JP5494309B2 - Laminated film - Google Patents

Description

  The present invention relates to a curable composition and a cured film containing a fatty acid ester surfactant having a (meth) acryloyl group. More specifically, the present invention relates to a curable composition and a cured film useful as a hard coat material.

  In recent years, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of each substrate has hardness, Curing composition capable of forming a cured film excellent in any of scratch resistance, antifouling property, abrasion resistance, surface slipperiness, low curling property, adhesion, transparency, chemical resistance and appearance of coating surface Things are requested.

  In recent years, touch panels have been increasingly used for input to information terminals. The touch panel performs data entry by directly touching the display screen with a finger or pen, etc., so scratch resistance and antifouling properties, particularly fingerprint visibility, fingerprint wiping properties, durability, transparency, etc. are required. The present condition is that the cured film which satisfy | fills all of these characteristics is not obtained.

  Patent Document 1 discloses a hard coat film for a touch panel or a display in which a nonionic surfactant of HLB 2 to 15 made of a fatty acid ester is added to an ionizing radiation curable resin. This film had good fingerprint visibility and fingerprint wiping properties, but was inferior in scratch resistance and in transparency. This is because the fatty acid ester-based surfactant bleeds out to the surface of the cured film in order to develop fingerprint visibility and fingerprint wiping properties, thereby reducing the scratch resistance and transparency of the cured film.

  Patent Document 2 discloses a polyalkylene oxide chain-containing polymer (specifically a fatty acid ester surfactant) having a predetermined structure and having polymerizable unsaturated groups at all terminals, and two or more (meta) There is disclosed a curable resin composition for a hard coat layer, which contains a compound having an acryloyl group and inorganic fine particles having a polymerizable unsaturated group on the surface, and these components can react with each other. In the cured film obtained by curing this curable resin composition, the polyalkylene oxide chain-containing polymer, the compound having a (meth) acryloyl group, and inorganic particles having a polymerizable functional group on the surface react with each other. As a result, the polyalkylene oxide chain-containing polymer does not bleed out on the surface of the cured film, and the components can be cross-linked with each other, thereby improving the scratch resistance. The cured film of Patent Document 2 is excellent in fingerprint visibility, fingerprint wiping property, and scratch resistance, but there is room for improvement in durability such as dry heat resistance and wet heat resistance.

JP 2004-114355 A JP 2008-165040 A

  The present invention has been made in view of the above-mentioned problems. In addition to excellent fingerprint visibility, fingerprint wiping properties, and scratch resistance, the cured film obtained has durability such as wet heat resistance and dry heat resistance, and is high. It aims at providing the curable composition useful as a laminated film and hard-coat material which have transparency.

In order to achieve the above object, the present inventors conducted extensive research and found that all hydroxyl groups present at the terminals of the fatty acid ester surfactants are polymerizable unsaturated groups ((meth) acryloyl groups). It discovered that durability, such as tolerance and dry heat tolerance, was impaired. Therefore, when a fatty acid ester-based surfactant having a hydroxyl group and a (meth) acryloyl group is used, it has excellent fingerprint visibility and fingerprint wiping properties, excellent scratch resistance, and durability such as wet heat resistance and dry heat resistance. The present invention has been completed by finding that a cured film having excellent properties can be obtained.
Furthermore, by having a polymerizable unsaturated group in the fatty acid ester surfactant, the compatibility with the binder component is improved, and even when the fatty acid ester surfactant is blended at a high concentration, it is cured. It has also been found that whitening of the film (coating film) does not occur and high transparency is obtained.

That is, the present invention provides the following laminated film and curable composition.
1. A laminated film having a cured film formed using a curable composition containing the following components (A) to (C) on at least one surface of a transparent film substrate.
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) Fatty acid ester surfactant having a hydroxyl group and a (meth) acryloyl group and having an HLB value in the range of 2 to 15. 2. The laminated film according to 1 above, wherein the component (C) has an HLB value in the range of 2 to 12.
3. 3. The laminated film according to 1 or 2 above, wherein the molar ratio of the hydroxyl group and the (meth) acryloyl group contained in the component (C) is in the range of hydroxyl group: (meth) acryloyl group = 1: 6 to 3: 1.
4). The laminated film according to any one of 1 to 3, wherein the component (C) has a linear or branched monovalent or divalent hydrocarbon group having 8 to 30 carbon atoms.
5. The component (C) is a compound obtained by reacting a hydroxyl group of a fatty acid ester surfactant having a hydroxyl group but not having a (meth) acryloyl group with a compound having a (meth) acryloyl group The laminated film in any one of 1-4.
6). 6. The laminated film according to 5 above, wherein the compound having a (meth) acryloyl group described in 5 is a compound having an isocyanate group and a (meth) acryloyl group.
7). Furthermore, (D) The laminated | multilayer film in any one of said 1-6 containing the inorganic oxide particle of number average particle diameter 1-200 nm.
8). 8. The laminated film according to 7 above, wherein the component (D) is inorganic oxide particles surface-treated with an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule.
9. The cured film is a film that does not contain the component (D), and when the total of the components (A) and (B) is 100 parts by weight, the component (C) is in the range of 0.1 to 30 parts by weight. The laminated film according to any one of 1 to 6, which is an inner layer.
10. The laminate according to 7 or 8 above, wherein the component (C) is in the range of 0.1 to 30 parts by weight when the total of the components (A), (B) and (D) is 100 parts by weight. the film.
11. Furthermore, (E) The laminated | multilayer film in any one of said 1-10 containing the organic or inorganic particle | grains whose number average particle diameter is 0.5-10 micrometers.
12 A curable composition containing the following components (A) to (C).
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) Fatty acid ester surfactant having a hydroxyl group and a (meth) acryloyl group and having an HLB value in the range of 2 to 15. 13. The curable composition as described in 12 above, which is used for forming a hard coat.
14 A cured film obtained by curing the curable composition as described in 12 or 13 above.

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in fingerprint visibility and fingerprint wiping off property, the laminated | multilayer film which has durability, such as abrasion resistance, wet heat resistance, and dry heat resistance, can be provided.
According to the present invention, a laminated film having further excellent transparency can be provided.
According to the present invention, it is excellent in fingerprint visibility, fingerprint wiping property, scratch resistance, durability such as resistance to moist heat and dry heat, and a cured film with excellent transparency. Sex compositions can be provided.

Hereinafter, the present invention will be described in detail.
I. Curable composition The curable composition of this invention (henceforth the composition of this invention) may contain the following component (A)-(G). Among these, components (A) to (C) are essential components, and components (D) to (G) are optional components that are added as necessary.
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) Fatty acid ester-based surfactant having a hydroxyl group and a (meth) acryloyl group and having an HLB value in the range of 2 to 15 (D ) Inorganic oxide particles having a number average particle size of 1 to 200 nm (E) Organic or inorganic particles having a number average particle size of 0.5 to 10 μm (F) Organic solvent (G) Other additives

In the composition of the present invention, the component (C) is a fatty acid ester surfactant having a fatty acid ester group and a (meth) acryloyl group and having an HLB value (Hydrophile-Lipophile Balance) of 2 to 15. ) On the surface of the cured film is prevented, the scratch resistance of the cured film is improved, and further, durability such as wet heat resistance and dry heat resistance is improved. Moreover, fingerprint visibility improves by having a hydroxyl group.
Moreover, since the said component (C) has both a (meth) acryloyl group and a hydroxyl group, compatibility with a binder component (A) improves, and the hardening obtained even if it mix | blends a component (C) at high concentration. The film (coating film) is not whitened, and gives a cured film having high transparency.
Hereinafter, each component of the composition of the present invention will be described.

(A) Polyfunctional (meth) acrylic monomer Component (A) The polyfunctional (meth) acrylic monomer used in the present invention is a (meth) acrylic monomer having two or more (meth) acryloyl groups. The component (A) is a so-called binder component for improving the film formability of the composition. By combining with the component (C) described later, the component (C) can be immobilized on the cured film.
In addition, although the component (D) mentioned later is a reactive particle (Dc) and the component (C) mentioned later may also have a plurality of (meth) acryloyl groups, the polyfunctional (meth) acrylic monomer ( A) does not contain reactive particles (Dc) and component (C).

  Specific examples of polyfunctional (meth) acrylic monomers include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Polyfunctional having 3 or more (meth) acryloyl groups such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate (Meth) acrylic monomer; ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-he (Meth) acryloyl groups such as sundiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate Hydroxyl group-containing polyfunctional (meth) acrylates such as bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and ethylene oxide or propylene oxide adducts to these hydroxyl groups Poly (meth) acrylates; oligoester (meth) acrylates having two or more (meth) acryloyl groups, oligoether (meth) acrylates, oligoepoxy (meth) acrylates, etc. Kill. The polyfunctional (meth) acrylic monomer mentioned above may be used individually by 1 type, and can also use 2 or more types together.

  Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like are preferable.

  As a commercial item of such a polyfunctional (meth) acryl monomer (A), Toagosei Co., Ltd. Aronix M-400, M-404, M-408, M-450, M-305, M- 309, M-310, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO- 1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, KAYARAD D-310, D-330, DPHA, DPC manufactured by Nippon Kayaku Co., Ltd. -20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415 SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR -268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA , TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. ) Light acrylate PE-4A, DPE-6A, DTMP-4A, NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.

  Component (A), based on the total amount of 100% by weight, preferably contains 50% by weight or more of a polyfunctional (meth) acrylic monomer having 3 or more (meth) acryloyl groups, more preferably 70% by weight or more, More preferably, it is 100% by weight.

  The compounding amount of the component (A) in the composition of the present invention is in the range of 10 to 95 parts by weight when the total of the components (A), (B) and (D) is 100 parts by weight. It is preferably within the range of 80 parts by weight, and more preferably within the range of 20 to 70 parts by weight. When the component (A) is blended in the above range, a cured film having high hardness can be obtained.

(B) Photopolymerization initiator Component (B) in the present invention is a photopolymerization initiator. As a photoinitiator (B), it is a compound (radiation (light) polymerization initiator) which generates active radical seed | species by radiation (light) irradiation, and can use what is used widely.

  The photopolymerization 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, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- -Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON, 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.

  Examples of commercially available photopolymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG24-61, Darocur 1116, manufactured by Ciba Specialty Chemicals Co., Ltd. 1173, Lucylin TPO manufactured by BASF, Ubekril P36 manufactured by 8893UCB, Ezacure KIP150 manufactured by Lamberti, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, and the like.

  The content of the component (B) in the composition of the present invention is usually within the range of 0.1 to 10 parts by weight when the total of the components (A), (B) and (D) is 100 parts by weight. It is preferably within the range of 0.1 to 5 parts by weight, and more preferably within the range of 0.5 to 5 parts by weight. In addition, content of a component (B) can also be determined on the basis of content of a component (A) within said range. For example, when the content of the component (A) is 100 parts by weight, the content of the component (B) is preferably 0.5 to 20 parts by weight, and is preferably 0.5 to 15 parts by weight. More preferred. By setting the content of the component (B) within the above range, it is possible to obtain a high hardness coating film.

(C) A fatty acid ester surfactant having a hydroxyl group and a (meth) acryloyl group and having an HLB value in the range of 2 to 15 (hereinafter, component (C) is referred to as “(C) fatty acid ester surfactant”. Sometimes.)
Since the component (C) has a (meth) acryloyl group and can be bonded and fixed to the binder component in the composition of the present invention, the (C) fatty acid ester surfactant is a cured film surface. Bleeding out can be prevented. Thereby, durability, such as abrasion resistance of a cured film obtained, wet heat resistance, and dry heat resistance, improves. Furthermore, since component (C) has a hydroxyl group, fingerprint visibility and fingerprint wiping properties can be imparted to the resulting cured film. Here, “fingerprint visibility” means the difficulty of seeing with the naked eye when a fingerprint is attached to the film surface.
Furthermore, when the component (C) has a hydroxyl group and a (meth) acryloyl group, compatibility with other components in the composition is improved, and (C) a fatty acid ester surfactant is blended at a high concentration However, the effect that whitening does not arise in the cured film obtained is also acquired.

The HLB (Hydrophile-Lipophile Balance) value is an important index indicating the properties of a surfactant and indicates the degree of hydrophilicity or lipophilicity. The HLB value can be obtained by the following calculation formula.
HLB = 7 + 11.7Log (M _W / M _O )
Here M _W is the molecular weight of the hydrophilic groups, M _O is the molecular weight of the lipophilic group. M _W + M _O = M (molecular weight of the surfactant). The HLB value of the (C) fatty acid ester surfactant used in the present invention is required to be within the range of 2 to 15, preferably within the range of 2 to 12, and within the range of 2 to 10. More preferably. By setting the HLB value within the above range, the affinity with the fingerprint liquid is increased and the visibility is improved.

The fatty acid ester structure of component (C) is preferably derived from a linear or branched aliphatic carboxylic acid having 8 to 30 carbon atoms.
The fatty acid ester group is preferably a group containing a polyoxyalkylene group or a glyceryl group.

Component (C) can be obtained by converting a part of the hydroxyl group of the fatty acid ester surfactant having a hydroxyl group but not having a (meth) acryloyl group into a (meth) acryloyl group. Preferably, the component (C) can be obtained by reacting the hydroxyl group of the fatty acid ester surfactant with a compound having a (meth) acryloyl group.
As the compound having a (meth) acryloyl group, for example, a compound having an isocyanate group and a (meth) acryloyl group can be used. By using such a compound, the hydroxyl group of the fatty acid ester surfactant and the isocyanate group react to form a urethane bond, whereby a (meth) acryloyl group is introduced.
Specific examples of the compound having an isocyanate group and a (meth) acryloyl group include 2- (meth) acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl]. Ethyl isocyanate and the like can be used. It can also be obtained by reacting a diisocyanate compound with a compound containing a hydroxyl group and a (meth) acryloyl group. Examples of such diisocyanate compounds include isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like.

Specific examples of the fatty acid ester surfactant having a hydroxyl group but not having a (meth) acryloyl group include, for example, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene fatty acid ester, and the like, and polyoxyethylene hydrogenated castor Oils and polyoxyethylene fatty acid esters are preferred.
Examples of commercially available polyoxyethylene hydrogenated castor oil include EMALEX HC series (manufactured by Nippon Emulsion Co., Ltd.) and Neugen HC series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
Examples of commercially available polyoxyethylene fatty acid esters include EMALEX GWIS-100EX (glyceryl isostearate, manufactured by Nippon Emulsion Co., Ltd.), Neugen GIS series (produced by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

The reaction between a fatty acid ester surfactant having a hydroxyl group but not having a (meth) acryloyl group and a compound having an isocyanate group and a (meth) acryloyl group can be carried out as follows.
That is, it is a reaction between an isocyanate compound and a hydroxyl group-containing compound. Usually, copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, It is preferable to use 0.01 to 1 part by weight of a urethanization catalyst such as 7-trimethyl-1,4-diazabicyclo [2.2.2] octane with respect to 100 parts by weight of the total amount of the reactants. Moreover, in the reaction of these compounds, it can also carry out without a catalyst. The reaction temperature is usually from 0 to 90 ° C, preferably 40 to 80 ° C. The reaction may be carried out without a solvent or by dissolving in a solvent.

式（１）中、各記号の意味は下記の通りである。Ｘは置換されていてもよい炭素数３〜１０の（ｍ^１＋ｍ^２）価の炭化水素基を示す。複数個あるＹ^１及びＹ^２はそれぞれ独立にエーテル結合、エステル結合、或いはウレタン結合を含む２価の基又は単結合を示し、Ｙ^１及びＹ^２の少なくとも１個は脂肪酸に由来する構造を有する。Ｚは（メタ）アクリロイル基を１個以上有する基を示す。複数個あるＲ^１１及びＲ^１２はそれぞれ独立に炭素数１〜４の直鎖又は分岐の炭化水素基を示す。ｍ^１及びｍ^２はそれぞれ１〜１０の整数であり、ｎ^１及びｎ^２はそれぞれ独立に０〜２０の整数である。 The component (C) can have a structure represented by the following formula (1), for example.

In formula (1), the meaning of each symbol is as follows. X represents an optionally substituted (m ¹ + m ² ) -valent hydrocarbon group having 3 to 10 carbon atoms. A plurality of Y ¹ and Y ² each independently represent a divalent group or a single bond containing an ether bond, an ester bond, or a urethane bond, and at least one of Y ¹ and Y ² has a structure derived from a fatty acid. . Z represents a group having one or more (meth) acryloyl groups. A plurality of R ¹¹ and R ¹² each independently represent a linear or branched hydrocarbon group having 1 to 4 carbon atoms. m ¹ and m ² are each an integer of 1 to 10, and n ¹ and n ² are each independently an integer of 0 to 20.

The compound of component (C) can be synthesized as follows.
It is obtained by reacting an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group in such a ratio that one or more hydroxyl groups remain on average per molecule among the hydroxyl groups of a surfactant having two or more hydroxyl groups. be able to. For example, when a surfactant having three hydroxyl groups is used as a raw material, an isocyanate compound or (meth) acrylic acid having a (meth) acryloyl group of 2/3 molar equivalent or less of the hydroxyl group may be reacted.
The molar ratio of the hydroxyl group to the (meth) acryloyl group in the component (C) is preferably in the range of hydroxyl group: (meth) acryloyl group = 1: 6 to 3: 1. By making the ratio of the hydroxyl group and the (meth) acryloyl group within the above range, both the fingerprint visibility and the durability of the cured film can be achieved.

  The content of the component (C) in the composition of the present invention is based on a total of 100 parts by weight of the components (A) and (B) when the composition of the present invention does not include the component (D) described later. 0.1 to 30 parts by weight is preferable, 0.1 to 20 parts by weight is more preferable, and 1 to 15 parts by weight is even more preferable. On the other hand, when the composition of this invention contains the component (D) mentioned later, the range of 0.1-30 weight part with respect to a total of 100 weight part of a component (A), (B) and (D). The inside is preferable, more preferably within the range of 0.1 to 20 parts by weight, and even more preferably within the range of 1 to 15 parts by weight. If the content of the component (C) is less than 0.1 parts by weight, there is a possibility that sufficient fingerprint visibility may not be obtained when it is a cured film. If it exceeds 30 parts by weight, the hardness of the cured film is May decrease.

(D) Inorganic oxide particle The composition of this invention may contain the inorganic oxide particle as a component (D). The component (D) is not particularly limited as long as it is a particle mainly composed of an inorganic oxide. Component (D) is expected to have an effect of improving the hardness of the laminated film or reducing the curl.

  Component (D) can be selected and used from the viewpoints of transparency and hue of the cured film of the resulting curable composition.

  Preferred examples of the component (D) include particles mainly composed of an inorganic oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Specific examples include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Can do. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more. Furthermore, the component (D) is preferably used as a powder or a solvent-dispersed sol. When used as a solvent dispersion sol, the dispersion medium is not particularly limited, such as water or an organic solvent, but the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the component (D) is preferably in the range of 1 to 200 nm, more preferably in the range of 5 to 150 nm, and still more preferably in the range of 10 to 100 nm. When the number average particle diameter is in the above range, both transparency and hardness can be achieved when a cured product is obtained. The number average particle diameter of the inorganic oxide particles (D) refers to an average value of 20 particle diameters measured by observation with a transmission electron microscope. Various surfactants and amines may be added to improve the dispersibility of the particles.

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

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

The shape of the component (D) is spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, and preferably spherical. The specific surface area of the component (D) (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.

  Component (D) is an inorganic oxide particle surface-treated with an organic compound (Db) having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule (hereinafter referred to as “particle modifier (Db)”). (Hereinafter referred to as “reactive particles (Dc)”) is also preferable. The component (D) that is not surface-treated with the particle modifier (Db) with respect to the reactive particles (Dc) is referred to as “oxide particles (Da)”. Since the reactive particles (Dc) can form a covalent bond with the binder component, a cured film excellent in scratch resistance, heat resistance and transparency can be obtained.

Particle modifier (Db)
The particle modifier (Db) used in the present invention is not particularly limited as long as it is an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group. Examples of the polymerizable unsaturated group include ethylenically unsaturated groups such as vinyl group and (meth) acryloyl group. The hydrolyzable silyl group is a group that reacts with water to produce a silanol (Si-OH) group. For example, one or more methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups on silicon. Group, an alkoxy group such as n-butoxy group, an aryloxy group, an acetoxy group, an amino group, and a halogen atom bonded thereto.

  As the particle modifier (Db) used in the present invention, a commercially available product such as γ-methacryloxypropyltrimethoxysilane can be used, for example, a compound described in International Publication No. WO97 / 12942 is used. You can also.

Preparation of Reactive Particles (Dc) Reactive particles (Dc) are obtained by mixing particle modifier (Db) with oxide particles (Da), hydrolyzing them, and bonding them together. The ratio of the organic polymer component, that is, the hydrolyzate and condensate of hydrolyzable silane, in the resulting reactive particles (Dc) is usually determined by completely burning the dry powder of the reactive particles (Dc) in the air. For example, the constant weight value of weight loss% can be determined by thermogravimetric analysis from room temperature to normal 800 ° C. in air.

  The binding amount of the particle modifier (Db) to the oxide particles (Da) is preferably 100% by weight of the reactive particles (Dc) (the total of the oxide particles (Da) and the particle modifier (Db)). 0.01 to 40% by weight, more preferably 0.1 to 30% by weight, and particularly preferably 1 to 20% by weight. By setting the amount of the particle modifier (Db) to be reacted with the oxide particles (Da) within the above range, the dispersibility of the reactive particles (Dc) in the composition can be improved. The effect of improving transparency and scratch resistance can be expected.

The component (D) in the composition of the present invention is an optional component, but the content when added is the component (A) both in the case of the oxide particles (Da) and in the case of the reactive particles (Dc). ), (B) and (D) are 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 80 parts by weight. If the content of the component (D) is less than 10 parts by weight, the blended effect may not be exhibited, and if it exceeds 80 parts by weight, the scratch resistance as a hard coat may be reduced.
The content of the inorganic oxide particles (D) means a solid content, and when the inorganic oxide particles (D) are used in the form of a solvent-dispersed sol, the content does not include the amount of solvent. .

(E) Organic or inorganic particles having a number average particle diameter of 0.5 to 10 μm Component (E) in the composition of the present invention is a component that is blended as necessary, and the resulting cured film has antiglare properties. Give. As the component (E), organic or inorganic particles having a number average particle diameter in the range of 0.5 to 10 μm can be used. The number average particle diameter of the component (E) particles is a value measured by a dynamic light scattering method.

  Examples of the material of the inorganic particles that can be used as the component (E) include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, and the like, and silica is preferable.

  Examples of the material of the organic particles that can be used as the component (E) include acrylic resin, polystyrene, polyethylene, and styrene-ethylene copolymer.

  Content of the component (E) mix | blended as needed in the composition of this invention is 0.1-30 weight part with respect to a total of 100 weight part of a component (A), (B) and (D). Is preferably within the range of 0.5 to 20 parts by weight. Content of a component (E) can be changed with the design of an anti-glare film.

(F) Organic solvent The composition of the present invention can be used after being diluted with an organic solvent in order to adjust the thickness of the coating film. For example, the viscosity when used as a hard coat material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.
Examples of the organic solvent (F) include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples include amides such as N-methylpyrrolidone.

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

(G) Other additives In the composition of the present invention, in addition to the above components, radically polymerizable compounds other than the components (A), (C) and (Dc), antioxidants, and ultraviolet absorbers as necessary. A leveling agent or the like can be added.

In the composition of the present invention, the components (A) to (C) and, if necessary, components arbitrarily selected from the components (D) to (G) are added, respectively, at room temperature or under heating conditions. It can be prepared by mixing. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the polymerization initiator or polymerizable unsaturated group.
The composition of the present invention obtained as described above can be cured by radiation (light).

II. Cured film The cured film of the present invention can be obtained by coating the composition of the present invention on various transparent film substrates and curing them. Specifically, the composition is coated, and preferably, when volatile components such as (F) an organic solvent are contained at 0 to 200 ° C., these are volatilized and removed, and then a curing treatment is performed with radiation. Can be obtained.
Examples of the coating method on the substrate include normal coating methods such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, and brush coating. The thickness of the coating film in these coatings is the thickness after drying and curing, and is preferably 0.1 to 400 μm, more preferably 0.5 to 200 μm.

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

III. Transparent film substrate The transparent film substrate to be coated is not particularly limited. For example, polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene-based resin, etc. The plastic film is mentioned. The thickness of the plastic film is not particularly defined, but is preferably 40 μm to 5 mm from the viewpoint of ease of handling. It is preferable that the transparent film base material used for this invention has the transmittance | permeability of 85% or more in all the wavelength ranges of wavelength 400-800 nm.

IV. Laminated film The laminated film of this invention has the cured film formed using the curable composition containing the following component (A)-(C) in the at least one surface of a transparent film base material. The laminated film of the present invention can be obtained by coating the cured film of the present invention on various transparent film substrates and curing them. Suitable transparent substrates and methods for laminating the cured film are as described in the section of the cured film. The laminated film of the present invention has high transparency and hardness, and is excellent in antifouling properties, particularly fingerprint wiping and fingerprint visibility, wet heat resistance, and dry heat resistance. Suitable as a film or the like.

  The laminated film of the present invention is excellent in fingerprint visibility and fingerprint wiping property, excellent in scratch resistance, excellent in durability such as dry heat resistance and wet heat resistance, and further has high transparency. It is particularly preferably used as an antireflection film for touch panels, plastic optical components and the like. Further, the curable composition of the present invention is excellent in fingerprint visibility and fingerprint wiping properties, excellent in scratch resistance, excellent in durability such as dry heat resistance and wet heat resistance, and further obtained a cured film having high transparency. CD, DVD, MO and other recording disks, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials for building interior materials, wall materials, artificial marble, etc. It is suitably used as a protective coating material for preventing contamination.

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

（式中、Ｒ^１は、各々独立に、水素原子又は下記式で表される基である。ａ＋ｂ＋ｃ＝７である。）

Synthesis Example 1: Compound (C-1)

(In the formula, each R ¹ independently represents a hydrogen atom or a group represented by the following formula. A + b + c = 7)

  To a three-necked flask equipped with a stirrer, 0.013 g of 2,6-di-t-butyl-p-cresol (Yoshitomi Fine Chemical Co., Yoshinox BHT), pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A -TMM-3LM-N) 14.82 g, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur I) 6.66 g, and methyl isobutyl ketone (manufactured by Mitsubishi Chemical Corporation) ) 50.00 g was charged, and 0.044 g of dioctyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd., KS-1200-A) was added thereto, followed by stirring at room temperature for 2 hours. Subsequently, 28.47 g of polyoxyethylene hydrogenated castor oil (manufactured by Nippon Emulsion Co., Ltd., EMALEX HC-7; HLB value 6) was added. The temperature of the reaction solution was raised to 60 ° C. to obtain a compound (C-1) having an HLB value of 4. Further, since the acrylation reaction proceeds almost quantitatively, the molar ratio of the hydroxyl group of the compound (C-1) to the (meth) acryloyl group was determined from the charged amount.

Synthesis Examples 2-6 , Reference Synthesis Example 1
Except having used the compound shown in Table 1 in the ratio shown in Table 1, it carried out similarly to the synthesis example 1, and obtained compound (C-2)-(C-7).

（式中、Ｒ^２は、各々独立に、水素原子又は下記式で表される基である。ａ＋ｂ＋ｃ＝７である。）

Compound (C-2)

(In the formula, each R ² independently represents a hydrogen atom or a group represented by the following formula. A + b + c = 7)

（式中、Ｒ^３は、各々独立に、水素原子又は下記式で表される基である。ａ＋ｂ＋ｃ＝７である。）

Compounds (C-3), (C-4) and (C-5)

(In the formula, each R ³ independently represents a hydrogen atom or a group represented by the following formula. A + b + c = 7)

Compound (C-6)

Compound (C-7)

（式中、Ｒ^１は、下記式で表される基である。ａ＋ｂ＋ｃ＝７である。）

Comparative Synthesis Example 1: Compound (G-1)

(In the formula, R ¹ is a group represented by the following formula: a + b + c = 7)

  Compound (G-1) was obtained in the same manner as in Synthesis Example 1 except that the compounds shown in Table 1 were used in the proportions shown in Table 1.

  Table 1 shows the HLB values of the compounds (C-1) to (C-7). In addition, Table 1 shows the molar ratio of the hydroxyl groups: (meth) acryloyl groups of the compounds (C-1) to (C-7) and the compound (G-1).

ＥＭＡＬＥＸ ＨＣ−７（ａ＋ｂ＋ｃ＝７）、ＨＬＢ値：６ The compounds described in Table 1 are as follows.
HC-7: EMALEX HC-7, polyoxyethylene hydrogenated castor oil having a structure represented by the following formula, manufactured by Nippon Emulsion Co., Ltd.

EMALEX HC-7 (a + b + c = 7), HLB value: 6

GWIS-100EX: EMALEX GWIS-100EX, glyceryl isostearate (compound represented by the following formula), manufactured by Nippon Emulsion Co., Ltd., molecular weight: 358.56, HLB value: 6

TDI: manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., TOLDY-100, tolylene diisocyanate (compound represented by the following formula), molecular weight: 174.16

IPDI: Desmodur I, manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate (compound represented by the following formula), molecular weight: 222.29

Karenz MOI: Showa Denko, methacryloxyethyl isocyanate (compound represented by the following formula), molecular weight: 155.15

PETA: NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol triacrylate (compound represented by the following formula), molecular weight: 298.3

HEA: manufactured by Osaka Organic Chemical Co., Ltd., hydroxyethyl acrylate (compound represented by the following formula), molecular weight: 116.11.

BHT: Yoshinox BHT, manufactured by Yoshitomi Fine Chemicals Co., Ltd., 2,6-di-t-butyl-p-cresol (compound represented by the following formula), molecular weight: 220

KS-1200-A: manufactured by Kyodo Yakuhin Co., Ltd., dioctyltin dilaurate MIBK: methyl isobutyl ketone

Production Example 1
Synthesis of Particle Modifier (Db) To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour with stirring. The mixture was heated and stirred at 3 ° C for 3 hours. NK ester A-TMM-3LM-N (60% by weight of pentaerythritol triacrylate and 40% by weight of pentaerythritol tetraacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. Among them, the one involved in the reaction is pentaerythritol having a hydroxyl group. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain a particle modifier (Db) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, a total of 773 parts of particle modifier (Db) and 220 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2
Production of silica particles (I) as reactive particles (Dc) 2.98 parts of the composition produced in Production Example 1 (including 2.32 parts of particle modifier (Db)), silica particle dispersion (Da) ( Solid content: 35% by weight, MEK-ST-L, number average particle size 0.08 μm, manufactured by Nissan Chemical Industries, Ltd.) 89.90 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0 After stirring 0.012 parts of the mixed solution at 60 ° C. for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, which was 36.5% by weight. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 95 weight%. The resultant was concentrated to a solid content of 70% by weight to obtain a silica particle (I) dispersion. The number average particle diameter of the obtained silica particles (I) measured by transmission electron microscopy was 80 nm.

Production Example 3
Production of Silica Particles (S) as Reactive Particles (Dc) 3.14 parts of γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone SZ6030), silica particle dispersion (Da) (solid content: 35% by weight, MEK-ST-L, number average particle size 0.08 μm, manufactured by Nissan Chemical Industries, Ltd.) 89.90 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts After the mixture was stirred at 60 ° C. for 4 hours, 1.36 parts of methyl orthoformate was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, which was 36.5% by weight. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 93 weight%. The number average particle diameter of the obtained silica particles ( S ) measured by transmission electron microscopy was 50 nm.

Example 1
94.0 parts by weight of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 6.0 parts by weight of photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd .: Irgacure 184) and manufactured in Synthesis Example 1 6.5 parts by weight of compound (C-2) was added, methyl isobutyl ketone was added so that the solid content concentration was 50% by weight, and the mixture was stirred to obtain curable composition 1.

Example 2
A curable composition 2 was produced in the same manner as in Example 1 except that each component was used in the amount shown in Table 2 as the solid content.

Example 3
Silica particles (I) produced in Production Example 2 (78.1 parts by weight as a solid content), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 20.1 parts by weight, photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd .: Irgacure 184) 1.8 parts by weight and 4.2 parts by weight of compound (C-2) produced in Synthesis Example 2 were added, and the methyl content was adjusted to 50% by weight. Isobutyl ketone was added and stirred to obtain a curable composition.

Examples 4-11 and Comparative Examples 1-7
Each curable composition was produced in the same manner as in Example 3 except that each component was used in the amount shown in Table 2.

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

<Evaluation of physical properties of cured film>
The following properties of the cured film prepared as described above were evaluated, and the results obtained are shown in Table 2.
(1) Measurement of haze (%) The haze (%) of the cured film was measured using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7105.

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

(3) Fingerprint visibility The back surface of the film was blacked out, and the fingerprint was attached to the film surface. Then, it visually observed from the perpendicular | vertical upper direction of the film surface, and evaluated according to the following evaluation criteria.
○: Fingerprints are difficult to see ×: Fingerprints are clearly visible

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

(5) Solvent resistance After wiping the surface with a cloth soaked with a liquid glass crew (trade name: manufactured by Johnson Co., Ltd.), the above (4) fingerprint wiping test was conducted and evaluated according to the following evaluation criteria.
○: Can be wiped off.
Δ: It is difficult to wipe off.
X: Cannot be wiped off.

(6) Scratch resistance (steel wool resistance)
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was applied 10 times with a load of 500 g. Or it rubbed 10 times repeatedly at 900 g, the presence or absence of generation | occurrence | production of the damage | wound in the surface of the said cured film was confirmed visually, and it evaluated in accordance with the following evaluation criteria.
A: The cured film is not damaged.
B: Slight fine scratches are generated on the cured film.
C: Several scratches are generated on the cured film.
D: Many scratches are generated on the cured film.
E: Scratches occur on the entire surface of the cured film.

(7) Measurement of contact angle (°) The contact angle of the cured film with respect to water and hexadecane was measured according to JIS 6768 using a contact angle meter Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd.

(8) Moist heat resistance The cured film was placed in a constant temperature and humidity chamber of 60 ° C. × 90% RH, subjected to physical property evaluation after standing for 500 hours, and evaluated according to the following evaluation criteria.
○: Initial and no change.
X: There is a change from the initial stage.

(9) Dry heat resistance The cured film was placed in a constant temperature bath at 80 ° C., evaluated for physical properties after standing for 500 hours, and evaluated according to the following evaluation criteria.
○: Initial and no change.
X: There is a change from the initial stage.

ＥＭＡＬＥＸ ＨＣ−５（ａ＋ｂ＋ｃ＝５）、ＨＬＢ値：５
ＥＭＡＬＥＸ ＨＣ−１０（ａ＋ｂ＋ｃ＝１０）、ＨＬＢ値：１０
エマレックスＰＥＩＳ−３ＥＸ：ＥＭＡＬＥＸ ＰＥＩＳ−３ＥＸ、モノイソステアリン酸ポリエチレングリコール、日本エマルジョン社製、ＨＬＢ値：７

The compounds described in Table 2 are as follows.
Silica particles (I): reactive particles synthesized in Production Example 2 (Dc)
Silica particles (S): reactive particles (Dc) synthesized in Production Example 3
Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd., KAYARAD DPHA
Pentaerythritol triacrylate: Shin Nakamura Chemical Co., Ltd., NK Ester A-TMM-3LM-N
Irg. 184: Ciba Specialty Chemicals Co., Ltd., photopolymerization initiator Each compound of component (C) was synthesized in Synthesis Examples 1-6 .
Compound (C-6): Compound Emarex HC-10 synthesized in Reference Synthesis Example 1 , HC-5: Polyoxyethylene hydrogenated castor oil having a structure represented by the following formula, manufactured by Nippon Emulsion Co., Ltd.

EMALEX HC-5 (a + b + c = 5), HLB value: 5
EMALEX HC-10 (a + b + c = 10), HLB value: 10
EMALEX PEIS-3EX: EMALEX PEIS-3EX, polyethylene glycol monoisostearate, manufactured by Nippon Emulsion Co., Ltd., HLB value: 7

Emalex GWIS-100EX: described after Table 1 Compound (G-1): Compound synthesized in Comparative Synthesis Example 1 Sailor Plain FM0711: Chisso Corporation, methacryloyl-modified polysiloxane (compound represented by the following formula)

From the results of Table 2, it can be seen that the cured films of the examples are excellent in transparency, fingerprint visibility, fingerprint wiping properties, solvent resistance, scratch resistance, wet heat resistance, and dry heat resistance.
In contrast, Comparative Example 7 using a fatty acid ester surfactant in which all hydroxyl groups were (meth) acrylated was found to be inferior in scratch resistance, wet heat resistance and dry heat resistance.

Example 12
1 part by weight of acrylic resin particles (manufactured by Soken Chemical Co., Ltd., “MX-180”, average particle size 1.9 μm) is added to 100 parts by weight (solid content 50 parts by weight) produced in Example 3. Then, 103 parts by weight of methyl isobutyl ketone was added so that the solid content concentration was 25%, and stirred to obtain a curable composition 12. The curable composition 12 was coated on a TAC film having a thickness of 80 μm using a bar coater (3 mil). After drying at 80 ° C. for 2 minutes, a cured film was produced by photocuring by irradiating with ultraviolet rays at an intensity of 1.0 J / cm ^{2 in} air using a high-pressure mercury lamp. The back surface of the obtained film with a cured film was blacked out and the fluorescent lamp was reflected, but the shape of the fluorescent lamp could not be confirmed, and it was confirmed that the film had antiglare properties. Further, although fingerprints were attached to the film, it was difficult to visually confirm the fingerprints, and they could be easily wiped off with a tissue paper.

The composition of the present invention can provide a cured film having excellent fingerprint visibility and fingerprint wiping properties, excellent durability such as scratch resistance, wet heat resistance and dry heat resistance, and at the same time high transparency.
The composition of the present invention is useful as a curable composition for forming a hard coat.

  A cured film obtained by curing the composition of the present invention has excellent fingerprint visibility and fingerprint wiping properties, scratch resistance, dry heat resistance, wet heat resistance, and further high transparency. DVD, MO recording discs, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, flooring materials for building interior materials, wall materials, artificial marble, etc. It is particularly useful as a protective coating material, or an antireflection film for film-type liquid crystal elements, touch panels, plastic optical components and the like.

Claims (14)

A laminated film having a cured film formed using a curable composition containing the following components (A) to (C) on at least one surface of a transparent film substrate.
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) HLB value obtained by reacting the following compounds (1) and (2) with a hydroxyl group and (meth) acryloyl group is 2 Fatty acid ester surfactant in the range of -15
(1) Fatty acid ester surfactant having a hydroxyl group but no (meth) acryloyl group
(2) A compound having an isocyanate group and a (meth) acryloyl group obtained by reacting a diisocyanate compound with a compound containing a hydroxyl group and a (meth) acryloyl group   The laminated film according to claim 1, wherein the component (C) has an HLB value in the range of 2 to 12.   The laminated film according to claim 1 or 2, wherein a molar ratio of the hydroxyl group and the (meth) acryloyl group of the component (C) is in the range of hydroxyl group: (meth) acryloyl group = 1: 6 to 3: 1.   The laminated film according to any one of claims 1 to 3, wherein the component (C) has a linear or branched monovalent or divalent hydrocarbon group having 8 to 30 carbon atoms. The laminated film according to any one of claims 1 to 4, wherein the diisocyanate compound is isophorone diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate. Furthermore, (D) The laminated film of any one of Claims 1-5 which contains the inorganic oxide particle | grains of 1-200 nm of number average particle diameters in the said cured film. The laminated film according to claim 6 , wherein the component (D) is an inorganic oxide particle surface-treated with an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group in the molecule. The sum of the previous SL components (A) and (B) is 100 parts by weight, in any one of claims 1 to 5, wherein said component (C) is in the range of 0.1 to 30 parts by weight The laminated film as described. The said component (C) exists in the range of 0.1-30 weight part, when the sum total of the said component (A), (B) and (D) is 100 weight part, The claim of Claim 6 or 7 Laminated film. Further, the laminated film according to any one of claims. 1 to 9 (E) a number average particle diameter containing an organic or inorganic particles of 0.5 to 10 [mu] m. A curable composition containing the following components (A) to (C).
(A) Polyfunctional (meth) acrylic monomer (B) Photopolymerization initiator (C) HLB value obtained by reacting the following compounds (1) and (2) with a hydroxyl group and (meth) acryloyl group is 2 Fatty acid ester surfactant in the range of -15
(1) Fatty acid ester surfactant having a hydroxyl group but no (meth) acryloyl group
(2) A compound having an isocyanate group and a (meth) acryloyl group obtained by reacting a diisocyanate compound with a compound containing a hydroxyl group and a (meth) acryloyl group The curable composition according to claim 11, wherein the diisocyanate compound is isophorone diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate. The curable composition according to claim 11 or 12 , which is used for forming a hard coat. The cured film formed by hardening | curing the curable composition of any one of Claims 11-13 .