JP5157449B2 - Curable composition, cured layer and laminate thereof - Google Patents

Description

  The present invention relates to a curable composition and a cured film thereof. More specifically, it has excellent coating properties and has 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.], which has high hardness, scratch resistance and adhesion to the substrate and adjacent layers such as the substrate and the high refractive index layer, and has high transparency. The present invention relates to a curable composition for a hard coat film that can form a film (film), and a hard coat film that has low curl properties and excellent flexibility and chemical resistance. In the present specification, the hard coat film refers to a cured film having a pencil hardness of “H” or more when measured using an evaluation method described later. In a laminate obtained by laminating a hard coat film on a substrate, this hard coat film is also referred to as a hard coat layer.

In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. Hardness, flexibility, scratch resistance, abrasion resistance, low curl (meaning that the cured film has low warpage), adhesion, transparency, chemical resistance, and coating surface appearance on the surface of various substrates There is a demand for a curable composition capable of forming an excellent cured film in any of the above (Patent Documents 1 and 2).
In addition to the above requirements, curable compositions capable of forming a cured film having a high refractive index are required in addition to the above requirements in applications of antireflection films such as film-type liquid crystal elements, touch panels, and plastic optical components.

  For example, in the case of a laminate in which a hard coat layer mainly composed of an acrylic resin is provided on a TAC film generally used as a base material, since the refractive index of the base material and the hard coat layer is generally different, the film surface There is an interference fringe caused by the optical path difference between the light reflected by the film and the light reflected by the back surface of the film, and this interference fringe has a problem that it looks clearer as the transparency of the film is higher. The degree of interference fringes is evaluated using the amplitude of the wavy profile (referred to as “interference unevenness” in this specification) of the reflectance profile of the laminate (a plot of the reflectance with respect to the measurement wavelength) as an index. be able to.

  It has also been pointed out that it is necessary to improve the adhesion between the base material layer and the hard coat layer. Therefore, in the case of a polyester resin often used together with TAC as a base material, an easily adhesive film for optics has been proposed for the purpose of reducing interference fringes and improving adhesion (Patent Documents 3 and 4).

  In the case of using a TAC base material, for the purpose of reducing interference fringes, an antireflection layer whose refractive index continuously changes in the film thickness direction is provided on the base material. Although the boundary surface clearly exists, a technique in which the refractive index of the antireflection layer at the boundary surface is set higher than the refractive index of the base material layer is also disclosed (Patent Document 5).

Japanese Patent Laid-Open No. 9-254321 Japanese Patent Laid-Open No. 9-300533 JP 2001-129948 A JP 2001-71439 A JP 2004-12657 A

  However, when a hard coat layer is provided on a base material, it is not satisfactory from the viewpoint of interference fringes, hardness, and adhesion between the base material and the hard coat layer.

  The present invention has been made in view of the above-described problems, has excellent coating properties, has high hardness on the surface of various substrates, has few interference fringes, and has good adhesion to the substrate. An object is to provide a curable composition capable of forming a hard coat film having excellent transparency and high transparency, and a hard coat film excellent in chemical resistance.

According to the present invention, the following curable composition for a hard coat film and a hard coat film obtained by curing the same can be provided.
1. The total amount of the following components (A), (B) and (C) is 100% by mass,
(A) 60 to 94% by mass of a compound having a urethane bond and three or more ethylenically unsaturated groups in the molecule,
(B) 5-35 mass% of ethylenically unsaturated group containing compound whose molecular weight is 290 or less,
And (C) a radiation (photo) polymerization initiator 0.01 to 20% by mass,
And (D) a curable composition for a hard coat film, comprising 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.
2. The said (B) component contains one or more compounds selected from the group which consists of (meth) acryloyl morpholine, N-vinyl- 2-pyrrolidone, N-vinyl-epsilon-caprolactam, and lauryl acrylate, Said 1 A curable composition for a hard coat film.
3. 3. The curable composition for a hard coat 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). Any one of the above 1-3, wherein the total amount of the components (A), (B) and (C) is 100% by mass, and the content of the component (B) is 10% by mass or more and less than 20% by mass. The curable composition for hard coat films described in 1.
5. The hard coat film obtained by hardening the curable composition in any one of said 1-4.

  According to the present invention, a hard material having excellent coating properties, high hardness, few interference fringes, excellent adhesion to the substrate, and high transparency on the surface of various substrates. A curable composition capable of forming a coat film and a hard coat film excellent in chemical resistance can be provided.

From the inside of the hard coat layer of the evaluation laminate using the curable composition produced in Example 1 to the inside of the substrate, 0.3 μm in the direction perpendicular to the boundary surface between the hard coat layer and the substrate. It is a graph which shows the result of having measured the amount of osmium in each distance from this boundary surface, moving each.

Hereinafter, embodiments of the curable composition for a hard coat film of the present invention (hereinafter referred to as “the curable composition of the present invention”) and the hard coat film as the cured film will be specifically described.
I. Curable composition The curable composition of the present invention comprises a total amount of the following components (A), (B) and (C) as 100% by mass, and (A) a urethane bond and three or more ethylenic bonds in the molecule. 60 to 94% by mass of a compound having a saturated group, (B) 5 to 35% by mass of an ethylenically unsaturated group-containing compound having a molecular weight of 290 or less, and (C) a radiation (photo) polymerization initiator of 0. 01 to 20% by mass and (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, To do.

Hereinafter, each structural component of the curable composition of this invention is demonstrated concretely.
1. (A) Compound having a urethane bond and three or more ethylenically unsaturated groups in the molecule The component (A) used in the present invention may be a compound having a urethane bond and three or more ethylenically unsaturated groups in the molecule. Although not particularly limited, urethane (meth) acrylate is preferable.
The urethane (meth) acrylate which is a compound (A) having a urethane bond is not particularly limited, but is basically obtained by reacting a (a) polyisocyanate compound and (b) a hydroxyl group-containing (meth) acrylate monomer. . Urethane (meth) acrylate may have other oligomer as a main chain and urethane bond thereto.
Urethane (meth) acrylate must contain at least 3 (meth) acryloyl groups bonded to the main chain of the oligomer, preferably 4 or more, more preferably 6 or more. .

Preferable specific examples of the urethane (meth) acrylate (A) obtained by reacting the polyisocyanate compound (a) and the hydroxyl group-containing (meth) acrylate monomer (b) include, for example, compounds represented by the following formula (1). Can do.
Y _r —R ² —O—CO—NH—R ¹ —NH—CO—O—R ³ —Y _s (1)
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 and R ³ are (r + 1) -valent and (s + 1) -valent organic groups, and are preferably selected from chain-like, branched or cyclic saturated hydrocarbon groups and unsaturated hydrocarbon groups.
Y represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. R and s are preferably integers of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
In the formula, R ² , R ³ and Y _r , Y _s may be the same or different.

  The proportion of (a) polyisocyanate compound and (b) hydroxyl group-containing (meth) acrylate monomer used for the synthesis of urethane (meth) acrylate is hydroxyl group-containing with respect to 1 equivalent of isocyanate group contained in (a) polyisocyanate compound. It is preferable that the hydroxyl group of the (meth) acrylate monomer is 1.0 to 2 equivalents.

  As a specific method for producing such urethane (meth) acrylate (A), for example, (c) a polyol compound, (a) a polyisocyanate compound and (b) a hydroxyl group-containing (meth) acrylate monomer are charged together. (C) a polyol compound and (a) a polyisocyanate compound are reacted, and then (b) a hydroxyl group-containing (meth) acrylate monomer is reacted; (a) a polyisocyanate compound and (b) a hydroxyl group containing A method of reacting a (meth) acrylate monomer and then (c) a polyol compound; (a) reacting a polyisocyanate compound and (b) a hydroxyl group-containing (meth) acrylate monomer, and then reacting (c) a polyol compound. Finally, (b) hydroxyl-containing (meth) acrylate module A method of reacting the mer, and the like.

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

  The polyether diol is obtained by ring-opening polymerization of a kind of ion-polymerizable cyclic compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol. Examples include polyether olefin diol, or polyether diol obtained by ring-opening copolymerization of two or more kinds of ion-polymerizable cyclic compounds. Examples of the ion polymerizable cyclic compound include ethylene oxide, propylene oxide, butene-1-oxide, isobutene oxide, oxetane, 3,3-dimethyloxetane, 3,3-bischloromethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, and 3-methyl. Tetrahydrofuran, 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 Cyclic ethers such as glycidyl ether and benzoic acid glycidyl ester Ethers, and the like.

  Polyether diol obtained by ring-opening copolymerization of the above ion polymerizable cyclic compound with cyclic imines such as ethyleneimine, cyclic lactone acids such as γ-propiolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes. Can also be used. Specific combinations of the two or more kinds of ion-polymerizable cyclic compounds include tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, butene-1- Examples thereof include terpolymers of oxide and ethylene oxide, tetrahydrofuran, butene-1-oxide, and ethylene oxide. The ring-opening copolymer of these ion-polymerizable cyclic compounds may be bonded at random or may be bonded in a block form.

  These polyether diols are, for example, PTMG650, PTMG1000, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation), Exenol 1020, 2020, 3020, Preminol PML-4002, PML-5005 (above manufactured by Asahi Glass Co., Ltd.), Unisafe DC 1100 , DC1800, DCB1000 (above, manufactured by NOF Corporation), PPTG1000, PPTG2000, PPTG4000, PTG400, PTG650, PTG1000, PTG2000, PTG-L1000, PTG-L2000 (above, manufactured by Hodogaya Chemical Co., Ltd.), Z- 3001-4, Z-3001-5, PBG2000 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Acclaim 2200, 2220, 3201, 3205, 4200, 4220, 8200, 12 00 can be obtained as (or more Lion Dale Co., Ltd.) commercially available products such as.

  (C) Although the said polyether diol is preferable as a polyol compound, polyester diol, polycarbonate diol, polycaprolactone diol, etc. can also be used besides this, These diols can also be used together with polyether diol. The polymerization mode of these structural units is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.

  Examples of polycarbonate diols are those conventionally produced by alcoholysis of diethylene carbonate with diol. The diol may be an alkylene diol having 2 to 12 carbon atoms such as 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, and the like. Mixtures of these diols can also be used. The polycarbonate diol can contain an ether bond in the main chain in addition to the carbonate group. Therefore, for example, a polycarbonate copolymer of an alkylene oxide monomer and the aforementioned alkylene diol can be used. Examples of the alkylene oxide monomer include ethylene oxide and tetrahydrofuran. These copolymers produce a cured coating that has a lower modulus than the polycarbonate homopolymer and also prevents crystallization of the liquid coating composition. A mixture of a polycarbonate diol and a polycarbonate copolymer can also be used.

  Examples of the polycarbonate diol include Duracarb 122 (PPG Industries) and Permanol KM10-1733 (Permuthane, Mass., USA). Duracarb 122 is produced by alcoholysis of diethyl carbonate with hexanediol. Examples of polyester diols include the reaction products of saturated polycarboxylic acids or their anhydrides and diols. Examples of saturated polycarboxylic acids and anhydrides include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, Examples thereof include glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid and the like, and anhydrides thereof and mixtures thereof. Examples of the diol include 1,4-butanediol, 1,8-octanediol, diethylene glycol, 1,6-hexanediol, dimethylolcyclohexane, and the like. 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. Tone 0301 and 0310 are trifunctional.

  Examples of (a) polyisocyanate used for the synthesis of urethane (meth) acrylate include aromatic diisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate. The specific compound is not particularly limited as long as it can be used as a photocurable resin composition, but preferred examples include aromatic diisocyanates and alicyclic diisocyanates, more preferably 2,4-tolylene diisocyanate and Examples include isophorone diisocyanate. These diisocyanate compounds may be used alone or in combination of two or more.

  Examples of (a) polyisocyanate compounds used in the synthesis of urethane (meth) acrylates include isophorone diisocyanate (IPDI), tetramethylxylene diisocyanate (TMXDI), toluene diisocyanate (TDI), diphenylmethylene diisocyanate, hexamethylene diisocyanate, cyclohexane. Hexylene diisocyanate, methylene dicyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diene Isocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-deca Ji diisocyanate, 1,4-addition to cyclohexylene diisocyanate, and compounds at both ends attached diisocyanates such as toluene diisocyanate polyalkylene oxide and / or polyester glycol. Examples include TDI-terminated polytetramethylene ether glycol and TDI-terminated polyethylene adipate, respectively. These diisocyanates are preferably diisocyanates such as isophorone diisocyanate and toluene diisocyanate.

  As the (b) hydroxyl group-containing (meth) acrylate monomer used for the synthesis of urethane (meth) acrylate, from the viewpoint of reactivity with the isocyanate group of polyisocyanate, a hydroxyl group containing a hydroxyl group bonded to a primary carbon atom (meta ) Acrylate monomers (referred to as primary hydroxyl group-containing (meth) acrylates) and hydroxyl group-containing (meth) acrylates (referred to as secondary hydroxyl group-containing (meth) acrylates) in which the hydroxyl groups are bonded to secondary carbon atoms are preferred.

  Examples of the primary hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolethane di (meth) acrylate.

  As the secondary hydroxyl group-containing (meth) acrylate, for example, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meta) ) Acrylates, and the like, and compounds obtained by addition reaction of glycidyl group-containing compounds such as alkyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate and (meth) acrylic acid. These hydroxyl group-containing (meth) acrylate monomers can be used alone or in combination of two or more.

  In the synthesis of urethane (meth) acrylate, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl- It is preferable to use 0.01 to 1% by mass of a urethanization catalyst such as 1,4-diazabicyclo [2.2.2] octane based on the total amount of the reactants. Moreover, reaction temperature is 5-90 degreeC normally, Especially 10-80 degreeC is preferable.

  Preferable specific examples of urethane (meth) acrylate include urethane (meth) acrylate represented by the following formula (2) or the following formula (3).

［式（２）及び（３）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formulas (2) and (3), “Acryl” represents an acryloyl group. ]

  As the urethane (meth) acrylate used in the present invention, a commercially available product can be used in addition to those synthesized as described above. As a product marketed as urethane (meth) acrylate, for example, Arakawa Chemical Industries, Ltd. product name: Beam set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, Product name: Photomer 6008, 6210, Shin-Nakamura Chemical Co., Ltd. Product name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U- 324A, U-4H, U-6H, manufactured by Toagosei Co., Ltd. Trade name: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, manufactured by Kyoeisha Chemical Co., Ltd. Product name: AH-600, AT606, UA-306H, manufactured by Nippon Kayaku Co., Ltd. Product name: Kayarad DPHA-40H, UX-2 01, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Trade names: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-2010B, manufactured by Negami Kogyo Co., Ltd. Trade name: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB , UN-3320HC, UN-3320HS, H-61, HDP-M20, manufactured by Daicel UC Corporation Product names: Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 830 1 etc. can be mentioned. Of these, Kayrad DPHA-40H and the like are preferred as those having 6 or more (meth) acrylate groups.

  The compounding (containing) amount of the compound (A) having a urethane bond used in the present invention is 60 to 94% by mass with the total amount of the components (A), (B) and (C) as 100% by mass. It is preferably 70 to 90% by mass. If it is less than 60% by mass or more than 94% by mass, a cured product may not be obtained with a high hardness, and the adhesion of the coating film may be lowered.

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

  The presence of the component (B) that has penetrated into the substrate can be evaluated by the following method. A hard coat layer is formed on the substrate by the same operation as usual. However, the irradiation amount at that time is set to about 1/2 to 1/4 of the normal amount so that unreacted ethylenically unsaturated groups remain. A section is cut out in the same manner as observing a cross section of the base material on which the hard coat layer is formed with a transmission electron microscope, and the section and osmium tetroxide are put in a sealed container and left to stand overnight (16 hours). . This operation adds osmium tetroxide to the ethylenically unsaturated group. By observing the osmium in this section with an analytical electron microscope (TEM / AEM), the component (B) is incorporated into the base material near the boundary surface. It can be used as an alternative index indicating the presence of the derived ethylenically unsaturated group.

  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. Preferred examples thereof include (meth) acryloylmorpholine, N-vinyl-2- Examples include pyrrolidone, N-vinyl-ε-caprolactam, lauryl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate.

  The blending amount (addition amount) of the component (B) used in the present invention is usually 5 to 35% by mass, with the total amount of the components (A), (B) and (C) being 100% by mass, The amount is preferably less than ˜25% by mass, and more preferably less than 10% to 20% by mass. 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 | membrane which has high hardness will be obtained. On the other hand, if the blending amount of the component (B) exceeds 35% by weight, the transparency of the cured film may be lowered.

3. Radiation (photo) polymerization initiator (C)
The component (C) used in the curable composition of the present invention is a radiation (photo) polymerization initiator.
The radiation (light) polymerization initiator (C) is a compound or the like that generates active radical species by radiation (light) irradiation.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- ( 1-methylvinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Uvekril P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B and the like.

  The blending amount of the radiation (light) polymerization initiator (C) used in the present invention is 0.01 to 20% by mass with the total amount of the components (A), (B) and (C) as 100% by mass. It is preferably 0.1 to 10% by mass. If it is less than 0.01% by mass, the hardness when it is a cured product may be insufficient. If it exceeds 10% by mass, it may not be cured to the inside (lower layer) when it is a cured product.

When curing the curable composition of the present invention, a radiation (light) polymerization initiator and a thermal polymerization initiator can be used in combination as necessary.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

4). Organic solvent (D)
The curable composition of the present invention comprises (D) for the purpose of swelling the substrate to some extent in order to help the component (B) penetrate into the substrate and for the purpose of adjusting the thickness of the coating film. Dilute with organic solvent. Therefore, the organic solvent (D) is preferably a solvent that can swell the base material depending on the base material to be used.

(D) Specific examples of the organic solvent depend on the type of substrate, but are usually alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) , Ketones such as methyl amyl ketone (MAK) and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, diethylene glycol Ethers such as monobutyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethyl Acetamide, amides such as N- methylpyrrolidone and the like.
When the substrate is TAC, the organic solvent (D) is preferably acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, ethyl lactate, methylene chloride, chloroform, tetrahydrofuran, etc., and the substrate is a norbornene resin In this case, MEK, methylene chloride, tetrahydrofuran, cyclohexanone, cyclohexane and the like 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 all the compositions normally, and 40-60 mass% is preferable. If it exists in the range of 30-60 mass%, coating property is favorable. If it is the said range, the viscosity of the curable composition of this invention will be 0.1-50,000 mPa * second / 25 degreeC normally. In addition, it is preferable that it is 0.5-10,000 mPa * second / 25 degreeC from a viewpoint of applicability | paintability.

5. Compound (E) other than (A) component and (B) component having a polymerizable unsaturated group in the molecule
The curable composition of the present invention may contain a compound (E) having a polymerizable unsaturated group other than the component (A) and the component (B) as necessary. The component (E) may be a compound having one ethylenically unsaturated group in the molecule or a compound having two or more ethylenically unsaturated groups in the molecule. Are limited to compounds exceeding 290, many of the specific examples are (meth) acrylates having two or more ethylenically unsaturated groups in the molecule.

  As a preferred specific example of the component (E), (meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) ) Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopenty Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate And poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates And oligoepoxy (meth) acrylates. Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable.

  As a commercial item of a polyfunctional (meth) acrylate compound, Sanwa Chemical Co., Ltd. product name: Nicarak MX-302, Toagosei Co., Ltd. product 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. Trade names: 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, GP -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 Kyoeisha Chemical Co., Ltd. Trade name: Light acrylate PE-4A, DPE- 6A, DTMP-4A, and the like. Said compound can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (E) used in the present invention is 0 to 30% by mass, preferably 0 to 25% by mass, based on 100% by mass of the total composition excluding the organic solvent. If it is in the range of 0 to 30% by mass, an improvement in the flexibility and curlability of the cured film can be expected.

6). Metal oxide particles (F) formed by bonding an organic compound having a polymerizable unsaturated group
In the curable composition of the present invention, metal oxide particles (F) formed by bonding an organic compound having a polymerizable unsaturated group may be blended as long as the effects of the invention are not impaired. It is a particle obtained by bonding metal oxide particles (Fa) and an organic compound (Fb) containing a polymerizable unsaturated group (hereinafter referred to as “reactive particles”). 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 composed of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and the like from the viewpoints of hardness and colorlessness of the cured film of the resulting curable composition. Metal oxide particles of at least one element selected from the group consisting of cerium are preferred.

  Examples of these metal oxide particles (Fa) include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, antimony-containing tin oxide (ATO), and tin-containing indium oxide (ITO). And particles such as antimony oxide and cerium oxide. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness, and zirconia particles are particularly preferable. A cured film having a high refractive index can be obtained by using oxide particles such as zirconium and titanium, and conductivity can be imparted to the cured film by using ATO particles or the like. These can be used singly or in combination of two or more. Furthermore, the oxide particles (Fa) are preferably in the form of powder or dispersion. In the case of a dispersion, the dispersion medium is preferably an organic solvent from the viewpoints of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide and dimethylacetamide And amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the metal oxide particles (Fa) is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm, as measured by electron microscopy. . When the number average particle diameter exceeds 2 μm, the transparency when cured is lowered, or the surface state when it is coated tends to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Examples of commercially available silica particles include colloidal silica manufactured by Nissan Chemical Industries, Ltd. Trade names: Methanol Silica Sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like. As the powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Product names: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd., trade names: SG flakes and the like.

  Moreover, as an aqueous dispersion product of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, product names manufactured by Sumitomo Osaka Cement Co., Ltd .: AS- As a toluene dispersion of alumina 150I, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; As a zirconia toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU-110JC; zinc antimonate powder Product name: Celnax; Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powder and solvent dispersion products are manufactured by C-Chemicals Co., Ltd. Name: Nanotech; Antimony-doped tin oxide aqueous dispersion sol manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100 ; The ITO powder, Mitsubishi Materials Co., Ltd. product; a cerium oxide aqueous dispersion, Taki Chemical Co., trade name: Nidoraru like.

The metal oxide particles (Fa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of the metal oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These metal oxide particles (Fa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine metal oxide particles known in the art as the dispersion can be used directly. In particular, it is preferable to use a dispersion of metal oxide particles in applications that require excellent transparency in the cured product.

(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 formula (4). Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. 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 | generates a silanol group by hydrolysis.

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

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Fb) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (4) The group [—A—C (═B) —NH—] represented by the formula (4) contained in the specific organic compound is specifically [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—]. , [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—A—C (═B) —NH—] represented by the formula (4) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when formed into a cured film. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (Fb) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the oxide particles (Fa) by a condensation reaction that occurs following a condensation reaction or hydrolysis.

(Iv) Preferred Embodiment Specific examples of the organic compound (Fb) include compounds represented by the following formula (5).

In the formula (5), R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁴ O) _j R ⁵ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is 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. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may 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 a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by formula (5) include compounds represented by the following formula (6) or formula (7).

［式（６）及び式（７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formulas (6) and (7), “Acryl” represents an acryloyl group. ]

  For the synthesis of the organic compound (Fb) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate, reacted at 60 to 70 ° C. for several hours, then added with pentaerythritol triacrylate, and further reacted at 60 to 70 ° C. for several hours. Manufactured.

(3) Reactive particles (F)
The organic compound (Fb) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with the metal oxide particles (Fa), hydrolyzed, and bonded together. The ratio of the organic polymer component in the resulting reactive particles (F), that is, the hydrolyzate and condensate of hydrolyzable silane, is usually the mass loss% when the dry powder is completely burned in air. The constant value of can be determined, for example, by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (Fb) bound to the oxide particles (Fa) is preferably 100% by mass of the reactive particles (F) (the total of the metal oxide particles (Fa) and the organic compound (Fb)), It is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Most 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 resulting cured product The transparency and scratch resistance of the object may not be sufficient. Moreover, the compounding ratio of the metal oxide particles (Fa) in the raw material during the production of the reactive particles (F) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass.

  The compounding (containing) amount of the reactive particles (F) in the curable composition needs to be in the range of 30 to 80% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass, and 40 It is preferable to be in the range of ˜60% by mass. If it is less than 30% by mass, the hardness of the cured film may be insufficient or a high refractive index may not be obtained. If it exceeds 80% by mass, the film formability may be insufficient. In this case, the content of the oxide particles (Fa) constituting the reactive particles (A) is preferably 65 to 95% by mass of the reactive particles (F). The amount of the reactive particles (F) means a solid content, and when the reactive particles (F) are used in the form of a dispersion, the amount of the reactive particles does not include the amount of the dispersion medium.

7). Other components In the curable composition of the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, an interface, as necessary. An activator, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.

8). Method for Producing Composition The curable composition of the present invention can be produced as follows.
The components (A), (B), (C), and (D) are optionally mixed with (E), (F), and other components in a reaction vessel equipped with a stirrer at 35 ° C to 45 ° C. Stir for 1 to 2 hours to obtain the curable composition of the present invention.

9. Application (Coating) Method of Composition The curable composition of the present invention is applied on a substrate, preferably (D) after volatilizing the solvent, and then cured to obtain a hard coat film. The curable composition of the present invention is suitable for use as an antireflection film or a coating material, and examples of a base material to be antireflection or coating include polycarbonate, polymethyl methacrylate, polystyrene, epoxy resin, and melamine resin. , Triacetyl cellulose (hereinafter referred to as “TAC”), ABS resin, AS resin, norbornene resin, and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned. The thickness of the coating film by these coatings is usually 0.1 to 400 μm after drying and curing, and preferably 1 to 200 μm.

10. Method of curing composition The curable composition of the present invention can be cured by radiation (light) and, if necessary, heat. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.
Moreover, when using heat, as the heat source, 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 carried out under an anaerobic condition such as nitrogen in an air atmosphere. Even when cured under an anaerobic condition, the cured product has excellent resistance to resistance. Has scratch properties.

II. Hard Coat Film The hard coat film of the present invention can be obtained by applying the curable composition to various substrates and preferably curing (D) after volatilizing the solvent. Specifically, by coating the curable composition, preferably drying the volatile component at 0 to 200 ° C., and then performing the curing treatment with the above-described radiation (light) and, if necessary, heat. It can be obtained as a coated molded body. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours.

  The cured layer of the present invention has a characteristic that it can form a coating film (film) having high hardness and excellent scratch resistance and adhesion to adjacent layers such as a substrate and a low refractive index layer. It is particularly suitably used for antireflection films such as liquid crystal elements, touch panels, and plastic optical components.

III. Laminated body The cured layer of the present invention is usually used by being laminated on a substrate as a hard coat layer, and by further laminating a high refractive index layer and a low refractive index layer thereon, an antireflection film. As such, a suitable laminate can be formed. The antireflection film may further include layers other than these. For example, a plurality of combinations of a high refractive index film and a low refractive index film are provided to provide a relatively uniform reflectance with respect to light in a wide wavelength range. A so-called wideband antireflection film having characteristics may be used, and an antistatic layer may be provided.
Although there is no restriction | limiting in particular as a base material, When using as an antireflection film, the above-mentioned plastics (a polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, an epoxy resin, a melamine resin, a triacetyl cellulose (TAC) resin, for example are mentioned. , ABS resin, AS resin, norbornene resin, etc.).
Examples of the high refractive index film used in the laminate of the present invention include a cured coating material film containing metal oxide particles such as zirconia particles having a refractive index of 1.65 to 2.20. .
Examples of the low refractive index film used in the laminate of the present invention include a metal oxide film such as magnesium fluoride and silicon dioxide having a refractive index of 1.38 to 1.45, a fluorine-based coating material cured film, and the like. Can be mentioned.

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

Examples of a method for forming a low refractive index film on a high refractive index cured film obtained by curing the curable composition include vacuum deposition and sputtering in the case of a metal oxide film. In addition, in the case of a fluorine-based coating material cured film, the same method as the method for applying (coating) the composition described above can be used.
Thus, by laminating the high refractive index cured film and the low refractive index film on the substrate, reflection of light on the substrate surface can be effectively prevented.
The laminate of the present invention is particularly suitable as an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like because it has excellent scratch resistance, low reflectance and excellent chemical resistance.
[Example]

Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to the description of these examples. In the examples, unless otherwise specified, the amount of each component means “parts” by mass and “%” means mass%.
Production Example 1:
To a solution consisting of 16 parts of 2,4-tolylene diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer, NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical) Is only pentaerythritol triacrylate having a hydroxyl group.) 93 parts were added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours to obtain a reaction solution.
When the amount of residual isocyanate in this reaction liquid was measured by FT-IR, it was 0.1 mass% or less, and it was confirmed that the reaction was carried out almost quantitatively. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
As a result, 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 Table 1 was added to a container equipped with a stirrer that shielded ultraviolet rays, and stirred at 40 ° C. for 1 hour to obtain a uniform composition.

[Manufacture of evaluation laminate]
Each composition obtained in each example or comparative example was coated on a TAC film using a coater equipped with a wire bar coater (# 12) according to the film thickness, and in an oven at 80 ° C., 3 It dried on the conditions for minutes, and formed the coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 0.3 J / cm ^{2 in} the atmosphere using a high-pressure mercury lamp to obtain a TAC film with a hard coat layer having a thickness of 6 μm. About the obtained TAC film with a hard coat layer, the following properties (1) to (4) were evaluated.

(1) Interference unevenness The reflectance profile was measured by the following method, and the amplitude of the wavy profile (interference unevenness) was used as an indicator of interference fringes. The reflectance profile of the cured product was determined using a reflection spectroscope manufactured by Otsuka Electronics Co., Ltd. Comparative Example 1 shows 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. The amplitude of the reflectance profile of the TAC film with a hard coat layer obtained using the composition in the same wavelength range (hereinafter referred to as “amplitude ₀ ”) was compared, and interference unevenness was evaluated as follows.
When the amplitude x is less than 1/4 times the amplitude ₀ , “◎”
“O” when the amplitude x is 1/4 to less than 1/2 times the amplitude ₀
“△” when the amplitude x is 1/2 to less than 1 times the amplitude ₀
“X” when the amplitude x is 1 or more times the amplitude ₀

(2) Pencil Hardness Using a pencil hardness tester, the hardness of the core of the hardest pencil that was scratched five times under the condition of a load of 500 g and was not damaged four times or more was used as an evaluation value.

(3) Adhesiveness The adhesiveness of the cured film formed on the substrate is determined according to the following criteria in terms of the remaining film rate at 100 mm grids in total of 1 mm square in accordance with the grid cellophane tape peeling test in JIS K5400. Adhesion was evaluated.
“○” when the remaining film rate is 100 to 90%
“△” when the remaining film ratio is less than 90 to 50%
When the remaining film rate is less than 50% to 0%, “×”

(4) Haze Using a color haze meter manufactured by Suga Seisakusho Co., Ltd., the haze value (%) was measured according to ASTM D1003 and evaluated as a value including a base film.

The contents of the commercially available products described in Table 1 are shown below.
DPHA-40H: 10-functional urethane acrylate represented by the following formula (8); manufactured by Nippon Kayaku Co., Ltd.

Irgacure 184: 1-hydroxycyclohexyl phenyl ketone; manufactured by Ciba Specialty Chemicals,
Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1; manufactured by Ciba Specialty Chemicals

From the results in Table 1, it can be seen that the cured films of the examples have few interference fringes, excellent pencil hardness and adhesion, and small haze.
On the other hand, in Comparative Examples 1-3 which do not contain the (B) component in this invention, it turns out that an interference fringe is large. In Comparative Examples 2 and 3, an ethylenically unsaturated group-containing compound having a molecular weight exceeding 290 is blended in place of the component (B), but the results are the same. In Comparative Example 4 in which the amount of component (B) is large, the interference fringes are good, but it can be seen that haze increases. Thus, by adopting the configuration of the example, a hard coat film having high hardness, less interference fringes, and high transparency can be obtained for the first time.

For reference, the same operation was performed except that the light irradiation condition was changed to 0.15 J / cm ² in the production of the evaluation laminate using the curable composition produced in Example 1, and the hard coat layer was attached. A TAC film was obtained. The TAC film with a hard coat layer was embedded with an epoxy resin, and cut out with a microtome perpendicular to the film surface to prepare a thin slice. The thin section and about 1 mm ³ of osmium tetroxide (OsO ₄ ) were placed in a 50 ml sealed container and allowed to stand for 17 hours, and then the section was observed with a transmission electron microscope EM-24015 manufactured by JEOL Ltd. Using the thermal dispersive X-ray analyzer VANTAGE manufactured by Thermon-Run Co., Ltd. attached to the same electron microscope, the interface between the hard coat layer and the base material is sandwiched, and from the inside of the hard coat layer to the inside of the base material. The amount of osmium at each distance from the boundary surface was measured while moving by 0.3 μm in a direction perpendicular to the boundary surface. More specifically, the result of elemental analysis obtained by scanning the electron beam with 1.2 μm in parallel with the boundary surface for each distance was used as the measurement result at each distance. Since osmium tetroxide is added to the ethylenically unsaturated group, it is an indicator of the amount of the ethylenically unsaturated group. The result is shown in FIG. The atomic% of osmium atoms (ratio of osmium atoms when the total number of detected atoms (carbon, oxygen, osmium) is 100%) is in the base material in contact with the reinforcing surface of the hard coat layer and the base material. , Substantially continuously depending on the distance from the boundary surface. The atomic% of osmium atoms rapidly decreased as the distance increased from 0.5 to 0.6 μm. That is, among the components of the resin composition for a hard coat layer used to form the hard coat layer, a compound having at least an ethylenically unsaturated group penetrates into the base material, and the concentration is substantially as described above. Thus, a continuously changing region is formed.

As described above, the curable composition of the present invention and the cured product thereof are, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. Protective coating materials to prevent scratches (scratches) and contamination; antireflection films for film-type liquid crystal elements, touch panels, plastic optical components, etc .; adhesives and sealing materials for various substrates; printing ink binder materials, etc. In particular, it can be suitably used as an antireflection film.
The curable composition of the present invention and the cured product thereof are particularly useful as a hard coat for optical films such as an antireflection film and a touch panel, and a hard coat for optical disks.

Claims (4)

The total amount of the following components (A), (B) and (C) is 100% by mass,
(A) 60 to 94% by mass of a compound having a urethane bond and three or more ethylenically unsaturated groups in the molecule,
(B) 5 to 35% by mass of one or more compounds selected from the group consisting of (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam and lauryl acrylate ,
And (C) a radiation (photo) polymerization initiator 0.01 to 20% by mass,
And (D) a curable composition for a hard coat film, comprising 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.   The curable composition for hard coat films according to claim 1, wherein the component (A) is a compound having a urethane bond and six or more ethylenically unsaturated groups in the molecule.   The hardware according to claim 1, wherein the total amount of the components (A), (B), and (C) is 100% by mass, and the content of the component (B) is 10% by mass or more and less than 20% by mass. A curable composition for a coating film. Hard coat film obtained by curing the curable composition according to any one of claims 1-3.

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