound (B-1). The same method as in Example 1 was obtained except that parts were used.

Example 7

The composition of Example 7 is composed of melamine compound (B-2) instead of melamine compound (B-1) ("XV805" from Mitsui-Cytec, Ltd., mixed alkylated melamine; in formula (2), n = average 2, X and hydrogen Or 6.2 mole% of Y, which is an alkyl group, isobutyl group and the remaining 75 mole% is a methyl group), and was obtained in the same manner as in Example 1.

Example 8

The composition of Example 8 is composed of melamine compound (B-3) instead of melamine compound (B-1) ("XM2819" from Mitsui-Cytec, Ltd., mixed alkylated melamine; in formula (2), n = average 2, X and hydrogen Or 75 mole% of Y, which is an alkyl group, isobutyl group and the remaining 25 mole% is a methyl group), and was obtained in the same manner as in Example 1.

Example 9

The composition of Example 9 used the reactive silica fine powder sol (A-2) prepared in Preparation Example 4 instead of the reactive particles (A-1), except that the amount of each compound disclosed in Table 1 was changed. Obtained in the same manner as 1.

Example 10

The composition of Example 10 is composed of melamine compound (B-4) instead of melamine compound (B-1) ("Simell 303" from Mitsui-Cytec, Ltd., fully methylated melamine; in Formula 2, n = average 1.8, X and A hydrogen or alkyl group (Y is a methyl group) was obtained in the same manner as in Example 1 except for using 6.2 parts.

Comparative Examples 1 and 2

The compositions of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except for changing the composition as disclosed in Table 1.

Comparative Example 3

The composition of Comparative Example 3 uses the reactive silica fine powder sol (A-2) prepared in Preparation Example 4 instead of the reactive particles (A-1), except that the amount of each compound was changed as disclosed in Table 1. Obtained in the same manner as in Example 1.

Laminate

Production Example 5: Preparation of the low refractive index curable composition for film (coating liquid A)

1) Preparation of Fluorine-Containing Polymer Having a hydroxyl Group

The atmosphere in the stainless steel autoclave (1.5 L) provided with the electromagnetic stirrer was fully substituted by nitrogen gas. 500 g of ethyl acetate, 34.0 g of ethyl vinyl ether (EVE), 41.6 g of hydroxyethyl vinyl ether (HEVE), 75.4 g of perfluoropropyl vinyl ether (FPVE), 1.3 g of lauroyl peroxide, silicon- 7.5 g of a containing polymeric azo initiator ("VPS1001" manufactured by Wako Pure Chemical, Ltd.) and 1 g of a reactive emulsifier ("NE-30" manufactured by Asahi Denka Co., Ltd.) were charged. The mixture was cooled to −50 ° C. with dry ice-methanol and then the oxygen contained in the system was removed by nitrogen gas.

After adding 119.0 g of hexafluoropropylene (HFP), the autoclave temperature was raised. When the autoclave temperature reached 70 ° C., the pressure was 5.5 × 10 ⁵ Pa. The reaction proceeded with stirring at 70 ° C. for 20 hours. When the pressure was reduced to 2.3 × 10 ⁵ Pa, the reaction was terminated by cooling the autoclave with water. When the temperature in the autoclave reached room temperature, unreacted monomers were removed. The autoclave was opened to obtain a polymer solution having a solids content of 30% by weight. The polymer solution obtained was poured into methanol to precipitate the polymer. The precipitate was washed with methanol and dried at 50 ° C. under vacuum to give 170 g of fluorine-containing polymer having hydroxyl groups.

The inherent viscosity of the obtained fluorine-containing polymer having a hydroxyl group measured at 25 ° C. using a N, N-dimethylacetamide solvent was 0.28 dl / g.

The glass transition temperature of the fluorine-containing polymer measured using a differential scanning calorimeter (DSC) at a temperature increase rate of 5 ° C./min in the nitrogen stream was 31 ° C.

The fluorine content of the fluorine-containing polymer measured by the alizarin complexone method was 51.7%.

The hydroxyl value of the fluorine-containing polymer measured by acetylation method using acetic anhydride was 102 mg KOH / g.

2) Preparation of the curable composition for film (coating liquid A) of low refractive index

In a vessel equipped with a stirrer, 100 g of a fluorine-containing copolymer having a hydroxyl group obtained in 1), 11.1 g of Simel 303 (manufactured by Mitsui-Cytec, Ltd.) and 3,736 g of methyl isobutyl ketone (MIBK) were charged. The mixture was stirred at 110 ° C. for 5 hours to react the fluorine-containing copolymer with hydroxyl groups with Simel 303.

After addition of 11.1 g of Catalyst 4040 (manufactured by Mitsui Cytec, Ltd., solid content: 40 wt.%), The mixture was stirred for 10 minutes for a low refractive index film having a viscosity of 1 mPa.s (measured at 25 ° C.). A curable composition (hereinafter referred to as "coating liquid A") was obtained.

The refractive index of the film of the low refractive index obtained from the curable composition for films (coating liquid A) of low refractive index was measured.

A low refractive index curable composition for film was applied to a silicon wafer (thickness: 1 mu m) using a wire bar coater (# 3), and air dried at room temperature for 5 minutes to form a coat. The coating film was heated and cured by a hot air dryer at 140 ° C. for 1 minute to obtain a low refractive index film having a thickness of 0.3 μm. Using a spectroscopic ellipsometer, the refractive index of the Na-D line of the obtained low refractive index film was measured at 25 ° C. The refractive index was 1.40.

Example 11: Preparation of Anti-Reflection Film Laminate

The compositions obtained in Examples 1-10 and Comparative Examples 1-3 of the present invention were each coated with a wire bar coater (# 6) using a polyester film (“A4300” manufactured by Toyobo Co., Ltd., thickness: 188 μm). It applied to and dried for 1 minute in 80 degreeC oven, and formed the coating film. The coating film was cured by irradiating with UV rays at an irradiation amount of 0.3 J / cm 2 using a metal halide lamp in air to obtain a high refractive index film having a thickness of 3 μm.

Coating liquid A was apply | coated to the film of high refractive index using the wire bar coater (# 3), and it air-dried at room temperature for 5 minutes, and formed the coating film. The coating film was cured by heating in an oven at 140 ° C. for 1 minute to form a low refractive index film having a thickness of 0.1 μm to obtain an antireflection film laminate.

Evaluation example: Evaluation of antireflection film laminate

The scratch resistance, reflectance, haze (Haze value) and total light transmittance of the antireflective film laminate obtained in Example 11 were measured or evaluated according to the following method.

1) reflectance

Spectrophotometer of Hitachi Ltd. equipped with a spectroscopic reflectance measuring device (large sample chamber integrating sphere accessory "150-09090") according to JIS K7105 (Measurement A). "U-3410" was used to measure at a wavelength of 340-700 nm.

In particular, the minimum reflectance of the antireflection film laminate (antireflection film) was measured at each wavelength with the reflectance of the aluminum vapor deposition film as a reference (100%). The results are shown in Table 1.

2) total light transmittance and turbidity (haze)

The total light transmittance and the haze value of the antireflection film laminate were measured in accordance with JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Table 1.

3) scratch resistance

The scratch resistance of the anti-reflective film laminate was evaluated by visual observation according to the following criteria by rubbing the surface of the anti-reflective film laminate 10 times with a load of 200 g / cm 2 with # 0000 steel wool. The results are shown in Table 1.

Evaluation 5: No scratch occurrence observed

Evaluation 4: 1-5 scratch occurrences are observed.

Evaluation 3: 6-50 scratches were observed.

Evaluation 2: 51-100 scratches observed.

Evaluation 1: coating film peeling was observed.

Evaluation The laminated body which has a scratch resistance of 2 or more exists in practically acceptable range. It is preferable that the laminated body which has a scratch resistance of evaluation 4 or more is excellent in durability practically. The laminated body which has abrasion resistance of evaluation 5 is more preferable that practical durability improved remarkably.

In Table 1, the amount of reactive particles (A) ^{* represents} the fine powder dry weight (excluding organic solvent) contained in each dispersion sol.

The meanings of the abbreviations disclosed in Table 1 are as follows:

A-1: Reactive Zirconia Sol Prepared in Preparation Example 3

A-2: Reactive Silica Sol Prepared in Preparation Example 4

B-1: melamine compound (Simel 238 manufactured by Mitsui-Cytec, Ltd.)

B-2: Melamine Compound (XV 805 from Mitsui-Cytec, Ltd.)

B-3: melamine compound (XM 2819 manufactured by Mitsui-Cytec, Ltd.)

B-4: melamine compound (Simel 303, manufactured by Mitsui-Cytec, Ltd.)

C-1: dipentaerythritol hexaacrylate

C-2: melamine acrylate (Nikalak MX-302, manufactured by Sanwa Chemical Co., Ltd.)

D-1: Catalyst 4050 (manufactured by Mitsui-Cytec, Ltd.)

E-1: 1-hydroxycyclohexyl phenyl ketone

E-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1

MEK: Methyl Ethyl Ketone

MIBK: Methyl Isobutyl Ketone

Claims (12)

(A) Particles prepared by combining an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, and an organic compound comprising a polymerizable group ; (B) a compound having a melamine group but no polymerizable unsaturated group; And (C) Curable composition containing the compound which has two or more polymerizable groups in molecules other than component (B). The method of claim 1, The curable composition of compound (A) and (C) is a polymerizable unsaturated group. The method according to claim 1 or 2, Curable composition, characterized in that the organic compound contained in the particles of component (A) includes not only a polymerizable unsaturated group, but also a group represented by the following formula (1). (Formula 1) (In Formula 1, U represents NH, O (oxygen atom) or S (sulfur atom); V represents O or S). The method according to any one of claims 1 to 3, The component (B) is a curable composition, characterized in that at least one of the compounds represented by the following formulas (2) and (3): (Formula 2) (In Formula 2, X represents a hydrogen atom or an organic group having 1-20 carbon atoms; Y represents a hydrogen atom, an organic group having 1-20 carbon atoms, or a monovalent organic group represented by Formula 3 below. N is an integer from 1 to 20) (Formula 3) (In Formula 3, X each represents a hydrogen atom or an organic group having 1-20 carbon atoms). The method of claim 4, wherein X represents a hydrogen atom or an alkyl group having 1-10 carbon atoms, and Y represents a hydrogen atom or an alkyl group having 1-10 carbon atoms. The method according to claim 4 or 5, At least 25 mol% of the substituents X and Y in the formula (2) is an isobutyl group. The method according to any one of claims 1 to 6, The content of compound (B) is a curable composition, characterized in that 0.01 to 30% by weight based on the total weight of components (A), (B) and (C). The method according to any one of claims 1 to 7, (D) Curable composition, characterized in that it further contains an acid generator. The method according to any one of claims 1 to 8, (E) Curable composition further containing a radical polymerization initiator. Cured product prepared by curing the curable composition according to any one of claims 1 to 9. As a method of manufacturing a laminate, A method of applying a curable composition of any one of claims 1 to 9 onto a substrate, curing the curable composition to form a cured film, and laminating a low refractive index film on the cured film Method comprising a. A laminate obtainable according to the method of claim 11.