KR20080047617A - Curable composition, cured layer thereof and multilayer body - Google Patents

Abstract

Disclosed is a curable composition for a hard coat which contains (A) 60-94% by mass of a compound having a urethane bond and 3 or more ethylenically unsaturated groups in a molecule, (B) 5-35% by mass of an ethylenically unsaturated group-containing compound having a molecular weight of not more than 290, and (C) 0.01-20% by mass of a radiation (photo)polymerization initiator when the total of (A), (B) and (C) is taken as 100% by mass, while additionally containing (D) one or more solvents selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, methylene chloride, chloroform and tetrahydrofuran.

Description

Curable composition, its cured layer, and laminated body {CURABLE COMPOSITION, CURED LAYER THEREOF AND MULTILAYER BODY}

The present invention relates to a curable composition and a cured film thereof. More specifically, it has excellent coating properties, and various substrates (for example, polycarbonate, polymethyl methacrylate, polystyrene, epoxy resin, melamine resin, triacetyl cellulose (hereinafter referred to as "TAC"), ABS resin, AS resin, norbornene-based resin, etc.] to form a coating film (film) having high hardness and excellent scratch resistance, adhesion to substrates and adjacent layers such as substrates and high refractive index layers, and having high transparency. The curable composition for hard-coat films, and the hard coat film | membrane which are small in curling property and excellent in flexibility and chemical-resistance are provided. In addition, in this specification, a hard coat film means the cured film whose pencil hardness at the time of using the evaluation method mentioned later is "H" or more. In the laminated body obtained by laminating | stacking a hard coat film on a base material, this hard coat film is also called a hard coat layer.

Recently, protective coating materials for preventing damage (scratches) or contamination of various substrate surfaces; Adhesives and sealing materials of various substrates; As a binder of printing ink, it has excellent coating property, and has hardness, bendability, abrasion resistance, abrasion resistance, low curling property (small deformation of hard film), adhesion, transparency, chemical resistance and coating surface on the surface of various substrates. The curable composition which can form the cured film excellent in all the external appearance is calculated | required (patent document 1 and 2 below).

Moreover, in the use of antireflection films, such as a film type liquid crystal element, a touchscreen, and a plastic optical component, the curable composition which can form not only the said request but the cured film of a high refractive index is calculated | required.

In the case of a laminate having a hard coating layer composed mainly of acrylic resin, for example, on a TAC film generally used as a substrate, since the refractive indexes of the substrate and the hard coating layer are generally different, the light and the film reflecting from the film surface There is a problem that interference fringes generated by the optical path difference of the light reflected from the back surface exist, and the interference fringes are clearly seen as the transparency of the film is higher. The degree of the interference fringe can be evaluated by using the magnitude of the amplitude of the wave profile of the reflectance profile (the figure plotting the reflectance with respect to the measurement wavelength) of the laminate (hereinafter referred to as "interference nonuniformity") as an index. .

It is also pointed out that it is necessary to improve the adhesion between the base layer and the hard coating layer. Therefore, in the case of the polyester resin used with TAC as a base material, the easily bonding film for optics is proposed for the purpose of reducing interference fringes, or improving adhesiveness (patent documents 3 and 4 below).

In the case of using a TAC substrate, for the purpose of reducing interference fringes, an antireflection layer having a refractive index continuously changed in the film thickness direction is provided on the substrate, and the interface between the antireflection layer and the substrate layer is clearly present, but the reflection at the boundary surface is provided. The technique which set the refractive index of a prevention layer higher than the refractive index of a base material layer is also disclosed (patent document 5 below).

Patent Document 1: Japanese Patent Application Laid-Open No. 9-254321

Patent Document 2: Japanese Patent Application Laid-Open No. 9-300533

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-129948

Patent Document 4: Japanese Patent Application Laid-Open No. 2001-71439

Patent Document 5: Japanese Patent Application Laid-Open No. 2004-12657

However, when the hard coating layer was provided on the substrate, it could not be satisfied in view of interference fringes, hardness, and adhesion between the substrate and the hard coating layer.

This invention is made | formed in view of the above-mentioned problem, and can form the hard-coating film which has the outstanding coating property, is high hardness on the surface of various base materials, there are few interference stripes, it is excellent in adhesiveness with a base material, and has high transparency It is an object of the present invention to provide a hard coating film having excellent curable composition and excellent chemical resistance.

According to this invention, the following curable compositions for hard-coat films and hard coat films obtained by hardening this can be provided.

[1] The total amount of the following components (A), (B) and (C) is 100 mass%,

(A) 60-94 mass% of compounds which have a urethane bond and 3 or more ethylenically unsaturated group in a molecule,

(B) 5-35 mass% of ethylenically unsaturated group containing compounds whose molecular weight is 290 or less, and

(C) 0.01-20 mass% of radiation (photo) polymerization initiators,

And

(D) at least one solvent selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, methylene chloride, chloroform and tetrahydrofuran

Curable composition for hard coating films containing these.

[2] The above-mentioned [1], wherein the component (B) is made of (meth) acryloyl morpholine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and lauryl acrylate Curable composition for hard-coat films containing 1 or more types of compound chosen from the group.

[3] The curable composition for hard coating film according to the above [1] or [2], wherein the component (A) is a compound having a urethane bond and 6 or more ethylenically unsaturated groups in the molecule.

[4] The content of the component (B) is any one of [1] to [3], wherein the total amount of the components (A), (B) and (C) is 100 mass%. Curable composition for hard-coat films which is more than 20 mass%.

[5] A hard coat film obtained by curing the curable composition according to any one of the above [1] to [4].

According to the present invention, a curable composition having excellent coatability, high hardness on the surface of various substrates, little interference fringes, excellent adhesion to the substrate, and a hard coating film having high transparency, and chemical resistance It is possible to provide an excellent hard coating film.

1: From the inside of the hard coating layer of the evaluation laminate using the curable composition prepared in Example 1 to the inside of the substrate while moving 0.3 μm each in the vertical direction with respect to the interface between the hard coating layer and the substrate. It is a graph showing the result of measuring the amount of osmium at each distance.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the hard coat film which is the curable composition for hard coat films (henceforth "the curable composition of this invention") of this invention, and its cured film is demonstrated.

I. Curable Compositions

The curable composition of this invention makes the total amount of the following (A), (B) and (C) component 100 mass%, 60-94 mass% of compounds which have a urethane bond and 3 or more ethylenically unsaturated groups in (A) molecule | numerator, (B) 5-35 mass% of ethylenically unsaturated group containing compounds whose molecular weight is 290 or less, and (C) 0.01-20 mass% of a radiation (photo) polymerization initiator, and (D) acetone, methyl ethyl ketone, cyclohexanone, and acetic acid It is characterized by containing at least one solvent selected from the group consisting of methyl, ethyl acetate, ethyl lactate, methylene chloride, chloroform and tetrahydrofuran.

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

1. (A) A compound having a urethane bond and at least 3 ethylenically unsaturated groups in the molecule

The component (A) used in the present invention is not particularly limited as long as it is a compound having a urethane bond and three or more ethylenically unsaturated groups in the molecule, but is preferably urethane (meth) acrylate.

Although the urethane (meth) acrylate which is a compound (A) which has a urethane bond is not specifically limited, It is basically obtained by making (a) polyisocyanate compound and (b) hydroxyl-containing (meth) acrylate monomer react. Urethane (meth) acrylate may be a thing obtained by urethane bond to another oligomer as a main chain.

Urethane (meth) acrylate should contain 3 or more of (meth) acryloyl groups couple | bonded with the main chain of the oligomer, It is preferable to contain 4 or more, It is more preferable to contain 6 or more.

As a preferable specific example of the urethane (meth) acrylate (A) which makes a polyisocyanate compound (a) and the hydroxyl group containing (meth) acrylate monomer (b) react, the compound represented by following formula (1) is mentioned, for example. .

Y _r -R ² -O-CO-NH-R ¹ -NH-CO-OR ³ -Y _S

R ¹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.

R <^2> , R <^3> is an organic group of (r + 1) and (s + 1) valence, Preferably it is selected from a chain, branched or cyclic saturated hydrocarbon group, and unsaturated hydrocarbon group.

Y represents the monovalent organic group which has in a molecule | numerator the polymerizable unsaturated group which crosslinks intermolecularly in presence of an active radical species. In addition, r and s are preferably integers of 1-20, More preferably, they are integers of 1-10, Especially preferably, they are integers of 1-5.

In addition, in the formula, R ² , R ³ and Y _r , Y _s may be the same or different.

The use ratio of the (a) polyisocyanate compound and (b) hydroxyl-containing (meth) acrylate monomer used for the synthesis | combination of a urethane (meth) acrylate is with respect to 1 equivalent of isocyanate groups contained in (a) polyisocyanate compound, It is preferable to make the hydroxyl group of a hydroxyl-containing (meth) acrylate monomer into 1.0-2 equivalent.

As a specific method of manufacturing such a urethane (meth) acrylate (A), the (c) polyol compound, (a) polyisocyanate compound, and (b) hydroxyl-containing (meth) acrylate monomer are collectively injected, for example. Reaction method; a method of reacting (c) the polyol compound and (a) the polyisocyanate compound and then (b) reacting the hydroxyl group-containing (meth) acrylate monomer; a method of reacting (a) a polyisocyanate compound and (b) a hydroxyl group-containing (meth) acrylate monomer, followed by (c) a polyol compound; a method of reacting (a) a polyisocyanate compound and (b) a hydroxyl group-containing (meth) acrylate monomer, followed by (c) a polyol compound, and finally (b) a hydroxyl group-containing (meth) acrylate monomer Can be mentioned.

As (c) polyol compound used for synthesis | combination of urethane (meth) acrylate, polyetherdiol, polyesterdiol, polycarbonate diol, polycaprolactone diol, etc. can be used. Of these, polyetherdiol is preferred, but other diols may be used in combination with polyetherdiol. The polymerization mode of these structural units is not particularly limited and may be any of random polymerization, block polymerization and graft polymerization.

As polyetherdiol, polyether olefindiol obtained by ring-opening-polymerizing 1 type of ionic polymerizable cyclic compounds, such as polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyhepta methylene glycol, polydecamethylene glycol, Or polyetherdiol obtained by ring-opening-copolymerizing 2 or more types of ionically polymerizable cyclic compounds is mentioned. Examples of the ionic polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, oxetane, 3,3-dimethyloxetane, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, dioxane, trioxane, tetraoxane, cyclohexene oxide, styrene oxide, epichlorohydrin, glycidyl methacrylate, allyl glycidyl ether, Allyl glycidyl carbonate, butadiene monooxide, isoprene monooxide, vinyl oxetane, vinyl tetrahydrofuran, vinyl cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, benzoic acid glycidyl ester Cyclic ethers, such as these, are mentioned.

Moreover, the polyetherdiol which ring-opened-copolymerized the said ionic polymerizable cyclic compound, cyclic imines, such as ethyleneimine, (gamma)-propiolactone, glycolic acid lactide, or dimethylcyclopolysiloxane can also be used. Specific combinations of the two or more ionic polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene jade Seed, propylene oxide, ethylene oxide, butene-1-oxide, ethylene oxide, tetrahydrofuran, butene-1-oxide, ternary polymer of ethylene oxide, etc. are mentioned. The ring-opening copolymer of these ionically polymerizable cyclic compounds may be bonded at random, or may be a block-like bond.

These polyether diols are, for example, PTMG650, PTMG1000, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation), ecsenol 1020, 2020, 3020, preminol PML-4002, PML-5005 (above, Asahi Glass Co., Ltd.) Manufactured), UNICEF DC1100, DC1800, DCB1000 (above, Nippon Yushi Co., Ltd.), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PTG2000, PTG-L1000, PTG-L2000 (above, Hodogaya Kagaku High School) Co., Ltd.), Z-3001-4, Z-3001-5, PBG2000 (above, Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim2200, 2220, 3201, 3205, 4200, 4220, 8200, 12000 (more) And Lionel Corporation).

(c) Although the said polyetherdiol is preferable as a polyol compound, polyesterdiol, polycarbonate diol, polycaprolactone diol, etc. can also be used, and these diol can also be used together with polyetherdiol. The polymerization mode of these structural units is not particularly limited and may be any of random polymerization, block polymerization and graft polymerization.

An example of the polycarbonate diol is one produced conventionally by alcohol-decomposing diethylene carbonate with diol. The diol may be, for example, alkylenediol having 2 to 12 carbon atoms such as 1,4-butanediol, 1,6-hexanediol, and 1,12-dodecanediol. Mixtures of these diols can also be used. Polycarbonate diols may contain ether bonds in the main chain in addition to the carbonate groups. Thus, for example, the polycarbonate copolymer of the alkylene oxide monomer and the alkylene diol described above can be used. As an alkylene oxide type monomer, ethylene oxide, tetrahydrofuran, etc. are mentioned, for example. These copolymers have a low modulus compared to polycarbonate homopolymers, and produce a cured coating that prevents crystallization of the liquid coating composition. Mixtures of polycarbonate diols and polycarbonate copolymers may also be used.

Examples of the polycarbonate diols include Duracarb 122 (PPG Industries Co., Ltd.) and Permanol KM10-1733 (Permuthane Co., Massachusetts, USA). Duracarb122 is prepared by alcohol degradation with hexanediol of diethylcarbonate. As an example of polyesterdiol, the reaction product of saturated polycarboxylic acid or these anhydrides, and diol is mentioned. As the saturated polycarboxylic acid and anhydride, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid And anhydrides thereof, such as malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid, and mixtures thereof. As a diol, 1, 4- butanediol, 1, 8- octane diol, diethylene glycol, 1, 6- hexanediol, dimethylol cyclohexane etc. are mentioned, for example. Polycaprolactones are included in this classification and are commercially available from Union Carbide under the trade names Tone Polylol series, for example, Tone 0200, 0221, 0301, 0310, 2201 and 2221. Tone0301 and 0310 are trifunctional.

As (a) polyisocyanate used for the synthesis | combination of urethane (meth) acrylate, aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate, etc. are mentioned. The specific compound is not particularly limited as long as it can be used as the photocurable resin composition, but preferred examples thereof include aromatic diisocyanate and alicyclic diisocyanate, more preferably 2,4-tolylene diisocyanate and isophorone diisocyanate. . These diisocyanate compounds may be used independently and may be used together 2 or more types.

Examples of the (a) polyisocyanate compound used for the synthesis of urethane (meth) acrylate include isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), toluene diisocyanate (TDI), diphenylmethylene diisocyanate, Hexamethylene diisocyanate, cyclohexylene diisocyanate, methylene dicyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenylenedi isocyanate, 4, 4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane Toluene diisocyanate and the like at both ends of the polyalkylene oxide and / or polyester glycol in addition to the silylene diisocyanate The isocyanate may include a combination of compounds. For example, TDI end stop polytetramethylene ether glycol and TDI end stop polyethylene adipate are mentioned, respectively. As these diisocyanate, diisocyanate, such as isophorone diisocyanate and toluene diisocyanate, etc. are preferable.

As the (b) hydroxyl group-containing (meth) acrylate monomer used in the synthesis of urethane (meth) acrylate, in view of the reactivity of the polyisocyanate with an isocyanate group, the hydroxyl group-containing (meth) acryl in which the hydroxyl group is bonded to a primary carbon atom Preferred are acrylate monomers (called first hydroxyl group-containing (meth) acrylates) and hydroxyl group-containing (meth) acrylates in which the hydroxyl groups are bonded to secondary carbon atoms (called second hydroxyl group-containing (meth) acrylates).

As the first hydroxyl group-containing (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi (meth) acrylate, and the like Can be mentioned.

As the second hydroxyl group-containing (meth) acrylate, for example, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acryl And 4-hydroxycyclohexyl (meth) acrylate; glycidyl group-containing compounds such as alkylglycidyl ether, allylglycidyl ether, and glycidyl (meth) acrylate; The compound obtained by addition reaction of meth) acrylic acid is mentioned. These hydroxyl-containing (meth) acrylate monomers can be used individually by 1 type or in combination of 2 or more types.

In the synthesis of urethane (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6 It is preferable to use 0.01-1 mass% of urethanization catalysts, such as a 7-trimethyl- 1, 4- diazabicyclo [2.2.2] octane, with respect to the total amount of a reactant. In addition, the reaction temperature is usually preferably 5 to 90 ° C, particularly 10 to 80 ° C.

As a preferable specific example of urethane (meth) acrylate, the urethane (meth) acrylate etc. which are represented by following formula (2) or following formula (3) are mentioned.

[In Formula 2 and 3, "Acryl" represents an acryloyl group.]

As a urethane (meth) acrylate used by this invention, you may use a commercial item other than synthesize | combining as mentioned above. As a product marketed as a urethane (meth) acrylate, Arakawa Chemical Industries Ltd. make brand name: Beamset 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90 , EM92, Sanofko Co., Ltd. Brand Name: Photomer 6008, 6210, Shinnakamura Kagaku Kogyo Co., Ltd. Brand Name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA , U-324A, U-4H, U-6H, Toagosei Co., Ltd. brand name: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, Kyoesha Kagaku Co., Ltd. product name: AH-600, AT606, UA-306H, Nippon Kayakaku Co., Ltd. brand name: Kayarrad DPHA-40H, UX-2201, UX-2301, UX-3204, UX-3301, UX -4101, UX-6101, UX-7101, Nippon Kosei Kagaku Kogyo Co., Ltd. product name: Shiko UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-2010B, Nagami High School Manufacture name: Atresin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H-61, HDP- M20, Daicel WBC The manufacture brand name: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, etc. are mentioned. Among them, Kayardrad DPHA-40H and the like are preferable as those having six or more (meth) acrylate groups.

As for the compounding (containing) amount of the compound (A) which has a urethane bond used for this invention, making a total amount of (A), (B) and (C) component 100 mass%, and mix | blending 60-94 mass% Preferably, 70-90 mass% is more preferable. When it is less than 60 mass% or exceeds 94 mass%, when it is set as hardened | cured material, a thing with high hardness may not be obtained, and the adhesiveness of a coating film may fall.

2. (B) Ethylenic unsaturated group containing compound whose molecular weight is 290 or less

(B) component used for this invention is an ethylenically unsaturated group containing compound whose molecular weight is 290 or less. Since the (B) component has a small molecular weight, it tends to penetrate to some extent, such as TAC, before hardening. For this reason, it penetrates into the inside of the base from the boundary (contact surface) of the base and the hard coating layer, and is cured in a state where a continuous concentration gradient of component (B) is formed in the thickness direction of the base, including the boundary between the base and the hard coating layer, A substantially continuous gradient of refractive index is formed between the substrate and the hard coating layer. As a result, interference fringes of the laminate having the hard coat layer on the substrate are reduced.

Presence of (B) component which permeated in a base material can be evaluated with the following method. A hard coat layer is formed on the substrate by the same operation as usual. However, the irradiation amount at this time is about 1/2 to 1/4 normally, and it is about the grade which an unreacted ethylenically unsaturated group remains. The sections are cut in the same manner as the cross section of the substrate on which the hard coating layer is formed, with a transmission electron microscope, and the sections and osmium tetraoxide are placed in an airtight container and left to stand overnight (about 16 hours). Since osmium tetraoxide is added to the ethylenically unsaturated group by this operation, the osmium of this fragment is observed with an analytical electron microscope (TEM / AEM), whereby the ethylenically unsaturated group derived from component (B) It can be used as an alternative indicator of existence.

The component (B) is not limited as long as it is an ethylenically unsaturated group-containing compound having a molecular weight of 290 or less, but preferred examples thereof include (meth) acryloyl morpholine, N-vinyl-2-pyrrolidone, and N-vinyl-ε- Caprolactam, lauryl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and the like.

The compounding quantity (addition amount) of (B) component used for this invention makes the total amount of (A), (B), and (C) component 100 mass%, and is 5 to 35 mass% normally, and 5 to 25 mass Less than% is preferable and less than 10-20 mass% is more preferable. If the compounding quantity of (B) component is 5 mass% or more, the interference fringe of the laminated body which has a hard-coat layer on a base material can be suppressed effectively. Moreover, if the compounding quantity of (B) component is 35 mass% or less, the hard coat film which has high hardness is obtained. On the other hand, when the compounding quantity of (B) component exceeds 35 weight%, transparency of a cured film may fall.

3. Radiation (Photo) Polymerization Initiator (C)

The component (C) used in the curable composition of the present invention is a radiation (photo) polymerization initiator.

Radiation (photo) polymerization initiator (C) is a compound etc. which generate | occur | produce active radical species by radiation (light) irradiation.

The radiation (photo) polymerization initiator is not particularly limited as long as it is decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenonebenzyl ketal, 1-hydroxycyclohexylphenyl 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, benzoinpropylether, benzoinethylether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methyl propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, thioxanthone, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -buta To non-1,4- (2-hydroxy Phenyl) (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Phosphine 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, the Ciba Specialty Chemicals Co., Ltd. brand name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Tarocure 1116, 1173, BASF Corporation brand name: Lucirin TPO, UCB company brand name: Uvecryl P36, Fratelli Lambertisa brand name: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B etc. can be mentioned.

As for the compounding quantity of the radiation (photo) polymerization initiator (C) used by this invention, it is preferable to mix | blend 0.01-20 mass%, making the total amount of (A), (B), and (C) component 100 mass%, 0.1-10 mass% is more preferable. When it is less than 0.01 mass%, the hardness at the time of using hardened | cured material may become inadequate, and when it exceeds 10 mass%, it may not harden to the inside (lower layer) when it is set as hardened | cured material.

When hardening the curable composition of this invention, a radiation (photo) polymerization initiator and a thermal polymerization initiator can be used together as needed.

As a preferable thermal polymerization initiator, a peroxide and an azo compound are mentioned, for example, A benzoyl peroxide, t-butyl- peroxy benzoate, azobisisobutyronitrile etc. are mentioned as a specific example.

4. Organic Solvents (D)

The curable composition of the present invention is used after dilution with (D) an organic solvent for the purpose of swelling the substrate to some extent and for controlling the thickness of the coating film in order to assist the component (B) to penetrate the substrate. Therefore, it is preferable that it is a solvent which can swell the base material as an organic solvent (D) according to the base material to be used.

(D) Although it changes also with the kind of base material as a specific example of an organic solvent, Usually, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), 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, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned.

When the base material is TAC, (D) As an organic solvent, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, methylene chloride, chloroform, tetrahydrofuran and the like are preferable, and the base material is norbornene-based. In the case of resin, MEK, methylene chloride, tetrahydrofuran, cyclohexanone, cyclohexane, etc. are preferable. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

The compounding quantity of the (D) solvent in the curable composition of this invention is 30-60 mass% in the whole composition normally, and 40-60 mass% is preferable. Coating property is favorable in it being in the range of 30-60 mass%. If it is the said range, the viscosity of the curable composition of this invention will be 0.1-50,000 mPa sec / 25 degreeC normally. Moreover, it is preferable that it is 0.5-10,000 mPa * sec / 25 degreeC from a viewpoint of applicability | paintability.

5. Compound (E) other than (A) component and (B) component which has a polymerizable unsaturated group in a molecule | numerator

To the curable composition of this invention, compounds (E) other than (A) component and (B) component which have a polymerizable unsaturated group can be added as needed. The component (E) may be a compound having one ethylenically unsaturated group in the molecule, or may be a compound having two or more ethylenically unsaturated groups in the molecule, but most of the specific examples are limited to compounds having a molecular weight of more than 290. Is a (meth) acrylate having two or more ethylenically unsaturated groups in the molecule.

Preferable specific examples of the component (E) include (meth) acrylic esters as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol. Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree (Meth) acrylate, ethylene glucol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylic Latex, neopentylglycoldi (meth) acrylate, diethyleneglucoldi (meth) acrylate, triethyleneglucoldi (meth) acrylate, dipropyleneglucoldi (meth) acrylate, bis (2-hydroxy Poly) isocyanurate di (meth) acrylate and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters having two or more (meth) acryloyl groups in the molecule (Meth) acrylates, oligoether (meth) acrylates, oligoepoxy (meth) acrylates, etc. are mentioned. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate are preferable.

As a commercial item of a polyfunctional (meth) acrylate compound, Sanwa Chemical Co., Ltd. brand name: Nikalak MX-302, Toagosei Co., Ltd. brand name: Aronix M-400, M-402, M-403, M- 404, M-408, M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-325, M-326, M-327, 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-1382, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd. Brand Name: 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-368, 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, Kyoesha Chemical Co., Ltd. -4A, DPE-6A, DTMP-4A, etc. are mentioned. Said compound can be used individually by 1 type or in combination of 2 or more types.

Content of (E) component used for this invention makes the composition whole quantity except the organic solvent 100 mass%, and is 0-30 mass%, Preferably it exists in the range of 0-25 mass%. If it exists in the range of 0-30 mass%, the improvement of the curvature and curling property of a cured film can be expected.

6. Metal oxide particle (F) formed by bonding organic compound which has a polymerizable unsaturated group

The metal oxide particle (F) formed by bonding the organic compound which has a polymerizable unsaturated group can be mix | blended with the curable composition of this invention as long as the effect of this invention is not impaired. It is a particle | grain formed by combining the metal oxide particle (Fa) and the organic compound (Fb) containing a polymerizable unsaturated group (henceforth "reactive particle"). Here, the bond may be a covalent bond or a non-covalent bond such as physical adsorption.

(1) metal oxide particles (Fa)

The metal oxide particles (Fa) used in the present invention are selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium from the viewpoint of the hardness and colorlessness of the cured film of the curable composition obtained. It is preferred that they are metal oxide particles of at least one element selected.

As these metal oxide particles (Fa), for example, silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, tin oxide-containing tin oxide (ATO), tin-containing indium oxide (ITO), and oxidation Particles, such as antimony and a cerium oxide, are mentioned. Among them, particles of silica, alumina, zirconia and antimony oxide are preferable, and zirconia particles are particularly preferable from the viewpoint of high hardness. Moreover, a high refractive index hardened film can be obtained by using oxide particles, such as zirconium and titanium, and electroconductivity can also be provided to a hardened film by using ATO particle | grains. These can be used individually by 1 type or in combination of 2 or more types. Furthermore, it is preferable that oxide particle (Fa) is powder form or a dispersion liquid. In the case of a dispersion liquid, an organic solvent is preferable from a viewpoint of compatibility with other components, and a dispersibility. As such an organic solvent, For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an 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, and N-methylpyrrolidone, are mentioned. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

The number average particle diameter of the metal oxide particles (Fa) 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 by measurement by electron microscopy. When a number average particle diameter exceeds 2 micrometers, there exists a tendency for the transparency at the time of using a hardened | cured material to fall, or the surface state at the time of using a film to deteriorate. Moreover, in order to improve the dispersibility of particle | grains, various surfactant and amines can also be added.

As a commercial item of a silica particle, Nissan Chemical Industries, Ltd. make is a colloidal silica, for example.The brand name: methanol silicazol, 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 and the like. Moreover, as powder silica, Nippon Aerosil Co., Ltd. brand name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. brand name: Sealdex H31, H32, H51, H52, H121, H122, Nippon Silica Co., Ltd. brand name: E220A, E220, Fuji-Silicia Co., Ltd. brand name: SYLYSIA470, Nippon Sheet Glass Co., Ltd. brand name: SG flake, etc. are mentioned.

Moreover, as a water dispersion product of alumina, Nissan Chemical Industries, Ltd. brand name: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, Sumitomo Osaka Cement Co., Ltd. brand name: AS-150I; As a toluene dispersion product of alumina, Sumitomo Osaka Cement Co., Ltd. brand name: AS-150T; As a toluene dispersion of zirconia, Sumitomo Osaka Cement Co., Ltd. brand name: HXU-110JC; As a water dispersion product of the zinc antimonate powder, Nissan Chemical Industries, Ltd. make brand names: Celnax; Examples of powders and solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide are manufactured by Sea Kasei Co., Ltd. Product Name: Nano-Tech; As a water dispersion sol of antimony dope tin oxide, Ishihara Sangyo Co., Ltd. brand name: SN-100D; As ITO powder, the product of Mitsubishi Material Co., Ltd. product; As a cerium oxide aqueous dispersion, Taki Chemical Co., Ltd. brand name: Nydral etc. are mentioned.

The shape of the metal oxide particles Fa is spherical, hollow, porous, rod-shaped, plate-like, fibrous or indefinite, preferably spherical. The specific surface area (measured by BET specific surface area measurement method using nitrogen) of a metal oxide particle (Aa) becomes like this. Preferably it is 10-1000 m <2> / g, More preferably, it is 100-500 m <2> / g. The use form of these metal oxide particles (Fa) can be used in the state which disperse | distributed to the dry powder, water, or the organic solvent. For example, a dispersion of fine metal oxide particles known in the art can be used directly as a dispersion. In particular, the use of the dispersion liquid of a metal oxide particle is preferable for the use which requires the transparency excellent in hardened | cured material.

(2) organic compound (Fb)

The organic compound (Fb) used in the present invention is a compound having a polymerizable unsaturated group, and is preferably an organic compound containing a group represented by the following general formula (4). It also contains a [-OC (= O) -NH-] group, and further includes at least one of a [-OC (= S) -NH-] group and a [-SC (= O) -NH-] group. It is desirable to. Moreover, it is preferable that this 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.

 -A-C (= B) -NH-

[In Formula 4, A represents NH, O (oxygen atom) or S (sulfur atom), and B represents O or S.]

(i) polymerizable unsaturated groups

Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in an organic compound (Fb), For example, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, A maleate group and an acrylamide group are mentioned as a suitable example.

This polymerizable unsaturated group is a structural unit which addition-polymerizes with active radical species.

(ii) a group represented by the above formula (4)

The group [-AC (= B) -NH-] represented by the formula (4) contained in the specific organic compound is specifically [-OC (= O) -NH-], [-OC (= S) -NH- ], [-SC (= O) -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], and [-SC (= S)- NH-] is 6 species. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, at least one of [-OC (= O) -NH-] group, [-OC (= S) -NH-] group and [-SC (= O) -NH-] group is used in combination from the viewpoint of thermal stability. It is desirable to.

The group [-AC (= B) -NH-] represented by the above formula (4) generates suitable cohesive force due to hydrogen bonding between molecules, and when the cured film is used, characteristics such as excellent mechanical strength, adhesion to a substrate, and heat resistance It is thought to give.

(iii) silanol groups or groups that produce silanol groups by hydrolysis

It is preferable that an organic compound (Fb) is a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis. As a compound which produces | generates 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, The compound which the alkoxy group or the aryloxy group couple | bonded with the silicon atom, That is, an alkoxy silyl group containing compound or an aryloxy silyl group containing compound is preferable.

The silanol group generating site of the silanol group or the silanol group-producing compound is a structural unit bonded to the oxide particles (Fa) by a condensation reaction occurring after the condensation reaction or hydrolysis.

(iv) preferred embodiments

As a preferable specific example of an organic compound (Fb), the compound represented by following formula (5) is mentioned, for example.

In Formula 5, R <^4> , R <^5> may be same or different and is a hydrogen atom or a C1-C8 alkyl group or an aryl group, For example, methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl group Etc., wherein j is an integer of 1 to 3;

Examples of the group represented by [(R ⁴ O) _j R ⁵ _{3 - j} Si-] include trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group, dimethylmeth A oxysilyl group etc. are mentioned. Among these groups, trimethoxysilyl group, triethoxysilyl group, and the like are preferable.

R ⁶ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may include a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.

R ⁷ is a divalent organic group and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. As a specific example, Chain 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 group substituents and aryl group substituents thereof. Moreover, these divalent organic groups may contain the atomic group containing elements other than carbon and a hydrogen atom, and may also contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.

R ⁸ is a (k + 1) valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

Z represents monovalent organic group which has a polymerizable unsaturated group which intermolecular crosslinking-reacts in a molecule | numerator in presence of an active radical species. In addition, 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.

As a specific example of the compound represented by General formula (5), the compound represented by following General formula (6) or 7 is mentioned.

[In Formula 6 and 7, "Acryl" represents an acryloyl group.]

The synthesis | combination of the organic compound (Fb) used by this invention can use the method of Unexamined-Japanese-Patent No. 9-100111, for example. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate, reacted for several hours at 60 to 70 캜, and then pentaerythritol triacrylate is added thereto. And further reacted at 60 to 70 ° C. for several hours.

(3) reactive particles (F)

An organic compound (Fb) having a silanol group or a group which generates a silanol group by hydrolysis is mixed with the metal oxide particles (Fa), and hydrolyzed to bind both. The ratio of the organic polymer component, ie, the hydrolyzate and condensate of the hydrolyzable silane, in the obtained reactive particles (F) is usually a drag value of the mass reduction percentage when the dry powder is completely burned in air, for example, in room temperature in air. It can be calculated | required by the thermal mass spectrometry from 800 to 800 degreeC normally.

The amount of the organic compound (Fb) bonded to the oxide particles (Fa) is 100% by mass of the reactive particles (F) (the sum of the metal oxide particles (Fa) and the organic compound (Fb)), preferably 0.01% by mass It is more than 0.1 mass%, More preferably, it is 1 mass% or more. When the amount of the organic compound (Fb) bonded to the metal oxide particles (Fa) is less than 0.01% by mass, the dispersibility of the reactive particles (F) in the composition is not sufficient, and the transparency and the scratch resistance of the cured product obtained are not sufficient. It may become. Moreover, the compounding ratio of the metal oxide particle (Fa) in the raw material at the time of manufacture of a reactive particle | grain (F) becomes like this. Preferably it is 5-99 mass%, More preferably, it is 10-98 mass%.

The compounding (containing) content of the curable composition (F) in the curable composition is required to be in the range of 30 to 80 mass%, with the total amount of the composition excluding the organic solvent being 100 mass%, which is in the range of 40 to 60 mass%. It is preferable. If it is less than 30 mass%, the hardness of a cured film may be inadequate or the thing of high refractive index may not be obtained. When it exceeds 80 mass%, film formability may become inadequate. In this case, it is preferable that content of the oxide particle (Fa) which comprises a reactive particle (A) is 65-95 mass% of reactive particle (F). In addition, the quantity of reactive particle | grains (F) means solid content, and when reactive particle | grains (F) are used in the form of a dispersion liquid, the quantity of a dispersion medium is not included in the compounding quantity.

7. Other Ingredients

In the curable composition of this invention, as long as the effect of this invention is not impaired, a photosensitizer, a polymerization inhibitor, a polymerization start adjuvant, a leveling agent, a wettability improving agent, surfactant, a plasticizer, a ultraviolet absorber, antioxidant, an electrification charge An inhibitor, an inorganic filler, a pigment, dye, etc. can be mix | blended suitably.

8. Preparation of Composition

The curable composition of this invention can be manufactured as follows.

(E) component, (F) component, and other components were added to said (A), (B), (C), and (D) component as needed in the reaction container with agitator for 1 to 2 hours at 35 degreeC-45 degreeC It is stirred for a curable composition of the present invention.

9. Method of Application (Coating) of Composition

The curable composition of this invention is apply | coated on a base material, Preferably, after volatilizing the (D) solvent, it hardens | cures and it is set as a hard coat film. The curable composition of this invention is suitable for the use of an antireflection film and a coating material, and as a base material which is an object of reflection prevention and a coating, for example, polycarbonate, polymethyl methacrylate, polystyrene, an epoxy resin, a melamine resin, Triacetyl cellulose (hereinafter referred to as "TAC"), ABS resin, AS resin, norbornene-based resin, and the like. The shape of these substrates may be plate-like, film-like or three-dimensional shaped bodies, and the coating method may be a conventional coating method such as dip coating, spray coating, flow coating, shower coating, roll coating, spin coating, hair coating, or the like. Can be mentioned. The thickness of the coating film by these coatings is 0.1-400 micrometers normally after drying and hardening, Preferably it is 1-200 micrometers.

10. Curing method of the composition

The curable composition of the present invention can be cured by radiation (light) and, if necessary, by heat. In the case of radiation (light), the source is not particularly limited as long as the composition can be cured in a short time after coating. For example, a lamp, a resistance heating plate, a laser, or the like is used as a source of visible light as a source of visible light. Lamps, fluorescent lamps, lasers, etc. Mercury lamps, halide lamps, lasers, etc., as a source of ultraviolet rays, using a hot electron generated from a commercially available tungsten filament as a source of electron beams, cold cathode And a secondary electron system using secondary electrons generated by collision of the ionized gas phase molecules with the metal electrode. As the source of alpha rays, beta rays, and gamma rays, for example, fission materials such as ⁶⁰ Co may be mentioned. For gamma rays, a vacuum tube may be used to impinge the accelerator electrons to the anode. These radiations can be irradiated alone or in combination of two or more thereof over a period of time. In the case of heat, for example, an electric heater, an infrared lamp, hot air, or the like can be used.

The curing reaction of the curable composition of the present invention can be performed even under an air atmosphere or under anaerobic conditions such as nitrogen, and the cured product has excellent scratch resistance even when cured under anaerobic conditions.

II. Hard coating film

The hard coat film of this invention can apply | coat the said curable composition to various base materials, Preferably, after volatilizing the (D) solvent, it can obtain it by hardening | curing. Specifically, after coating a curable composition, and drying a volatile component at 0-200 degreeC preferably, it can obtain as a coating molding by performing hardening treatment with the above-mentioned radiation (light) and further heat as needed. In the case of radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, preferable irradiation light quantity of ultraviolet-ray is 0.01-10 J / cm <2>, More preferably, it is 0.1-2 J / cm <2>. Moreover, the irradiation conditions of a preferable electron beam are 10-300 KV of pressurized voltages, 0.02-0.30 mA / cm <2> of electron densities, and the electron beam irradiation amount is 1-10 Mrad. Preferable hardening conditions in the case of heat are 20-150 degreeC, and it is performed in 10 second-24 hours.

Since the cured layer of the present invention has high hardness and has a feature of forming a coating film (film) having excellent scratch resistance and adhesion to adjacent layers such as a substrate and a low refractive index layer, a film type liquid crystal element, a touch panel, and a plastic It is especially preferably used for antireflection films such as optical parts.

III. Laminate

The cured layer of the present invention is usually used by being laminated on a substrate as a hard coating layer, and further, by laminating a high refractive index layer and a low refractive index layer thereon, a laminate suitable as a reflection preventing film can be formed. The anti-reflection film may further have layers other than these, for example, a so-called wide band anti-reflection film having a plurality of combinations of a high refractive index film and a low refractive index film and having a relatively uniform reflectance property with respect to light of a wide wavelength range. The antistatic layer may be provided.

Although there is no restriction | limiting in particular as a base material, When using as an anti-reflective film, For example, the above-mentioned plastics (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose ( TAC) resin, ABS resin, AS resin, norbornene-type resin, etc.) are mentioned.

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

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

The cured product of the present invention obtained by applying the curable composition of the present invention on a substrate and UV cured has reduced curling, excellent flexibility, haze, and high hardness.

As a method of forming a low refractive index film on the high refractive index cured film formed by hardening the said curable composition, for example, in the case of a metal oxide film, vacuum deposition, sputtering, etc. are mentioned, In the case of a fluorine-type coating material cured film, it mentioned above The same method as the coating (coating) method of a composition is mentioned.

Thus, by laminating | stacking the said high refractive index cured film and the low refractive index film on a base material, reflection of the light on the surface of a base material can be effectively prevented.

Since the laminated body of this invention is excellent in scratch resistance, low reflectance, and excellent chemical-resistance, it is especially preferably used as an anti-reflective film, such as a film type liquid crystal element, a touch panel, a plastic optical component.

Hereinafter, although the Example of this invention is described in detail, the scope of the present invention is not limited to description of these Examples. In addition, in the Example, unless otherwise indicated, the compounding quantity of each component "part" has shown the mass part, and "%" has shown the mass%.

Preparation Example 1:

NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. for a solution containing 16 parts of 2,4-tolylene diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer 93 parts of pentaerythritol triacrylate which has a hydroxyl group) was dripped at 10 degreeC on 1 hour conditions, and it stirred at 60 degreeC for 6 hours, and made it the reaction liquid.

When the amount of remaining isocyanate in this reaction liquid was measured by FT-IR, it was 0.1 mass% or less, and it confirmed that reaction was performed almost quantitatively. In addition, it was confirmed that the molecule contains a urethane bond and acryloyl group (polymerizable unsaturated group).

From the above, 72 parts of the compound represented by the formula (3) and 37 parts of pentaerythritol tetraacrylate were obtained.

Examples 1-8 and Comparative Examples 1-4

Each component shown in following Table 1 was added to the container equipped with the stirrer which shielded the ultraviolet-ray, and it stirred at 40 degreeC for 1 hour, and obtained the uniform composition.

[Manufacture of laminated body for evaluation]

Each composition obtained by each Example or the comparative example was coated on TAC film using the coater equipped with the wire bar coater (# 12) according to film thickness, and it dried on the conditions of 3 minutes at 80 degreeC in oven, and coats the coating film. Formed. Subsequently, the coating film was ultraviolet-hardened on 0.3 J / cm <2> light irradiation conditions using the high pressure mercury lamp in air | atmosphere, and the TAC film with a hard-coat layer with a film thickness of 6 micrometers was obtained. About the obtained TAC film with a hard coat layer, the characteristic of following (1)-(4) was evaluated.

(1) interference non-uniformity

The reflectance profile was measured by the following method, and the magnitude | size (interference nonuniformity) of the amplitude of the wave-shaped profile was made into the index of interference fringe. The reflectance profile of the hardened | cured material was calculated | required using the Otsuka Denshi Co., Ltd. reflection spectrometer. Using the composition shown in Comparative Example 1, the amplitude (hereinafter referred to as "amplitude x") in the wavelength range of 500 to 700 nm of the reflectance profile of the TAC film with a hard coat layer obtained using the composition of each example or comparative example was used. The interference nonuniformity was evaluated as follows by comparing with the amplitude in the in-phase wavelength range (henceforth "amplitude ₀ ") of the reflectance profile of the obtained TAC film with a hard coat layer.

"◎" when amplitude x is less than 1/4 times amplitude ₀

"○" when amplitude x is less than 1/4 to 1/2 times amplitude ₀

"Δ" when amplitude x is less than 1/2 to 1 times amplitude ₀

"×" when amplitude x is one or more times amplitude ₀

(2) pencil hardness

Using the pencil hardness tester, it scraped 5 times on the conditions of 500 g of loads, and made the hardness of the hardest pencil core which is four or more free of charge as an evaluation value.

(3) adhesion

The adhesiveness of the cured film formed into a film on the base material was evaluated based on the checkerboard scale cellophane tape peeling test in JISK5400 by the following reference | standards with the residual film ratio in 1 mm2 and a total of 100 checkerboard scales.

"○" when the residual film ratio is 100 to 90%

"△" when the residual film ratio is less than 90 to 50%

"X" when the residual film ratio is less than 50 to 0%

(4) haze

Haze value (%) was measured according to ASTMD1003 using the Suga Seisakusho Co., Ltd. color haze meter, and it evaluated as the value containing a base film.

The contents of the commercial items described in Table 1 are shown below.

DPHA-40H: 10-functional urethane acrylate represented by the following formula (8); Nippon Kayaku High School Co., Ltd.

Irgacure 184: 1-hydroxycyclohexylphenyl ketone; Shiva Specialty Chemicals Co., Ltd.

Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1; Manufacture of Shiba Specialty Chemicals

The result of Table 1 showed that the cured film of the Example had little interference fringe, was excellent in pencil hardness and adhesiveness, and had small haze.

On the other hand, in Comparative Examples 1-3 which do not contain the (B) component in this invention, it turned out that an interference fringe is large. In Comparative Examples 2 and 3, an ethylenically unsaturated group-containing compound having a molecular weight of more than 290 was blended in place of the component (B), but the results are the same. In Comparative Example 4, in which the amount of the component (B) was large, the interference fringes were good, but it was found that the haze increased. Thus, by setting it as the structure of an Example, a hard coating film with high hardness, few interference fringes, and high transparency is obtained for the first time.

In addition, except for setting light irradiation conditions to 0.15 J / cm <2> in manufacture of the laminated body for evaluation using the curable composition manufactured in the said Example 1, the same operation was performed and the TAC film with a hard coat layer was obtained. The TAC film with the hard coat layer was embedded with an epoxy resin, and cut into a microtome perpendicular to the film surface to prepare a thin section. After placing the thin slices and 1 s of osmium tetraoxide (OsO ₄ ) in a 50 ml sealed container and allowing them to stand for 17 hours, the slices were observed with a transmission electron microscope EM-24015 manufactured by Nippon Denshi Co., Ltd. Using an energy dispersive X-ray analyzer VANTAGE manufactured by Thermo-Norlon Co., Ltd. mounted on an electron microscope, the interface between the hard coat layer and the substrate is sandwiched between the interior of the substrate and the interior of the substrate in the direction perpendicular to the interface. The amount of osmium at each distance from the said interface was measured, moving by 0.3 micrometer. In more detail, the result of elemental analysis obtained by scanning the electron beam by 1.2 micrometer in parallel with the said interface at each said distance was made into the measurement result in each distance. Since osmium tetraoxide is added to the ethylenically unsaturated group, it is an index of the amount of the ethylenically unsaturated group. The result is shown in FIG. The atomic percentage of osmium atoms (ratio of osmium atoms when the sum of the number of detected atoms (carbon, oxygen, osmium) is 100%) is obtained from the interface in contact with the hard coating layer and the reinforcement surface of the substrate. It is changing substantially continuously depending on the distance of. Atomic% of the osmium atom decreased sharply over the distance of 0.5 to 0.6 m. That is, among the constituents of the resin composition for hard coating layers used to form the hard coating layer, at least a compound having an ethylenically unsaturated group penetrates into the substrate and forms a region in which the concentration thereof is changed substantially continuously as described above. .

As described above, the curable composition of the present invention and the cured product thereof may be used to prevent damage (scratches) of plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring as building interior materials, wall materials, and artificial marble. Protective coatings to prevent contamination; Anti-reflection films such as a film type liquid crystal element, a touch panel and a plastic optical component; Adhesives and sealants of various substrates; Especially as a binder material of printing ink, it can use preferably as an anti-reflective film.

The curable composition of this invention and its hardened | cured material are especially useful as hard coating for optical films, such as an antireflection film and a touch panel, and hard coating for an optical disk.

Claims (5)

Let the total amount of following (A), (B) and (C) component be 100 mass%, (A) 60-94 mass% of compounds which have a urethane bond and 3 or more ethylenically unsaturated group in a molecule, (B) 5-35 mass% of ethylenically unsaturated group containing compounds whose molecular weight is 290 or less, and (C) 0.01-20 mass% of radiation (photo) polymerization initiators, And (D) at least one solvent selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, methylene chloride, chloroform and tetrahydrofuran Curable composition for hard coating films containing these. The method of claim 1, wherein the component (B) is selected from the group consisting of (meth) acryloyl morpholine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, and lauryl acrylate. Curable composition for hard-coat films containing 1 or more types of compound. The curable composition for a hard coat film according to claim 1, wherein the component (A) is a compound having a urethane bond and 6 or more ethylenically unsaturated groups in the molecule. The curable composition for hard coating films according to claim 1, wherein the total amount of the components (A), (B) and (C) is 100 mass%, and the content of the component (B) is 10% by mass or more and less than 20% by mass. The hard coat film obtained by hardening | curing the curable composition in any one of Claims 1-4.

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