KR20140127770A - Curable composition, laminated film, touch sensor, touch panel, and device equipment - Google Patents

Abstract

The purpose of the present invention is to provide a hardening composition by which a hardening layer having excellent abrasion resistance and adhering properties and including outgas controlled can be produced. The present invention relates to a hardening composition containing a compound (I) represented by Chemical Formula (1). In Chemical Formula (1), R^1 and R^2 are independently groups represented by Chemical Formula (i) or groups represented by Chemical Formula (ii). R^3 and R^4 are independently hydrogen atoms or methyl groups. In Chemical Formulas (i) and (ii), R^5a is a C2 to 6 alkandiyl group. m is an integer of 0 to 20. When both R^1 and R^2 are represented by Chemical Formula (i), the sum of m is 1 or more. R^5b is a C1 to 14 alkandiyl group. n is an integer of 1 to 10. It is preferable that a compound (II) which is different from the compound (I) and has a polymerizable group is further contained.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition, a laminated film, a touch sensor, a touch panel, and a device device (CURABLE COMPOSITION, LAMINATED FILM, TOUCH SENSOR, TOUCH PANEL, AND DEVICE EQUIPMENT)

The present invention relates to a curable composition, a laminated film having a cured layer formed by the curable composition, and a touch sensor, a touch panel, and a device having the laminated film.

In recent years, a laminated film in which a cured layer is formed on the surface of a substrate layer by coating of a curable composition is widely used for prevention of scratching (scratching) of a film and prevention of contamination. Such a laminated film is used as an optical film for a display device such as a touch panel, a surface material such as a membrane switch or a keypad, an electrode substrate for a liquid crystal cell constituting a liquid crystal display element, a retardation film, .

In such a laminated film, it is required that the cured layer thereof is excellent in various performances such as scratch resistance, adhesion with the base layer, and hardness. In addition, it is further required to suppress the outgas from the cured layer or the like, for example, in the case of performing lamination by deposition, sputtering or the like on a laminated film.

As to the above requirements, various components of the curable composition for forming the cured layer have been variously investigated (see Japanese Patent Application Laid-Open No. 6-66481). However, Level to the level of the control.

Japanese Patent Application Laid-Open No. 6-66481

The present invention has been made based on the above-described circumstances, and an object thereof is to provide a curable composition which is excellent in scratch resistance and adhesion, and can form a cured layer inhibiting outgas.

As a result of intensive studies, the present inventors have found that by using a specific polymerizable compound as a component of the curable composition, it is possible to reduce outgas generated while satisfying the high scratch resistance and adhesion of the laminated film to be formed, It was completed.

In order to solve the above problems,

Is a curable composition containing a compound (I) represented by the following formula (1).

(Wherein R ¹ and R ² are each independently a group represented by the following formula (i) or a group represented by the following formula (ii), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group , R ^A is an alkyl group having 1 to 5 carbon atoms, k is an integer of 0 to 14, and when k is 2 or more, a plurality of R ^A's may be the same or different)

(In the formulas (i) and (ii), R ^5a is an alkanediyl group having 2 to 6 carbon atoms and m is an integer of 0 to 20, provided that R ¹ and R ² are all represented by the above formula (i) , and the sum of m is at least 1, R ^5b is C 1 -C 14, and the alkanediyl group, n is 1 an integer of 1 to 10, R ^5a and R ^5b are, if multiple individuals, respectively, a plurality of R ^5a and R ^5b are May be the same or different, and * represents a moiety bonded to the (meth) acryloyl group of the above formula (1)

By using the compound (I) having the specific structure, the curable composition can suppress the outgass while satisfying the high scratch resistance and adhesion of the cured layer to be formed.

It is preferable to further contain a compound (II) having a polymerizable group which is different from the compound (I).

Further use of the compound (II) in addition to the compound (I) can further enhance the curability, and as a result, the scratch resistance, adhesion and outgassing ability of the cured layer formed can be further improved.

The polymerizable group of the compound (II) is preferably a (meth) acryloyl group. By making the polymerizable group of the compound (II) the specific group, the copolymerization of the compound (I) and the compound (II) can be enhanced, and as a result, outgas can be further suppressed.

The compound (II) preferably has a urethane bond. By using such a curable composition, flexural resistance and the like can be further improved while satisfying the high scratch resistance, adhesion and outgassing properties of the cured layer.

A base layer,

The cured layer

And,

A laminated film in which the cured layer is formed by the curable composition is also included in the present invention.

Such a laminated film is excellent in scratch resistance and adhesiveness and suppresses outgassing because the cured layer is formed using the above-mentioned curable composition.

The base layer is preferably a transparent resin.

By using a transparent resin for the base layer, such a laminated film can be suitably used as a material for a touch panel or the like.

A touch sensor including the laminated film, a touch panel including the touch sensor, and a device device including the touch panel are also included in the present invention.

As described above, the laminated film has high scratch resistance and adhesion, and its high outgas suppressibility makes it possible to perform processing such as vapor deposition more effectively. Therefore, a touch sensor or the like using such a laminated film can exhibit superior performance have.

INDUSTRIAL APPLICABILITY As described above, according to the curable composition of the present invention, it is possible to form a cured layer having excellent scratch resistance and adhesion and suppressing outgas. The laminated film of the present invention is excellent in scratch resistance, adhesion, and outgassing property. INDUSTRIAL APPLICABILITY The touch sensor of the present invention, the touch panel having the same, and the device device having the touch sensor of the present invention exhibit high scratch resistance, adhesion, and outgas suppressibility, and can exhibit superior performance.

1 is a schematic cross-sectional view showing a laminated film according to an embodiment of the present invention.

≪ Curable composition >

The curable composition contains compound (I) and contains compound (II) as a suitable component (hereinafter, also referred to as "compound (A)" in combination of compound (I) and compound (II)). In addition to the compound (A), the curable composition may contain other components such as inorganic particles such as reactive particles (B), radical initiator (C), and solvent (D).

Hereinafter, each component will be described.

≪ Compound (A) >

≪ Compound (I) >

The compound (I) is a compound represented by the following formula (1). By containing the compound (I) having the specific structure described above, the curable composition can form a cured layer having excellent scratch resistance and adhesion and at the same time inhibiting outgas. The reason why the curable composition has the above-mentioned constitution has the above-mentioned effect is not necessarily clear, but can be estimated, for example, as follows. That is, the compound (I) has a bulky alicyclic structure of a tricyclodecane ring. The cured layer to be formed can exhibit high scratch resistance and high adhesion with the substrate layer due to this bulky alicyclic structure. Further, the compound (I) has a specific structure in which the (meth) acryloyl group which is a polymerizable group is bonded to the tricyclodecane ring through a polyoxyalkylene group or an oxycarbonylalkanedioxy group, so that the volatility of the compound is suppressed On the other hand, the polymerizability is considered to be high. As a result, it is possible to suppress out gas from the formed cured layer.

(1), R ¹ and R ² are each independently a group represented by the following formula (i) or a group represented by the following formula (ii), R ³ and R ⁴ are each independently a hydrogen atom or that a methyl group, R ^a is an alkyl group having 1 to 5, k is an integer from 0 to 14, when k is 2 or more, a plurality of R ^a is may be the same or may be different)

(In the above formulas (i) and (ii), R ^5a is an alkanediyl group having 2 to 6 carbon atoms and m is an integer of 0 to 20, provided that R ¹ and R ² are both represented by the above formula (i) case, the sum of m is at least 1, R ^5b is an alkanediyl group having 1 to 14, n is an integer from 1 to 10, R ^5a and R ^5b are, if multiple individuals, respectively, a plurality of R ^5a and R ^5b May be the same or different, and * represents a moiety bonded to the (meth) acryloyl group of the above formula (1)

Examples of the alkanediyl group having 2 to 6 carbon atoms represented by R ^5a in the above formula (i) include an ethanediyl group, a straight or branched propanediyl group, a butanediyl group, a pentanediyl group, Diary, and the like.

Of these, the ethanediyl group, straight-chain or branched propanediyl group is preferable, and 1,2-propanediyl group is more preferable.

As m, an integer of 1 to 10 is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is more preferable, and 2 is particularly preferable.

The sum of m in the case where both R ¹ and R ² are represented by the above formula (i) is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less, still more preferably 2 or 4, Particularly preferred.

Examples of the alkanediyl group having 1 to 14 carbon atoms represented by R ^5b in the above formula (ii) include a methanediyl group, an ethanediyl group, a linear or branched propanediyl group, a butanediyl group, A diaryl group, a diaryl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a dodecanediyl group, and a tetradecanediyl group.

Of these, a methanediyl group, an ethanediyl group, and a linear pentanediyl group are preferable, and a 1,5-pentanediyl group is more preferable.

The n in the above formula (ii) is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

As R ¹ and R ² , a group represented by the above-mentioned formula (i) is preferable from the viewpoint that the outgas of the cured layer formed by the curable composition is reduced.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- And the like.

As R ³ and R ⁴ , a hydrogen atom is preferable from the viewpoint of higher polymerizability.

Examples of the compound (I) include compounds represented by the following formulas (1-1) to (1-14).

In the above formulas (1-1) to (1-14), R ³ and R ⁴ have the same meanings as in the above formula (1).

Among them, the compound (I) is preferably the compound represented by the formula (1-2), the compound represented by the formula (1-6), and the compound represented by the formula (1-8).

The content of the compound (I) in the compound (A) is usually 3 mass% to 80 mass%, preferably 5 mass% to 60 mass%, more preferably 7 mass% to 50 mass% By mass to 40% by mass, particularly preferably from 15% by mass to 35% by mass, and most preferably from 20% by mass to 30% by mass.

≪ Process for producing compound (I) >

The compound (I) can be produced by, for example, reacting bis (hydroxymethyl) -tricyclo [5.2.1.0 ^2,6 ] decane with an epoxide such as propylene oxide (R ¹ and R ² in the above formula (i)) or a lactone such as epsilon -caprolactone (in the case where R ¹ and R ² in the above formula (1) are the above formula (ii)) in a solvent such as toluene (Meth) acrylic group-containing compound such as 2-hydroxyethyl acrylate in the presence of an acid such as para-toluenesulfonic acid or the like to a dihydroxy compound obtained by reacting a dihydroxy compound obtained by reacting a dihydroxy compound in the presence of an alkali such as sodium.

≪ Compound (II) >

The compound (II) is a compound other than the compound (I) and is a compound having a polymerizable group. The curable composition can further improve the curability by further containing the compound (II) in addition to the above-mentioned compound (I), and as a result, the scratch resistance, adhesion and outgassing ability of the cured layer formed can be further improved.

The polymerizable group is not particularly limited as long as it is a polymerizable group, and examples thereof include a carbon-carbon double bond such as a (meth) acryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, a cinnamoyl group, A group containing a carbon-carbon triple bond such as an ethynyl group, and the like. Among them, a group containing a carbon-carbon double bond is preferable, a (meth) acryloyl group and a styryl group are more preferable, and a (meth) acryloyl group is more preferable. When the polymerizable group of the compound (II) is used as the group, the copolymerization with the compound (I) improves, and as a result, the outgas suppressibility of the laminated film can be further improved.

The compound (II) is not particularly limited as long as it has a polymerizable group, and examples thereof include (meth) acrylate compounds in which the polymerizable group is a (meth) acryloyl group. Examples of the (meth) acrylate compound include a urethane (meth) acrylate compound having a urethane bond (hereinafter also referred to as "urethane (meth) acrylate compound (A2)") (Hereinafter also referred to as " other (meth) acrylate compound (A3) "). The curable composition may contain other polymerizable compound (hereinafter also referred to as " other polymerizable compound (A4) ") other than the (meth) acrylate compound as the compound (II).

[Urethane (meth) acrylate compound (A2)]

The urethane (meth) acrylate compound (A2) has a function of increasing the bending resistance and the like of the cured layer to be formed.

The urethane (meth) acrylate compound (A2) preferably has two or more (meth) acryloyl groups, and more preferably has 2 to 15 (meth) acryloyl groups.

As the urethane (meth) acrylate compound (A2), urethane (meth) acrylate having a number average molecular weight of 500 to 50,000 in terms of polystyrene in gel permeation chromatography (GPC) is suitably used. The GPC pattern of the urethane (meth) acrylate compound (A2) was measured by using a HLC-8020 high-performance liquid chromatograph (manufactured by Tosoh Corporation), using a styrene / divinylbenzene copolymer resin as a GPC column, Measure using hydrofuran.

The urethane (meth) acrylate compound (A2) is not particularly limited as long as it is a compound having a (meth) acryloyl group and a urethane bond. Commercial products thereof include ARTREX UN-333, KY-111, UN EBECRYL230, EBECRYL270, EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8807, EBECRYL9260, EBECRYL9270 (which are all manufactured by Negami Kogyo Co., (Manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like were prepared in the same manner as in Example 1, except that U-6HA, U-6LPA, UA-1100H, UA-200PA, UA-4200, UA-122P and UA- . These may be used alone or in combination of two or more.

[Other (meth) acrylate compound (A3)]

The other (meth) acrylate compound (A3) is suitably used for enhancing the adhesion between the cured layer and the base layer and controlling the hardness. The (meth) acrylate compound (A3) is a compound having at least one (meth) acryloyl group in one molecule, and examples thereof include (meth) acrylic esters.

Examples of the (meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (Meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di Poly (meth) acrylates of ethylene oxide or propylene oxide adducts to the hydroxyl groups thereof, poly (meth) acrylates of two or more (meth) acrylates in the molecule, (Meth) acrylates having an acryloyl group, oligoether (meth) acrylates, oligourethane (meth) acrylates and oligoepoxy (meth) acrylates.

Among them, tricyclodecane dimethanol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferable.

Examples of commercial products of such (meth) acrylate compounds (A3) include Aronix M-400, M-408, M-450, M-305, M-309, M- M-320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M- 270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO- KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku, TO-904, TO-902, TO- , DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR- -492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR- T-1420, GP-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, SR-609, SR-609, , HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, , KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., FA-512AS manufactured by Hitachi Chemical Co., Ltd., NK ester A-TMM-3LM-N manufactured by Shin Nakamura Chemical Industry Co., Ltd., and A-DPH .

[Other polymerizable compound (A4)]

The curable composition may contain other polymerizable compound (A4). Examples of the polymerizable compound (A4) include vinyl compounds and the like.

Examples of the vinyl compound include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

The content of the compound (II) in the compound (A) is usually 20 mass% to 97 mass%, preferably 40 mass% to 95 mass%, more preferably 50 mass% to 93 mass% To 90% by mass, particularly preferably from 65% by mass to 85% by mass, and most preferably from 70% by mass to 80% by mass.

The content of the compound (A) in the curable composition is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more, of the total solid content.

<Other ingredients>

<Inorganic Particles>

The curable composition may contain inorganic particles as other components. The inorganic particles are not particularly limited, but oxide particles are preferable, and reactive particles (B) are more preferable.

&Lt; Reactive particles (B) >

The reactive particles (B) can be obtained by bonding oxide particles (hereinafter also referred to as "oxide particles (B1)") with an organic compound (B2) having a specific reactive group.

[Oxide particles (B1)]

The oxide particle (B1) is preferably an oxide particle of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. By using such oxide particles (B1), it becomes possible to obtain a cured layer having high transparency and the like.

Examples of the oxide particles (B1) include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, have. Of these, particles of silica, alumina, zirconia and antimony oxide are preferable from the viewpoint of high hardness. These may be used alone or in combination of two or more.

The oxide particles (B1) are preferably used as powdery or dispersed sols. When used as a dispersion sol, an organic dispersion medium is preferable as the dispersion medium from the viewpoint of dispersibility with other components and the like. Examples of such an organic dispersion medium include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; And amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Among these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

In order to improve the dispersibility of the particles, various surfactants, amines and the like may be added.

Examples of commercially available products as silicon oxide particles (for example, silica particles) include methanol silica sol, IPA-ST-S, IPA-ST-ZL and IPA-ST-ZL manufactured by Nissan Chemical Industries, L, IPA-ST-UP, MEK-ST-L, MEK-ST-ZL, NBA-ST, XBA-ST, DMAC- ST, ST- ST-40, ST-C, ST-N, ST-O, ST-50 and ST-OL. Examples of the powdery silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 manufactured by Nippon Aerosil Co., Dex H31, H32, H51, H52, H121 and H122 manufactured by Asahi Glass E220A, E220 manufactured by Nippon Silica High School, SYLYSIA470 manufactured by Fuji Silysia Chemical Co., Ltd., SG flake manufactured by Nippon Itagaras, and the like.

As the water dispersion of the alumina particles, alumina sol-100, -200, -520 manufactured by Nissan Chemical Industries, Ltd., As the isopropanol dispersion product of alumina particles, AS-150I manufactured by Sumitomo Osaka Cement; As the toluene dispersion product of alumina particles, AS-150T manufactured by Sumitomo Osaka Cement; As a toluene dispersion product of zirconia particles, HXU-110JC manufactured by Sumitomo Osaka Cement; Examples of the water content of the zinc antimonate powder include Celanacs manufactured by Nissan Chemical Industries, Ltd.; Examples of powder and solvent dispersion products of alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide include Nanotech manufactured by Shiite Kasei; As the water-dispersed sol of antimony-doped tin oxide, SN-100D manufactured by Ishihara Sangyo; Examples of the ITO powder include products of Mitsubishi Materials; Examples of cerium oxide aqueous dispersions include Nidral manufactured by Dakigaku KK.

As commercial products of zirconia particles, N-PC, PCS, TZ-3Y-E, TZ-4YS, TZ-6YS, TZ manufactured by Daicheng Chemical Industries, Ltd. under the trade names EP, UEP, RC, -8YS, TZ-10YS, TZ-0, and the like.

The shape of the oxide particles (B1) is not particularly limited and may be spherical, hollow, porous, annular, filmy, platy, fibrous, straight or irregular. As used herein, chain phase refers to a chain having an elongated shape with 2 to 200, preferably 10 to 100, oxide particle units having a unit length of 0.05 μm or less, preferably 0.02 μm or less. The chain oxide particles may have a straight chain structure or a branched structure.

As the oxide particles, it is preferable to mix spherical particles and chain particles. Although the reason is not clear, by using oxide particles of these two shapes, it is possible to form a hardened layer having high flex resistance, blocking resistance and hardness while suppressing the deterioration of transparency.

The average particle diameter of the oxide particles (B1) is preferably 0.001 to 2 탆, more preferably 0.003 to 1 탆, and particularly preferably 0.005 to 0.5 탆. If the average particle diameter exceeds 2 탆, the transparency after curing tends to deteriorate or the surface state tends to decrease. On the other hand, when the average particle diameter is less than 0.001 탆, sufficient blocking resistance may not be exhibited.

The average particle size can be determined from the scattered light data measured by a batch type measurement method using a laser diffraction / scattering type particle size distribution measuring device (for example, HORIBA LB-550) according to the Mie theory Means the median diameter obtained by automatic calculation. The median diameter is the particle size at which the frequency distribution corresponds to a cumulative 50%.

[Organic compound (B2)]

The organic compound (B2) is an organic compound having a polymerizable unsaturated group and a hydrolyzable silyl group as a reactive group.

The polymerizable unsaturated group is not particularly limited and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, acrylamide group And the like. The polymerizable unsaturated group is a group that undergoes addition polymerization by an active radical species.

The hydrolyzable silyl group is a silanol group or a group that generates a silanol group by hydrolysis. Examples of the group capable of forming a silanol group include groups in which a silicon atom is bonded with an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, or the like, and a group in which a silicon atom is bonded with an alkoxy group or an aryloxy group , That is, an organic compound containing an alkoxysilyl group or an aryloxysilyl group is preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and the aryloxy group is preferably an aryloxy group having 6 to 18 carbon atoms. The hydrolyzable silyl group (a silanol group or a silanol group-generating group) is a group that bonds with the oxide particle (B1) by a condensation reaction that occurs following condensation reaction or hydrolysis.

As the organic compound (B2), for example, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 2 3-acryloyloxypropyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyltriethoxysilane, - acryloyloxyethyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and the like. At least one kind of silane compound.

Of these, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, At least one silane compound selected from the group consisting of a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, and a silane coupling agent.

The organic compound (B2) preferably has not only a polymerizable unsaturated group and a hydrolyzable silyl group but also a group represented by the following formula (2).

(2), X is NH, O or S, and Y is O or S,

Specifically, the group represented by the formula (2) is [-OC (═O) -NH-], [-OC (═S) -NH-], [ -NH-C (= O) -NH-], -NH-C (= S) -NH-] and [-SC (= S) -NH-]. These groups may be used alone or in combination of two or more. Among them, in view of thermal stability, at least one of [-OC (= S) -NH-] group and [-SC (= O) -NH-] group in addition to [-OC It is preferable to have a number of teeth. The group represented by the above formula (2) generates an appropriate cohesive force by hydrogen bonding between molecules, and when it is a cured product, excellent mechanical strength, adhesion with a base layer, heat resistance and flexibility can be imparted.

As the organic compound (B2), a compound represented by the following formula (3) is preferable.

Wherein at least one of R ⁶ , R ⁷ and R ⁸ is a hydroxy group, an alkoxy group or an aryloxy group and the remaining is a hydrogen atom, an alkyl group or an aryl group, R ⁹ is an aliphatic or aromatic group having 1 to 12 carbon atoms, is a divalent organic group having an aromatic structure, R ¹⁰ is a divalent organic group, R ¹¹ is a (q + 1) valent organic group, Z is having a polymerizable unsaturated group to the intermolecular crosslinking reaction in the presence of active radical species Monovalent organic group, and q is an integer of 1 to 20.

Examples of the alkoxy group and the alkyl group represented by R ⁶ , R ⁷ and R ⁸ in the above formula (3) include those having 1 to 8 carbon atoms, and include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, A methyl group, an ethyl group, a propyl group, a butyl group and an octyl group are preferable. Examples of the aryloxy group and aryl group include those having 6 to 18 carbon atoms, and a phenoxy group, a xylyloxy group, a phenyl group, and a xylyl group are preferable. Examples of the group represented by R ⁶ (R ⁷ ) (R ⁸ ) Si- (hydrolyzable silyl group) include trimethoxysilyl group, triethoxysilyl group, triphenoxysilyl group, methyldimethoxysilyl group , Dimethylmethoxysilyl group and the like. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ⁹ may contain a chain, branched or cyclic structure in its structure. Examples of such structures include aliphatic groups having 1 to 12 carbon atoms such as methylene, ethylene, propylene, methylethylene, butylene, methylpropylene, octamethylene, and dodecamethylene; An alicyclic group having 3 to 12 carbon atoms such as a cyclohexylene group; And aromatic groups having 6 to 12 carbon atoms such as a phenylene group, a 2-methylphenylene group, a 3-methylphenylene group and a biphenylene group. Of these, a methylene group, a propylene group, a cyclohexylene group, and a phenylene group are preferable.

R ¹⁰ is preferably a divalent organic group having a molecular weight (total atomic weight of atoms constituting the group) of 14 to 10,000, particularly a molecular weight of 76 to 500. These organic groups include a divalent organic group having an aliphatic or aromatic structure, and the structure thereof may include a chain, branched or cyclic structure. Examples of such a structural unit include linear or branched alkyl groups such as methylene, ethylene, propylene, tetramethylene, hexamethylene, 2,2,4-trimethylhexamethylene and 1- (methylcarboxy) A divalent organic group having a skeleton of a structure; Divalent organic groups having an alicyclic structure skeleton such as isophorone, cyclohexylmethane, methylenebis (4-cyclohexane), hydrogenated dienylmethane, hydrogenated xylene, and hydrogenated toluene; And divalent organic groups having an aromatic ring skeleton such as benzene, toluene, xylene, paraphenylene, diphenylmethane, diphenylpropane, naphthalene, and the like.

As R ¹¹ , a saturated hydrocarbon group or unsaturated hydrocarbon group of (q + 1) -valent straight or branched chain may be mentioned. More specifically, in addition to the above-mentioned divalent organic group of R ¹⁰ , trivalent organic groups such as 2-ethyl-2-methylenepropylene, trivalent organic groups having an isocyanurate skeleton, 2,2-dimethylpropylene Tetravalent organic groups such as a substituted alkylene group, and alkylene group derived from dipentaerythritol. Of these, preferred are ethylene, 2-ethyl-2-methylene propylene, trivalent organic group having an isocyanurate skeleton, substituted alkylene such as 2,2-dimethylpropylene, and alkylene derived from dipentaerythritol.

Examples of Z include acryloxy, methacryloxy, vinyl, propenyl, butane dienyl, styryl, ethynyl, cinnamoyl, maleate, Of these, an acryloxy group, a methacryloxy group and a vinyl group are more preferable.

q is an integer of 1 to 20, but an integer of 1 to 10 is preferable, and an integer of 1 to 5 is more preferable.

These organic compounds (B2) can be produced, for example, by the method described in JP-A-9-100111.

The method of bonding the oxide particles (B1) and the organic compound (B2) is not particularly limited,

A method in which the oxide particles (B1) and the organic compound (B2) are mixed with an organic solvent containing water to carry out the hydrolysis and condensation reaction at one time,

A method in which the organic compound (B2) is subjected to a hydrolysis treatment in the presence of an organic solvent containing water in advance, followed by condensation reaction with the oxide particle (B1)

The oxide particles (B1) and the organic compound (B2) are mixed with water, an organic solvent and other components, for example, a compound having two or more polymerizable unsaturated groups in the molecule, a radical polymerization initiator, How to do it

And the like.

By these methods, at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium on the surface of the oxide particle (B1) By bonding the atom through the oxygen atom, the reactive particle (B) in which the oxide particle (B1) and the organic compound (B2) are chemically bonded is obtained.

When the oxide particles (B1) are silica particles and the organic compound (B2) is an organic compound (B2) having a silanol group or a silanol group-generating group, they are mixed with an organic solvent containing water or water Thereafter, water or an organic solvent is distilled off under reduced pressure or normal pressure to produce a polymerizable reactive silica particle in which the silica particles and the organic compound (B2) are bonded through a silyloxy group. This reaction can be carried out based on the description in, for example, Japanese Patent Laid-Open No. 9-100111.

When a plurality of oxide particles (B1) are used, each of the oxide particles (B1) can be subjected to a hydrolysis and condensation reaction with the organic compound (B2), and a plurality of oxide particles (B1) , And then hydrolysis / condensation reaction with the organic compound (B2) may be performed. Further, by reacting the spherical and chain oxide particles (B1) with the organic compound (B2) at the same time, a cured product excellent in blocking resistance is obtained, which is preferably used.

The bonding amount of the organic compound (B2) is preferably 0.1% by mass or more, more preferably 1% by mass or less based on 100% by mass of the reactive particles (B) (the sum of the oxide particles (B1) and the organic compound Mass% or more, particularly preferably 3 mass% or more and 40 mass% or less. If the bonding amount of the bound organic compound (B2) is less than 0.01% by mass, the dispersibility of the reactive particles (B) in the composition is not sufficient and the transparency and blocking resistance of the obtained cured layer may become insufficient.

The content of the reactive particles (B) in the curable composition is preferably 25% by mass or more and 85% by mass or less, more preferably 30% by mass or more and 80% by mass or less, of the total solid content. If it is less than 25% by mass, sufficient hardness may not be obtained when it is made into a cured product. On the other hand, if it exceeds 85% by mass, the film-forming property becomes insufficient and the adhesion with the base layer is lowered. The content of the reactive particles (B) means a solid content, and when the reactive particles (B) are used in the form of a dispersion medium-dispersed sol, the content thereof does not include the amount of the dispersion medium.

&Lt; Radical polymerization initiator (C) >

The curable composition may further contain a radical polymerization initiator (C). Examples of the radical polymerization initiator (C) include a compound (radiation (light) polymerization initiator) that generates active radical species by irradiation with light (light), a compound that generates thermally active radical species . If necessary, a radiation (light) polymerization initiator and a thermal polymerization initiator may be used in combination.

Examples of the radiation (light) polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-ethylhexyl cyclohexyl phenyl ketone and the like, as long as they are capable of decomposing by light irradiation to generate radicals to initiate polymerization. , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, , 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropane-1-one, 2-methylpropane-1-one, 2-hydroxy- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- 1,4- (2-hydroxy- 2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).

Examples of commercial products of radiation (photo) polymerization initiators include commercially available products such as Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24- Manufactured by BASF, trade name: Lucirin TPO, manufactured by UCB, trade name: Yubecryl P36, manufactured by Pratelli Lamberti, trade name: Ejecure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B .

Examples of the thermal polymerization initiator include peroxides and azo compounds, and specific examples thereof include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyronitrile.

The content of the radical polymerization initiator (C) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, based on the total solid content. When the content is less than 0.01% by mass, the hardness may be insufficient. When the content is more than 10% by mass, the inside (the base layer 2 side) may not be sufficiently cured.

&Lt; Solvent (D) >

The curable composition is usually diluted with a solvent for adjusting the viscosity (coating property) and the thickness of the coating film. The viscosity of the curable composition is usually 0.1 to 50,000 mPa · sec / 25 ° C, preferably 0.5 to 10,000 mPa · sec / 25 ° C.

Examples of the solvent (D) include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; Esters such as ethyl acetate and butyl acetate; Alcohols such as isopropyl alcohol and ethyl alcohol; Aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, and 1,2-dimethoxybenzene; Phenols such as phenol and para-chlorophenol; And halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, tetrachloroethane, trichlorethylene, tetrachlorethylene and chlorobenzene. These solvents may be used singly or in combination of two or more.

The content of the solution (D) is preferably 70 mass% or less, and more preferably 20 mass% or more and 60 mass% or less.

[Other additives]

The curable composition may further contain other additives. Examples of the additive include a leveling agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a pigment, a dye, a filler, a dispersant, a plasticizer, a surfactant and a thixotropic agent.

As the leveling agent, it is preferable to appropriately select and use a silicon-based or fluorine-based leveling agent. Examples of the silicone leveling agent include polydimethylsiloxane, polymethylalkylsiloxane, polyether-modified polydimethylsiloxane, polysiloxane having (meth) acryl group, and the like.

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic-acid-based, and cyanoacrylate-based ultraviolet absorbers.

Examples of the antioxidant include hindered phenol-based, sulfur-based and phosphorus-based antioxidants.

Examples of the light stabilizer include hindered amine light stabilizers.

Each of these additives may be used alone or in combination of two or more. The content of these other additives is preferably 10% by mass or less, more preferably 3% by mass or less, of the total solid content.

The coating method of the curable composition is not particularly limited and a known method can be used, and examples thereof include a dipping coating, a spray coating, a flow coating, a shower coating, a roll coating, a spin coating and a brush coating.

After the application of the curable composition, the cured layer can be formed by drying the solvent (volatile component) at 0 to 200 캜, preferably, by heat and / or radiation.

When heat is generated, for example, electric heaters, infrared lamps, hot winds and the like can be used as the heat source thereof. The preferred curing conditions in the case of heat are 20 to 150 캜, and are performed within a range of 10 seconds to 24 hours.

In the case of radiation (light), the source of the radiation is not particularly limited as long as it can cure the composition in a short time after application. Examples include a lamp, a resistance heating plate and a laser as a source of infrared rays, A mercury lamp, a halide lamp, a laser as a source of ultraviolet rays, a thermoelectric material generated from a tungsten filament commercially available as a source of electron beams, a cold cathode And a secondary electron system using secondary electrons generated by collision between ionized gas molecules and metal electrodes. As a source of alpha rays, beta rays and gamma rays, for example, a nuclear fission material such as Co ₆₀ can be used, and for gamma rays, a vacuum tube or the like in which acceleration electrons collide with an anode can be used. These radiation can be irradiated alone, or two or more species may be irradiated at the same time or for a certain period of time.

As the radiation, ultraviolet rays or electron beams are preferably used. In this case, the irradiation amount of ultraviolet rays is preferably 0.01 to 10 J / cm ² , more preferably 0.1 to 2 J / cm ² . The irradiation conditions of the electron beam are preferably 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 dose of 1 to 10 Mrad.

The laminated film is excellent in scratch resistance, adhesion, and outgassing property as described above. Therefore, the laminated film is suitably used as a surface material for a display device such as a touch panel, a membrane switch, a keypad, and the like.

<Laminated film>

The laminated film 1 of Fig. 1 has a base layer 2 and a cured layer 3 laminated on at least one surface (front side) of the base layer 2.

(Base layer 2)

The material for forming the base layer 2 is not particularly limited, but a transparent resin is preferable. When the base layer 2 is made of a transparent resin, the laminated film can be suitably used as a material for a touch panel or the like. Examples of the material include polycarbonate resin, polymethacrylate resin, polystyrene resin, polyester resin, polyolefin resin, epoxy resin, melamine resin, cyclic olefin resin, triacetylcellulose, ABS , Synthetic resin such as AS, glass and the like. Among these, a synthetic resin is preferable, and a cyclic olefin resin and a polyester resin are more preferable, and a cyclic olefin resin is more preferable. By using such a resin, higher heat resistance, durability and transparency can be exhibited.

The cyclic olefin-based resin is not particularly limited as long as it is a resin obtained by polymerizing a monomer containing a cyclic olefin (cycloolefin). As the cyclic olefin resin, any of cycloolefin polymer (COP) and cycloolefin copolymer (COC) may be used, and a cycloolefin copolymer is more preferable. The cyclic olefin resin is preferably a resin obtained by polymerizing a monomer containing at least one monomer selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ) A resin obtained by hydrogenation is preferable. Examples of the polymerization include addition polymerization, ring-opening metathesis polymerization and the like.

(Formula (X ₀₎ of, R ^x1 to R ^x4 are each independently selected from to (i ') to (ix') is the atom or group selected from, k ^x, m ^x and p ^x are each independently 0 or Positive integer)

(i ') hydrogen atom

(ii ') a halogen atom

(iii ') a trialkylsilyl group

(iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a connecting group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(v ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi ') polar group (except for (iv') above)

(vii ') R ^x1 and R ^x2, or an alkylidene group formed by bonding R ^x3 and R ^x4 to each other (provided that R ^x1 to R ^{x4 which} are not involved in the bond are independently selected from the above (i') to (vi ' ) &Lt; / RTI &gt;

(viii ') a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (provided that R ^x1 to R ^{x4 which} do not participate in the bonding are each independently ') Or (vi').

(ix ') a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding R ^x2 and R ^x3 to each other, provided that R ^x1 and R ^{x4 which} do not participate in the bonding are each independently selected from the above (i') to (vi ') Selected atom or group)

(Formula (Y ₀₎ of, R ^y1 and R ^y2 are each independently selected from the above (i ') to (vi' or atom or a group selected from a), or R ^y1 and R ^y2 are monocyclic or are formed in combination with each other An alicyclic hydrocarbon ring, an aromatic hydrocarbon ring or a heterocyclic ring, and each of k ^y and p ^y is independently 0 or a positive integer)

The base layer (2) may contain, for example, an ultraviolet absorber, a plasticizer, a stabilizer, and the like as other additives.

The average thickness of the base layer 2 is not particularly limited, but is preferably 10 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. By making the base layer 2 have an average thickness in the above range, the bending resistance and strength can be more balanced.

The method for producing the base layer 2 is not particularly limited, but it can be produced by forming a material containing the above-mentioned resin as a main component. Such a film-forming method is not particularly limited, and for example, a known film-forming method such as a solvent casting method, a melt extrusion method, and a calender method can be used. After the film formation, the base layer 2 may be subjected to stretching treatment.

(Cured layer 3)

The cured layer 3 is formed by application of the curable composition of the present invention.

The average thickness of the cured layer 3 is preferably 0.05 탆 or more and 10 탆 or less, more preferably 0.1 탆 or more and 5 탆 or less. By setting the average thickness of the cured layer 3 within the above range, transparency and the like can be improved while maintaining scratch resistance, adhesion and outgassing properties.

<Touch sensor>

The touch sensor of the present invention comprises the above-mentioned laminated film.

The touch sensor further includes a conductive layer such as a transparent conductive layer on at least one surface of the laminated film. This conductive layer is usually formed on the side opposite to the cured layer 3 with respect to the base layer 2 of the laminated film 1 in question.

The conductive layer is not particularly limited as long as it exhibits conductivity, but a transparent conductive layer is preferable. Examples of the transparent conductive layer include metal oxide layers such as tin oxide, indium oxide, antimony oxide, zinc oxide, cadmium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) A composite film, and a metal layer of gold, silver, copper, tin, nickel, aluminum, palladium, or the like. Further, a transparent conductive layer may be formed by coating a polythiophene-based or polyaniline-based conductive polymer on the above laminated film and forming the film. The conductive film may be a single layer or a multilayer. In the case where the conductive layer has a multilayer structure, it may be a multilayer film made of the same material or a multilayer film made of different materials.

The method of forming the conductive layer is not particularly limited, but known methods such as physical vapor deposition methods such as vacuum deposition, sputtering and ion plating, and chemical vapor deposition (CVD) are available. The uniformity of the film, From the viewpoint of the adhesion of the layer, the vacuum vapor deposition method and the sputtering method are preferable, and the sputtering method is more preferable.

Since the touch sensor uses the above-mentioned laminated film suppressed outgassing, even when the conductive layer is formed by a vacuum deposition method, a sputtering method, or the like, the formation can be effectively performed. As a result, the adhesion between the conductive layer and the laminated film . Further, as described above, the scratch resistance of the surface and the adhesion between the base layer and the cured layer are excellent. Therefore, the touch sensor of the present invention can exhibit better performance than the conventional touch sensor.

When the touch sensor is used for a capacitive touch panel, it is preferable that the conductive layer is patterned. As a method of patterning, a method of applying a resist on the conductive layer, chemically dissolving the conductive film after the pattern is formed by exposure and development, a method of vaporizing by chemical reaction in vacuum, a method of sublimating the conductive layer by laser And the like. However, it can be appropriately selected according to the shape, precision, and the like of the pattern.

<Touch panel>

The touch panel of the present invention includes the aforementioned touch sensor.

The touch panel further includes a display panel unit under the touch sensor. A general LCD (Liquid Crystal Display) or the like is used as the display panel unit.

Since the touch panel is provided with the above-described touch sensor, the touch panel can exhibit better performance than the conventional touch panel.

<Device device>

The device device comprises the above-mentioned touch panel. Examples of such device devices include mobile phones, smart phones, portable information terminals, tablet PCs, notebook computers, sales devices, ATMs, FA devices, OA devices, medical devices, and car navigation systems .

Since the device device is provided with the above-described touch panel, the device device can exhibit better performance than the conventional device.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Means a residue (nonvolatile component) obtained by drying the composition for 1 hour on a hot plate at a predetermined temperature (175 DEG C). The term &quot; solid component &quot; means a component excluding a volatile component such as a solvent from the composition.

[Synthesis of organic compound (B2)

Synthesis Example 1

To a solution containing 7.8 parts by mass of mercaptopropyltrimethoxysilane and 0.2 part by mass of dibutyltin dilaurate under dry air, 20.6 parts by mass of isophorone diisocyanate was added dropwise at 50 DEG C over 1 hour while stirring, Lt; / RTI &gt; for 3 hours. 71.4 parts by mass of pentaerythritol triacrylate was added dropwise thereto at 30 DEG C over 1 hour, followed by stirring at 60 DEG C for 3 hours to obtain an organic compound (B2). The amount of residual isocyanate in the product was analyzed to be 0.1% or less, indicating that the reaction was almost quantitatively terminated.

[Production of reactive particles (B)

Production Example 1

(Methyl ethyl ketone silica sol, MEK-ST-L manufactured by Nissan Chemical Industries, Ltd., number-average particle diameter 0.056 mu m, silica concentration 30 mass%, spherical shape), 15.0 parts by mass of the organic compound (B2) synthesized in Synthesis Example 1, 166.7 parts by mass (50 parts by mass as silica particles) and 0.2 part by mass of ion-exchanged water were stirred at 60 DEG C for 3 hours and then 2.4 parts by mass of methyl orthoformate were added and heated and stirred at the same temperature for 1 hour to obtain reactive particles B) dispersion (dispersion (B-1)). This dispersion (B-1) was weighed in an aluminum dish to 2 g, dried on a hot plate at 175 DEG C for 1 hour and weighed to obtain a solid content of 30.2% by mass.

Production Example 2

(Methyl ethyl ketone silica sol, MEK-ST-L manufactured by Nissan Chemical Industries, Ltd., number-average particle diameter 0.056 mu m, silica concentration 30 mass%, spherical shape), 30.0 parts by mass of the organic compound (B2) synthesized in Synthesis Example 1, 166.7 parts by mass (50 parts by mass as silica particles), 238.1 parts by mass of silica particle sol (methyl ethyl ketone silica sol, MEK-ST-UP manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.042 占 퐉, silica concentration 21 mass% (50 parts by mass as silica particles) and 0.4 part by mass of ion-exchanged water was stirred at 60 占 폚 for 3 hours and then 4.8 parts by mass of methyl orthoformate was added and the mixture was heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles (Dispersion (B-2)). The dispersion (B-2) was weighed in an aluminum dish to 2 g, dried on a hot plate at 175 DEG C for 1 hour and weighed to determine the solid content, which was 25.3 mass%.

Production Example 3

(Methyl ethyl ketone silica sol, MEK-ST-L manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.056 mu m, silica concentration 30 mass%, spherical shape), 45.0 parts by mass of the organic compound (B2) synthesized in Synthesis Example 1, 166.7 parts by mass (50 parts by mass as silica particles), 238.1 parts by mass of silica particle sol (methyl ethyl ketone silica sol, MEK-ST-UP manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 0.042 占 퐉, silica concentration 21 mass% (50 parts by mass as silica particles) and 0.6 part by mass of ion-exchanged water was stirred at 60 DEG C for 3 hours, 7.2 parts by mass of methyl orthoformate was added and the mixture was heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles (Dispersion (B-3)). This dispersion (B-3) was weighed in an aluminum dish to 2 g, then dried on a hot plate at 175 DEG C for 1 hour and weighed to obtain a solid content of 31.2% by mass.

[Preparation of compound (I)

Compounds (A1-1) to (A1-3) (compounds represented by the following formulas (A1-1) to (A1-3)) used in the preparation of the curable composition were prepared according to the following method.

Production Example 4

(4), 8 (9) -bis (hydroxymethyl) -tricyclo [5.2.1.0 ^2,6 ] decane (manufactured by Mitsubishi Chemical Corporation) was added to a four-necked flask equipped with a stirrer, a stirring motor, a thermometer and a brine condenser. 1,162 g (20 mol) (molar ratio 1: 4) of propylene oxide (manufactured by Showa Chemical Co., Ltd.) and 2,000 g of toluene were charged and reacted in the presence of sodium hydroxide at room temperature under nitrogen stream.

The obtained product solution was washed with 0.1N hydrochloric acid using a separatory funnel until the pH of the aqueous layer became neutral with a litmus test paper, and the organic layer was recovered.

The organic layer thus recovered was mixed with 1,160 g (10 moles) of 2-hydroxyethyl acrylate (Osaka Kikai Kagaku) and 1.72 g (0.01 mole) of para-toluenesulfonic acid in a synthetic stirrer, a stirring motor, a thermometer and a Dean- And the mixture was reacted at 110 ° C. Water generated by the reaction was appropriately discharged out of the system into a Dean Stark tube, and the reaction was terminated when the discharge of water ceased.

After completion of the reaction, the reaction solution was washed with 0.1N sulfuric acid using a separating funnel until the pH of the aqueous layer became neutral with a litmus test paper, and the organic layer was recovered.

The recovered organic layer was dried using an evaporator to obtain 207 g of a compound (A1-1). As a result of gas chromatography analysis, the purity of the compound (A1-1) was 99.2%.

Production Example 5

Except that the amount of propylene oxide used in Production Example 4 was changed to two times the molar amount relative to 3 (4) -8 (9) -bis (hydroxymethyl) -tricyclo [5.2.1.0 ^2,6 ] decane, In the same manner as in Example 4, 184 g of the compound (A1-2) was obtained. The purity of the compound (A1-2) was 99.4%.

Production Example 6

210 g of the compound (A1-3) was obtained in the same manner as in Production Example 4, except that an equimolar amount of this? -Caprolactone was used in place of the propylene oxide in Production Example 4. The purity of the compound (A1-3) 98.2%.

[Preparation of curable composition]

Components other than the reactive particles (B) used in the production of the curable composition are shown below.

(Compound (I))

A1-1: A compound represented by the following formula (A1-1) (the compound prepared in Preparation Example 4)

A1-2: A compound represented by the following formula (A1-2) (the compound prepared in Preparation Example 5)

A1-3: A compound represented by the following formula (A1-3) (the compound prepared in Preparation Example 6)

(Compound (II))

A2-1: Art Resin H-34 (tetrafunctional urethane acrylate) manufactured by Negami Chemical Industry Co.,

A2-2: Art Resin UN-904 (10-functional urethane acrylate) manufactured by Negami Kogyo Co.,

A3-1: tricyclodecane dimethanol diacrylate (compound represented by the following formula (A3-1)):

A3-2: A-DPH (dipentaerythritol hexaacrylate) manufactured by Shin-Nakamura Chemical Industry Co.,

(Radical polymerization initiator (C))

C-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (BASF Irugacure 907)

C-2: 1-Hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 from BASF)

(Solvent (D))

D-1: Methyl ethyl ketone (MEK)

[Example 1]

21.4 parts by mass of (A1-1) as the compound (I), 48.2 parts by mass of (A2-1) as the compound (II) and 19.4 parts by mass of (A2-2) , 2.0 parts by mass of a radical polymerization initiator (C-2) as a radical polymerization initiator (C-2), and 60.0 parts by mass of (D-1) as a solvent (D) And the mixture was stirred at 40 DEG C for 2 hours to obtain a uniform curable composition.

The obtained curable composition was coated on one side of a norbornene resin film (Atton FEKE100, manufactured by JSR Corporation, thickness: 100 mu m) as a base layer so as to have a dry film thickness of 1.7 mu m using a bar coater. Then, the resultant was dried in a hot-air dryer at 80 ° C for 3 minutes, and irradiated with a light amount of 1 J / cm ² under a nitrogen atmosphere using a conveyor mercury lamp to form a cured layer. A cured layer was similarly formed on the other surface of the substrate layer to obtain a laminated film.

[Examples 2 to 5 and Comparative Examples 1 to 7 and 9]

Each of the curable compositions of Examples 2 to 5 and Comparative Examples 1 to 7 and 9 was prepared in the same manner as in Example 1 except that the compositions shown in Table 1 and Table 2 were used. Each laminated film was obtained by the same operation.

[Examples 6 to 10 and Comparative Examples 8 and 10]

The curable compositions of Examples 6 to 10 and Comparative Examples 8 and 10 were prepared in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were used. Based resin film (PET film Lo Mirror U48 manufactured by Toray Co., Ltd., film thickness 50 mu m) was used instead of the above-mentioned laminated film.

[evaluation]

Each laminated film thus obtained was subjected to the following evaluations. The evaluation results are shown in Tables 1 and 2 together.

(1) Steel wool (SW) in scratch

The surface of the coated film was examined visually by scratching the surface of the coated film tested by reciprocating 10 times with # 0000 steel wool charged with 200 g by a tester abrasion resistant abrasion tester manufactured by a tester mountain bridge. When the number of scratches was 10 or less, it was evaluated as &quot;? &Quot;, and when the number of scratches exceeded 10, it was evaluated as &quot;

(2) Adhesion between the cured layer and the substrate layer

(%) In a lattice of 100 squares on each side in total, in accordance with the lattice cellophane tape peeling test in JIS-K5400.

(3) Out gas amount

A sample (mass: about 20 mg) cut into a size of 4 mm x 40 mm was placed in a glass tube whose cleanliness was confirmed, and heated at 150 ° C for 10 minutes while passing a high purity helium gas. The gas component generated from the sample was cooled and concentrated. - The amount thereof was measured by a mass spectrometer (GC-MS) (unit: ppm). The ionization method of the mass spectrometer was an electron impact method (EI method, 70 eV).

(4) Pencil Hardness

And measured according to JIS-K5600-5-4.

(5) Crack test

A transparent thin film containing a tin-indium composite oxide was formed on one side of the laminated film. The film formation was performed by applying DC power of 7 W / cm ² using tin oxide (manufactured by Mitsui Kinzoku Kogyo Co., Ltd.) containing 10 mass% of indium oxide as a target and then supplying Ar gas at 190 sccm and O ₂ gas at a flow rate of 3.5 sccm Followed by DC magnetron sputtering under an atmosphere of 0.4 Pa. At this time, the temperature of the center roll was set to 24 캜 to form a sputtering film. A sample cut into a size of 50 mm x 70 mm was prepared from the laminated film having the sputtering film formed thereon and heat-treated at 150 ° C for 60 minutes.

Subsequently, a sputtered surface of a glass plate 100 mm x 100 mm (thickness 5 mm) and a sample of the laminated film was bonded to the pressure sensitive adhesive sheet (Sumikomo 3M manufactured pressure sensitive adhesive sheet 8146-4) so as not to bubble.

Subsequently, the thus-obtained bonded sample was subjected to a pencil hardness test (method according to JIS-K5600-5-4, the pencil was HB and the load was fixed at 80 g), and the sample was allowed to stand for 10 seconds without sliding, Were visually observed.

As a result of visual observation, it was evaluated as &quot;? &Quot; when cracks were not confirmed, and &quot; x &quot;

As shown in Table 1 and Table 2, according to the curable composition of the examples, it is possible to form a cured layer having excellent scratch resistance and adhesion and at the same time suppressing outgas.

According to the curable composition of the present invention, it is possible to form a cured layer having excellent scratch resistance and adhesion and at the same time suppressing outgas. The laminated film of the present invention is excellent in scratch resistance, adhesion, and outgassing property. INDUSTRIAL APPLICABILITY The touch sensor of the present invention, the touch panel having the same, and the device device having the touch sensor of the present invention exhibit high scratch resistance, adhesion, and outgas suppressibility, and can exhibit superior performance.

1 laminated film
2 substrate layer
3 cured layer

Claims (9)

A curable composition containing a compound (I) represented by the following formula (1).

(Wherein R ¹ and R ² are each independently a group represented by the following formula (i) or a group represented by the following formula (ii), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group , R ^A is an alkyl group having 1 to 5 carbon atoms, k is an integer of 0 to 14, and when k is 2 or more, a plurality of R ^A's may be the same or different)

(In the formulas (i) and (ii), R ^5a is an alkanediyl group having 2 to 6 carbon atoms and m is an integer of 0 to 20, provided that R ¹ and R ² are all represented by the above formula (i) , and the sum of m is at least 1, R ^5b is C 1 -C 14, and the alkanediyl group, n is 1 an integer of 1 to 10, R ^5a and R ^5b are, if multiple individuals, respectively, a plurality of R ^5a and R ^5b are May be the same or different, and * represents a moiety bonded to the (meth) acryloyl group of the above formula (1) The curable composition according to claim 1, further comprising a compound (II) which is a compound different from the compound (I) and has a polymerizable group. The curable composition according to claim 2, wherein the polymerizable group of the compound (II) is a (meth) acryloyl group. The curable composition of claim 3, wherein the compound (II) further has a urethane bond. A base layer,
The cured layer
And,
Wherein the cured layer is formed from the curable composition according to any one of claims 1 to 4. The laminated film according to claim 5, wherein the base layer is a transparent resin. A touch sensor comprising the laminated film according to claim 5 or 6. A touch panel comprising the touch sensor according to claim 7. A device device comprising the touch panel according to claim 8.

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