JP5186768B2 - Antistatic curable composition, cured film and laminate - Google Patents

Description

  The present invention relates to an antistatic curable composition having hard coat properties and transparency, a cured film thereof, and a laminate thereof.

  Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a hard coat film having anti-scratch property, adhesion, etc., and an antistatic film using a photocurable composition on the surface of the device Has been made to form.

  In recent years, the development and generalization of information and communication equipment has been remarkable, and further improvements in performance and productivity such as hard coat coating film and antistatic coating film have been demanded. There have been various proposals.

  For example, the following technical proposals can be cited (see Patent Documents 1 to 3). Patent Document 1 discloses a method for producing a conductive paint using a ball mill or the like in an organic solvent with a conductive powder such as tin oxide and a plurality of monomer components. Patent Document 2 discloses a method of preparing a dispersion for a conductive paint using an antimony-doped tin oxide and an ultraviolet curable silane coupling agent in an organic solvent using a ball mill. Further, Patent Document 3 discloses a method of preparing a conductive coating material by dispersing conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling point solvent and a hardly dispersible high boiling point solvent.

On the other hand, in addition to the above hard coat properties and antistatic properties, many attempts have been made to supplement all of the anti-reflection properties in addition to the above hard coat properties and antistatic properties. A technique of controlling the refractive index to a predetermined refractive index while holding it has also been proposed (Patent Documents 4 to 7). Patent Document 4 discloses a method of controlling the refractive index of conductive inorganic fine particles themselves by using core / shell type fine particles that enclose cavities in the conductive fine particles. Further, Patent Document 5 discloses a method for controlling the refractive index of conductive inorganic fine particles to be low by using core / shell type fine particles that enclose silica in the conductive fine particles. Patent Document 6 discloses a method of controlling the refractive index of conductive inorganic fine particles themselves to be high by using core / shell type fine particles in which titanium oxide is included in the conductive fine particles. Furthermore, Patent Document 7 discloses a method of controlling the refractive index of the entire coating film by controlling the refractive index of the binder resin by using a fluorine resin together.
Japanese Patent Laid-Open No. 04-172634 Japanese Patent Laid-Open No. 06-264209 JP 2001-131485 A JP 2002-279917 A JP 2005-119909 A JP 2002-363442 A JP 2004-122611 A

  However, even if it is possible to create a photocurable composition having good physical properties in terms of hard coat properties, antistatic properties, light resistance, etc. by the above method, it can be applied to highly hydrophobic media such as organic solvents. In view of the transparency of the coating film and the stability over time of the photo-curing paint, the conductive inorganic fine particles having an average primary particle diameter of 100 nm or less are not effectively dispersed and stabilized at the primary particle level. Prone to problems.

  In addition, as a method for adjusting the refractive index of the coating film, when the content of the conductive inorganic fine particles (high refractive index) in the coating film is changed, the conductivity changes greatly, and in particular, the conductive inorganic fine particles ( If the content in the coating film having a high refractive index is reduced, the surface resistance value of the coating film may be lowered and the predetermined antistatic property may not be obtained. The method of controlling the refractive index of the conductive inorganic fine particles themselves to a predetermined refractive index is a method that can achieve a good balance between the refractive index and the antistatic property, but the synthesis method becomes complicated, resulting in a decrease in production efficiency and a significant increase in cost I can not escape. Furthermore, in the method of controlling the refractive index of the entire coating film by controlling the refractive index of the binder resin, the refractive index of the commonly used hard coat binder resin is very narrow, so let's change the refractive index forcibly. In this case, there is a concern that the hard coat property may be significantly reduced, the cost may be significantly increased, and the compatibility with other binder components may be directly deteriorated.

  Therefore, the present invention can form a coating film having excellent physical properties in all of antistatic properties, hard coat properties, transparency and light resistance while containing conductive inorganic fine particles having an average primary particle size of 100 nm or less. Anti-static curable composition that is stable over time, and anti-static composition that can freely and easily change the refractive index of the anti-static curable composition between 1.5 and 1.8 It aims at providing the curable composition, the cured film using them, and its laminated body.

The present invention comprises conductive inorganic fine particles having an average primary particle size of 5 to 100 nm,
Silicon oxide having an average primary particle size of 5 to 100 nm;
An amino group-containing photocurable compound having a functional group obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, and an unreacted ethylenically unsaturated double bond;
The present invention relates to an antistatic curable composition containing

  The present invention also relates to the antistatic curable composition, wherein the conductive inorganic fine particles contain at least one element selected from the group consisting of antimony, indium, tin and zinc.

  The present invention also relates to the above antistatic curable composition, wherein the conductive inorganic fine particles are not surface-treated with an insulating metal oxide and / or a hydrolyzable organometallic compound. .

  In the present invention, the conductive inorganic fine particles are antimony pentoxide, and the relative ratio (D2 / D1) between the average primary particle diameter (D1) of antimony pentoxide and the average primary particle diameter (D2) of silicon oxide is 0. The present invention relates to the above-mentioned curable composition for antistatic, which is characterized by being 1 to 1.2.

  The present invention also relates to an antistatic curable composition characterized in that silicon oxide is treated with a hydrolyzable organometallic compound.

  Further, in the present invention, the amino group-containing photocurable compound is obtained by reacting a compound represented by the following general formula (1) with a primary amine or a secondary amine. The present invention relates to a curable composition for prevention.

General formula (1)

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group, R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group, and R ⁹ represents a tetravalent aliphatic group or an aromatic group.
The present invention also relates to the antistatic curable composition, wherein the primary amine or the secondary amine is an aliphatic monoamine.

  The present invention further relates to the antistatic curable composition, further comprising a solvent, wherein the solvent comprises 10 to 100% by weight of a hydroxyl group-containing solvent with respect to the total solvent.

  The present invention also relates to a cured film obtained by curing the antistatic curable composition.

The present invention also relates to the above cured film, wherein the surface resistance value is 1 × 10 ¹² Ω / □ or less.

  Moreover, this invention relates to the said cured film characterized by the thickness of a cured film being 0.1-30 micrometers.

  The present invention also relates to the cured film as described above, wherein the refractive index of the cured film is in the range of 1.5 to 1.8.

  Moreover, this invention relates to the laminated body formed by forming the said cured film on a base material.

  The present invention also relates to the above laminate, wherein the substrate is a plastic substrate.

  Moreover, this invention relates to the said laminated body, wherein a base material is a lens shape.

  The present invention also relates to the above laminate, wherein the difference in refractive index between the cured film and the substrate is within ± 0.02.

  Further, the present invention is characterized in that it further comprises one or more lower layers between the cured film and the substrate, and the difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02. It is related with the said laminated body.

  Moreover, this invention relates to the said laminated body containing an information recording layer.

  Moreover, this invention relates to the said laminated body which is an antireflection film.

  Moreover, this invention relates to the manufacturing method of the cured film formed by apply | coating the said curable composition for antistatic to a base material, and irradiating an active energy ray and making it harden | cure.

  The antistatic curable composition of the present invention comprises an amino group-containing photocurable compound obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine, conductive inorganic fine particles, Furthermore, since it contains silicon oxide, it has excellent curability, antistatic properties, hard coat properties, transparency and light resistance, and a cured film and a laminate thereof that can freely adjust the refractive index while maintaining the above physical properties. It is particularly suitable for hard coating agents such as plastic optical components, optical disks, antireflection films, touch panels, film-type liquid crystal elements, and plastic laminates. Furthermore, when the refractive index adjustment range is wide and a coating film having the same refractive index is applied to various base materials, no reflection interference fringes are generated, and it is suitably used for optical applications.

  First, the antistatic curable composition of the present invention will be described.

  The antistatic curable composition of the present invention comprises at least conductive inorganic fine particles having an average primary particle diameter of 5 to 100 nm, silicon oxide having an average primary particle diameter of 5 to 100 nm, ethylenically unsaturated double bonds, It contains a functional group obtained by reacting with a primary amine or a secondary amine, and an amino group-containing photocurable compound having an unreacted ethylenically unsaturated double bond. Inorganic fine particles and / or silicon oxide, and two or more kinds of amino group-containing photocurable compounds may be included.

  In the present invention, the average primary particle size can be obtained by directly measuring the particle size of the particle itself with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like.

  When the average primary particle diameter of the conductive inorganic fine particles is less than 5 nm, it is very difficult to disperse the highly transparent primary particles because the cohesive force between the fine particles is very large. In addition, when the average primary particle diameter exceeds 100 nm, it becomes easy to disperse at the primary particle level, but since the particle diameter is large, scattering of visible light or the like is likely to occur, and the transparency of the cured film is deteriorated. Cause problems.

  As the conductive inorganic fine particles, those containing at least one element selected from the group consisting of antimony, indium, tin, zinc, aluminum, titanium, gallium, phosphorus and fluorine are preferable. In particular, those containing any one element of antimony, indium, tin and zinc are more preferable because of their good conductivity. The element-containing form is preferably a metal oxide, specifically, antimony pentoxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide. (PTO), zinc antimonate (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and the like. Two or more kinds of these conductive inorganic fine particles may be used in combination.

As a commercial item of conductive inorganic fine particles, manufactured by Nissan Chemical Industries: San Epoque EFR-6N, San Epoque EFR-6NP (antimony pentoxide), manufactured by Ishihara Sangyo: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO-coated titanium oxide), manufactured by Mitsubishi Materials: T-1 (ITO), S-1200, S-2000 (tin oxide), EP T- 1-5L (ATO), EP SP- 2 (PTO), Mitsui Mining & Smelting made: Pastran (ITO, ATO), manufactured by CI Kasei Co.: Nanotech ITO, NANOTEC SnO _2, catalysts & Chemicals Industries Co., Ltd.: TL-20 (ATO), TL -30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO), manufactured by Hakusui Tech: PazetCK (Aluminum-doped zinc oxide), PazetGK (gallium-doped zinc oxide), Sakai Chemical Industry: SC-18 (aluminum-doped zinc oxide) and the like.

  Furthermore, as a commercially available conductive inorganic fine particle dispersion in which conductive inorganic fine particles are dispersed in a solvent or water, Ishihara Sangyo SNS-10M (ATO), SNS-10T (ATO), FSS-10M (ATO) , FSS-10T (ATO), manufactured by Nissan Chemical Industries, Ltd .: Celnax CX-Z603M-F2 (AZO), Celnax CX-Z610M-F2 (AZO), Celnax CX-Z210IP-F (AZO), Celnax CX- Z210IP-F2 (AZO), Celnax CX-Z410M-F (AZO), Celnax CX-Z401M-F (AZO), HX-305M5, HIT-301M1, ATM-330S, HX-305M5, manufactured by Catalytic Chemical Industries: ELCOM P-30 (ATO), ELCOM P-32 (ATO), ELCOM P-3 (PTO), ELCOM P-45 (antimony pentoxide), ELCOM P-120 (ITO), include ELCOM P-130 (ITO) and the like.

  The conductive inorganic fine particles contained in the antistatic curable composition of the present invention are preferably those that are not surface-treated with an insulating metal oxide and / or a hydrolyzable organometallic compound.

  Examples of the insulating metal oxide include silicon oxide, aluminum oxide, and zirconium oxide.

Examples of hydrolyzable organometallic compounds include general formula R ¹ _{nM m} (OR ² ) _mn [wherein R ¹ , R ² : alkyl group, aryl group, vinyl group, acrylic group, methacryl group, amino Group, hydrocarbon group containing a functional group such as glycidyl group, mercapto group, M: metal atom, m = coordination number of element, silicon represented by n = 0, 1, 2, or 3], titanium, Examples thereof include alkoxides such as zirconium and aluminum, and metal diketonates.

  Specific hydrolyzable organometallic compounds include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, vinyltriethoxysilane, phenyltriethoxy. Organosilicon compounds such as silane, aminopropyltrimethoxysilane, glycidoxypropyltriethoxysilane, styryltrimethoxysilane, mercaptopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, aluminum (III) Organic aluminum compounds such as n-butoxide, aluminum (III) 2,4-pentanedionate, diethylaluminum ethoxide, titanium n-butoxide, titanium Organic titanium compounds such as nium oxide bis (pentanedionate) and titanium dibutoxide (bis-2,4-pentanedionate), zirconium n-butoxide, zirconium 2,4-pentanedionate, zirconium dibutoxide (bis-2) , 4-pentanedionate) and the like.

  When the surface of the conductive inorganic fine particles is treated with an insulating metal oxide and / or a hydrolyzable organometallic compound, the conductivity of the conductive inorganic fine particles themselves decreases, and further, when mixed with silicon oxide The conductivity tends to decrease. In particular, in the case of antimony pentoxide, which is referred to as proton conductivity, when the surface of the fine particles is treated with an insulating metal oxide, the acidic protons on the surface of antimony pentoxide involved in the conductivity are reduced, and the conductivity is reduced. Since it becomes easy to inhibit, it is preferable that the surface treatment is not performed with an insulating metal oxide and / or a hydrolyzable organometallic compound as much as possible.

  When the average primary particle diameter of silicon oxide is less than 5 nm, there are few commercially available products at first, and even if they are present, they are very expensive and not practical. Further, when trying to disperse a silicon oxide powder having an average primary particle diameter of less than 5 nm, it is very difficult to disperse at a primary particle level with high transparency because the cohesive force between the fine particles is very large. In addition, in the case of silicon oxide having an average primary particle diameter of more than 100 nm, it is easy to disperse at the primary particle level. However, since the particle diameter is large, the cured film is likely to be scattered with respect to light such as visible light. The problem of worsening sex occurs.

  Commercially available products of silicon oxide powder include AEROSIL 50, AEROSIL 90G, AEROSIL 130, AEROSIL 200, AEROSIL 200V, AEROSIL 200CF, AEROSIL 200FAD, AEROSIL 300, AEROSIL 300CF, AEROSIL 380, AEROSIL 380, AEROSIL 380, AEROSIL 380, 2 AEROSIL R972CF, AEROSIL R974, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL OX50, AEROSIL TT600, AEROSIL MOX80, AEROSIL COK84, AEROSIL RX200, AEROSIL 0, manufactured by Tosoh Silica: Nipsil E-150J, Nipsil E-170, Nipsil E-200, Nipsil E-220, Nipsil E-200A, Nipsil E-220A, Nipsil K-500, Nipsil E-1009, Nipsil E- 1011, Nipsil E-1011, Nipsil E-1030, Nipsil E-75, Nipsil E-743, Nipsil E-74P, Nipsil L-250, Nipsil G-300, Nipsil N-300A, Nipsil HD-2, Nipsil E- 170, Nipsil E-200, Nipsil E-220, Nipsil SS-10, Nipsil SS-15, Nipsil SS-20, Nipsil SS-30 P, Nipsil SS-50, Nipsil SS-50A, Nipsil SS-50B, Nipsil SS-50C, Nipsil SS-50F, Nipsil SS-70, Nipsil SS-72F, Nipsil SS-100, Nipsil SS-170X, Nipsil SS- 178B, NIPGEL AY-200, NIPGEL AY-220, NIPGEL AY-420, NIPGEL AY-451, NIPGEL AY-460, NIPGEL AY-601, NIPGEL AY-603, NIPGEL AY-6A3, NIPGEL AZ-200 201, NIPGEL AZ-204, NIPGEL AZ-260, NIPGEL AZ-360, NIPGEL AZ-400, NIP EL AZ-410, NIPGEL AZ-6A0, NIPGEL BY-200, NIPGEL BY-400, NIPGEL BY-601, NIPGEL BY-001, NIPGEL CX-200, NIPGEL CX-400, NIPGEL CY-200, manufactured by Fuji Silysia Chemical: Thylisia 250, Thylisia 250N, Thylisia 256, Thylisia 256N, Thylisia 310P, Thylisia 320, Thylisia 350, Thylisia 370, Thylisia 380, Thylisia 430, Thylisia 440, Thylisia 450, Thylisia 470, Thylisia 435, Thylisia 445, Thylisia 436, Thylisia 436 , Siricia 456, Siricia 476, Siricia 530, Siricia 550, Siricia 730, Rhino Shea 740, Silysia 770, manufactured by Mizusawa Chemical Industry: Mizukasil P-801, Mizukasil P-802, Mizukasil P-526, Mizukasil P-527, Mizukasil P-603, Mizukasil P-604, MizukaSil P-604, MizukaSil P-604 , Mizukasil P-78A, Mizukasil P-78D, Mizukasil P-78F, Mizukasil P-707, Mizukasil P-740, Mizukasil P-752, Mizukasil P-50, Mizukasil Pz 766K, Mizukasil P-78M, Mizukasil P-78F , Manufactured by Tokuyama: Leolo Seal QS-09, Leoro Seal QS-10, OroSeal QS-102, LeoloSeal CP-102, LeoloSeal QS-20, LeoloSeal QS-20L, LeoloSeal QS-30, LeoloSeal QS-30C, LeoloSeal QS-40, LeoloSeal MT-10, LeoloSeal MT-10C, LeoloSeal DM-10, LeoloSeal DM-10C, Leoroseal DM-30, Leoroseal DM-30S, Leoroseal KS-20SC, Leoroseal HM-20L, Leoloseal HM-30S, Leoloseal PM-20, Leoloseal PM-20L, Toxeal U, Toxeal UR, Toxeal NP, Toxeal NR, Toxeal PR, Toxeal GU-N, Toxeal USA, Toxeal T, Toxeal USG-A, Toxeal GU, Fine Seal A, Fine Seal B, Fine USF, Fine seal T-32, Fine seal E-50, Fine seal E-70, Fine seal X-37, Fine seal X-70, Fine seal RX-70, Fine seal X-37B, Fine seal X-12, Fine seal X-40, Fine seal X-30, Fine seal X-45, Fine seal X-60, Fine seal X-69, Fine seal X-80, Fine seal K-41, Fine seal F- 80, fine seal F-80B, fine seal G-70, fine seal G-71, fine seal G-80, fine seal G-81, fine seal G-86, fine seal CM-F, fine seal FM-14, Fine seal FM-22, fine seal F-30, etc. are mentioned.

  Furthermore, a commercially available silicon oxide dispersion in which silicon oxide having an average primary particle diameter of 5 to 100 nm is dispersed in an organic solvent or water from the beginning can be used. For example, manufactured by Nissan Chemical Industries: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex C, Snowtex N, Snowtex O, Snowtex S, Snowtex 20L, Snowtex OL, Methanol Silica Sol, MA-ST- MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK-ST, XBA-ST, PMA-ST, DMAC-ST, PGM-ST, manufactured by Catalytic Kasei Kogyo: OSCAL Series, manufactured by Fuso Chemical Industries: Quatron PL-1, Quatron PL-1-MA, Quatron PL-1- TOL, Quattron PL-2L-PGME, Quattron PL-3, Qu Toron PL-7, Quartron PL-20, and the like Quartron PL-30-IPA. In particular, from the viewpoint of solubility of the amino group-containing photocurable compound, among organic solvent-based dispersions, MEK-ST, MEK-ST-MS, MIBK-ST, PGM- dispersed in MEK, MIBK, PGM, etc. ST, quartztron PL-2L-PGME, etc. are preferable. These may be used as they are or may be subjected to a surface treatment with a hydrolyzable organometallic compound or the like. The surface treatment is preferable because the compatibility with the binder component is improved and the transparency of the cured film can be improved.

Examples of hydrolyzable organometallic compounds include general formula R ¹ _{nM m} (OR ² ) _mn [wherein R ¹ , R ² : alkyl group, aryl group, vinyl group, acrylic group, methacryl group, amino Group, hydrocarbon group containing a functional group such as glycidyl group, mercapto group, M: metal atom, m = coordination number of element, silicon represented by n = 0, 1, 2, or 3], titanium, Examples thereof include alkoxides such as zirconium and aluminum, and metal diketonates.

  Specific hydrolyzable organometallic compounds include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, octyltriethoxysilane, vinyltriethoxy. Organosilicon compounds such as silane, phenyltriethoxysilane, aminopropyltrimethoxysilane, glycidoxypropyltriethoxysilane, styryltrimethoxysilane, mercaptopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane Organoaluminum compounds such as aluminum (III) n-butoxide, aluminum (III) 2,4-pentanedionate, diethylaluminum ethoxide, Organic titanium compounds such as titanium n-butoxide, titanium oxide bis (pentanedionate), titanium dibutoxide (bis-2,4-pentanedionate), zirconium n-butoxide, zirconium 2,4-pentanedionate, zirconium di Organic zirconium or a compound such as butoxide (bis-2,4-pentanedionate) can be used. Of these hydrolyzable organometallic compounds, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methyltrimethoxysilane, octyltrimethylsilane, which do not add Michael to ethylenically unsaturated double bonds, are used for photocurable applications. More preferred are ethoxysilane, styryltrimethoxysilane, and the like.

  Examples of commercially available organic silicon compounds include: Shin-Etsu Chemical Co., Ltd .: KBM04, KBE04, KBM13, KBE103, KA1003, KBM1003, KBE1003, KBM303, KBM403, KBE402, KBE403, KBM502, KBM503, KBE502, MBE503, BBE503, BBE503, , KBE603, KBM903, KBE903, KBM573, KBM703, KBM803, KBM1403, LS5580 and the like. Examples of commercially available organic titanium compounds include Ajinomoto Fine Techno: KR TTS, KR 46B, KR 55, KR 41B, KR 38S, KR 138S, 338X, KR 44, KR 9SA, KR ET, and the like. Furthermore, as a commercially available organoaluminum compound, Ajinomoto Fine Techno: AL-M and the like can be mentioned.

  When the conductive inorganic fine particles contained in the antistatic curable composition of the present invention are antimony pentoxide, the relative relationship between the average primary particle size (D1) of antimony pentoxide and the average primary particle size (D2) of silicon oxide. The ratio (D2 / D1) is preferably 0.1 to 1.2. If this relative ratio (D2 / D1) is greater than 1.2, silicon oxide may inhibit the conductivity of antimony pentoxide. On the other hand, when the relative ratio (D2 / D1) is smaller than 0.1, the average primary particle diameter (D1) of antimony pentoxide is relatively increased, and thus transparency may be lowered.

  The amino group-containing photocurable compound functions as a dispersant for the conductive inorganic fine particles, and is a functional group (amino) obtained by reacting an ethylenically unsaturated double bond with a primary amine or a secondary amine. Group) and an unreacted ethylenically unsaturated double bond. The ethylenically unsaturated double bond of the amino group-containing photocurable compound is preferably derived from an acrylate group or a methacrylate group.

  Here, the “primary amine or secondary amine” is a concept that includes or includes both a primary amine and a secondary amine. Similarly, “acrylate group or methacrylate group” is a concept that includes or includes both acrylate groups and methacrylate groups. Hereinafter, acrylate and methacrylate may be collectively referred to as “(meth) acrylate”.

  Further, the amino group-containing photocurable compound is preferably a compound obtained by reacting an acrylate compound or methacrylate compound having a pencil hardness after photocuring of H or more and a primary or secondary amine. . The (meth) acrylate compound is more preferably one having a pencil hardness after photocuring of 2H or more, and more preferably 3H or more.

  Here, the pencil hardness refers to a pencil density symbol that does not cause scratches on a cured film having a thickness of 10 μm, based on JIS-K5600 (base material: easy-adhesion-treated PET film having a thickness of 100 μm, load: 500 g).

  When an amino group-containing photocurable compound obtained by reacting a (meth) acrylate compound with a pencil hardness of less than H after photocuring and a primary or secondary amine is contained, the metal oxide is dispersed. Since there is no major problem in the properties, the transparency of the cured film after photocuring is good, but there is a possibility of causing problems in hard coat properties, which may cause problems in use for hard coat applications. .

  As a (meth) acrylate compound in which the pencil hardness of the cured film after photocuring is H or more, a polyfunctional acrylate compound containing 3 or more acryloyl groups, or a polyfunctional methacrylate compound containing 3 or more methacryloyl groups However, photocurability is also good and preferable.

  Among the (meth) acrylate compounds in which the cured film after photocuring has a pencil hardness of H or higher, monomers include dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hydroxypentaacrylate, dipentaerythritol tetraacrylate (PETTA). Etc. Examples of the oligomer or polymer include polyester (meth) acrylate compounds, epoxy (meth) acrylate compounds, and urethane (meth) acrylate compounds. In particular, since the dispersibility of the metal oxide becomes better, the compound is preferably a compound having a molecular weight of 1000 to 20000, more preferably a polyester acrylate compound, an epoxy acrylate compound, or a urethane acrylate compound having a molecular weight of 1000 to 20000.

  A commercially available compound can be used as the (meth) acrylate compound in which the cured film after photocuring has a pencil hardness of H or higher. Specific examples include the following products.

Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400
Kayaku Sartomer Co., Ltd .: SR-295,
Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6 , NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A,
Manufactured by BASF: LaromerEA81,
Sannopco: Photomer 3016,
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710,
Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T,
Nippon Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B,
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

  Furthermore, as the amino group-containing photocurable compound that can be used in the present invention, for example, a compound obtained by reacting a compound represented by the following general formula (1) with a primary amine or a secondary amine. Can be mentioned.

General formula (1)

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group, R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group, and R ⁹ represents a tetravalent aliphatic group or an aromatic group.
In the formula, examples of the tetravalent aliphatic skeleton represented by R ⁹ include a tetravalent aliphatic group that is an alkyl skeleton having 4 to 10 carbon chains. Specifically, a butane skeleton, a cyclobutane skeleton, a hexane skeleton, a cyclohexane Examples include skeleton and decalin skeleton. Specific examples of the tetravalent aromatic group represented by R ⁹ include a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenyl ether skeleton, a diphenyl sulfone skeleton, a diphenyl sulfide skeleton, a perylene skeleton, a fluorene skeleton, a tetrahydronaphthalene skeleton, and a naphthalene. Examples include skeletons.

  The compound represented by the general formula (1) includes, for example, an aliphatic skeleton or an aromatic skeleton, and a compound (x1) having two or more carboxylic anhydride groups and a functional group capable of reacting with the carboxylic anhydride group. It is obtained by reacting a compound (X) having a carboxyl group obtained by reacting a compound (x2) having a group with a compound (Y) having a functional group capable of reacting with the carboxyl group.

  Here, examples of the “functional group capable of reacting with a carboxylic acid anhydride group” in the compound (x2) include a hydroxy group, an amino group, a glycidyl group, and the like. Particularly preferred. In addition, examples of the “functional group capable of reacting with a carboxyl group” in the compound (Y) include an epoxy group, an oxazoline group, a hydroxy group, an amino group, a carbodiimide group, an isocyanate group, an isothiocyanate group, and a vinyl ether group.

  Furthermore, an example is given and demonstrated. The following general formula (2), which is a compound (x1) having an aliphatic skeleton or an aromatic skeleton, and two or more carboxylic anhydride groups:

General formula (2)

(Where R ⁹ is as defined in general formula (1))
A compound (x2) having a functional group capable of reacting an aliphatic or aromatic tetracarboxylic dianhydride represented by the following general formula (3):
^{_{CH 2 = C (R 1)}} COOR 5 OH Formula (3)
(Where R ¹ and R ⁵ are as defined in formula (1))
And a first hydroxyl group-containing acrylate compound or methacrylate compound represented by the following general formula (4):
^{_{CH 2 = C (R 2)}} COOR 6 OH Formula (4)
(Where R ² and R ⁶ are as defined in Formula (1))
Is reacted with a second hydroxyl group-containing acrylate compound or methacrylate compound represented by the following general formula (5):

General formula (5)

(Where R ¹ , R ² , R ⁵ , R ⁶ and R ⁹ are as defined in formula (1))
The compound (X) shown by can be obtained.

  Examples of the aliphatic tetracarboxylic dianhydride represented by the general formula (2) include butanetetracarboxylic dianhydride.

  On the other hand, as aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride having biphenyl skeleton, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic 9,9-bis (3,4-di) having a fluorene skeleton, such as acid dianhydride, diphenyl sulfide tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride having a naphthalene skeleton Carboxyphenyl) fluorene dianhydride, or 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, tetrahydronaphthalenecarboxylic dianhydride having a tetrohydronaphthalene skeleton, ethylene glycol Bis (anhydro Rimeriteto), glycerin bis (anhydrotrimellitate) monoacetate, and the like. Commercially available products include “Ricacid TMTA-C”, “Ricacid MTA-10”, “Ricacid MTA-15”, “Ricacid TMEG Series”, “Ricacid TDA”, “Ricacid DSDA”, etc. It is done.

  Among these aromatic tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound represented by formula (1). This is particularly preferable because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.

  The first and second hydroxyl group-containing (meth) acrylate compounds may be the same or different from each other. Examples of such hydroxyl group-containing (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth). Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, dihydroxy Acrylate, glycerol (meth) acrylate, isocyanuric acid EO-modified diacrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol Ritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Is mentioned. In the case of increasing the hardness, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

  Specific commercial products include Biscoat # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.), PETIA (manufactured by Daicel UCB Corporation), Aronix M305 (manufactured by Toagosei Co., Ltd.) ), NK ester A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-444 (manufactured by Sartomer Co., Ltd.), light acrylate DPE-6A (Kyoeisha Chemical Co., Ltd.) KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), Aronix M402 (manufactured by Toagosei Co., Ltd.) and the like. In particular, KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) containing pentaerythritol tri (meth) acrylate as a main component is more preferable because the dispersibility of the metal oxide is good. In the case of a polyfunctional (meth) acrylate compound, by containing about 5 to 15% of a polyfunctional (meth) acrylate having two hydroxyl groups as an accessory component, the weight average after curing of the resulting amino group-containing photocurable compound It is preferable because the molecular weight tends to increase and the dispersibility of the metal oxide becomes better.

  The reaction between the aliphatic or aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds is carried out by using two carboxylic acids possessed by the aliphatic or aromatic tetracarboxylic dianhydride. This is a reaction between an anhydride group and a hydroxyl group contained in each of the first and second hydroxyl group-containing (meth) acrylate compounds, and as such is well known in the art. For example, the aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds are mixed with 1,8-diazabicyclo [5.4.0] -7 in an organic solvent such as cyclohexanone. The reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of a catalyst such as undecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.

After the reaction, the reaction product containing the compound (X) of the formula (5), which is a reaction product, is purified without purification, for example, the following general formula (6), which is the compound (Y):
General formula (6)

(Where R ⁰ is a CH ₂ ═C (R ³ ) —C (O) O— group and a CH ₂ ═C (R ⁴ ) —C (O) O— group; R ³ and R ⁴ are As defined)
And a compound represented by the general formula (1) can be obtained (in this case, R ⁷ and R ⁸ are —CH ₂ CH (OH) CH ₂ — groups). is there.).

  Examples of the compound represented by the formula (6) include glycidyl methacrylate, epoxy group-containing (meth) acrylate such as glycidyl acrylate; o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, monostyrenated phenol glycidyl ether, Examples include aromatic glycidyl ether compounds such as 4-cyano-4-hydroxybiphenyl glycidyl ether, 4,4′-biphenol monoglycidyl ether, and 4,4′-biphenol diglycidyl ether.

  The reaction between the compound represented by formula (5) and the compound represented by formula (6) is a reaction between the carboxyl group possessed by the compound represented by formula (5) and the epoxy group possessed by the compound represented by formula (6). As such, it is well known in the art. For example, this reaction can be performed at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

  These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

  The primary or secondary amine constituting the amino group-containing photocurable compound is an amine compound having at least one primary amino group or secondary amino group in one molecule, and has a low rigidity. More preferred are group amines. Furthermore, when an amine compound having two or more primary or secondary amino groups in the molecule is used, a plurality of acrylate compounds or methacrylate compounds react in a complex manner with respect to one amine compound molecule. It has a problem of high molecular weight and easy gelation. Therefore, it is preferable to obtain a versatile amino group-containing photocurable compound by reducing the amount of amine compound added to the (meth) acrylate compound or by controlling the reaction conditions.

  The amine compound may have a polar functional group other than the amino group that does not react with the (meth) acrylate compound. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  Among the primary amines constituting the amino group-containing photocurable compound, monoamines include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2 -Aminopentane, 3-aminopentane, isoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2 -Methylpropane, 3- Mino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauri Loxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-aminoben Phenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol And allylamine.

  Among the secondary amines constituting the amino group-containing photocurable compound, monoamines include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, and di-n-propyl. Amine, di-n-butylamine, disec-butylamine, N-ethylisoamylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-methylaminoethanol, 3-methylamino -1,2-propanediol, 1-piperazi Ethanol, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-pyrrolidinol, indoline, N-butylaniline, N-methylbenzylamine, 3-benzylaminopropio Examples include nic acid ethyl ether, 4-benzylpiperidine, and diphenylamine.

  Further, among the primary amine and secondary amine constituting the amino group-containing photocurable compound, examples of the amine compound having a plurality of amino groups in the molecule include 3-aminopyrrolidine, dimethylaminoethylamine, ethylamino Ethylamine, diethylaminoethylamine, N, N-diisopropylaminoethylamine, 1,2-diaminopropane, 1,3-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 2-hydroxyethyl Aminopropylamine, bis- (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2 -Jimee Rupropane, 1,2-diaminobutane, 1,4-diaminobutane, laurylaminopropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl4-pipecoline, N-aminopropylpiperidine, N-aminopropyl 2-Pipecoline, N-aminopropyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylmorpholine, iminobispropylamine, methyliminobispropylamine, 4-piperidinecarboxamide, 4-aminomethyl- 1-butylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-piperidinopiperidine, N-aminopropylaniline, 3-aminopyrrolidine, N-methylpiperazine, N- Ethyl piperazine N-allylpiperazine, N-isobutylpiperazine, N-aminopropylpiperazine, 1-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine, 1- (4-pyridyl) piperazine, homopiperazine, N-methyl Examples include homopiperazine.

  The amine compounds shown above may be used alone or in combination of two or more.

  Among these, an aliphatic monoamine having only a secondary amino group is preferable because the dispersibility of the metal oxide is good, and the Michael addition reaction is completed in one stage and the coloring due to the reaction is small.

  Aliphatic monoamines having only secondary amino groups include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, Disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 2 -Methylaminoethanol, 3-methylamino-1,2-propanediol, 1-piperazineethanol, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3- Pyrrolidinol, etc. . In particular, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, and di-n-butylamine have dispersibility and dispersion stability of metal oxides. It is preferable because it becomes better.

  In obtaining the amino group-containing photocurable compound used in the present invention, the (meth) acrylate compound and the primary or secondary amine are 100 moles of ethylenically unsaturated double bonds in the (meth) acrylate compound. On the other hand, the primary or secondary amine is preferably reacted at a ratio of 0.5 to 50 mol, more preferably 1.0 to 30 mol. That is, in the amino group-containing photocurable compound, 0.5 to 50 mol (more preferably 1.0 to 30 mol) of amino group (that is, ethylenically unsaturated double bond and primary or secondary). It is preferable that 50-95.5 mol (more preferably 70-99 mol) of an unreacted ethylenically unsaturated double bond is included.

  When the reaction ratio of the primary or secondary amine is less than 0.5 mol, since the ratio of amino groups in the resulting amino group-containing photocurable compound is small, good dispersibility of the metal oxide can be obtained. It becomes difficult and the transparency of the cured film tends to deteriorate. Further, when this reaction ratio exceeds 50 mol, the ratio of amino groups in the resulting amino group-containing photocurable compound becomes very large, so that good metal oxide dispersibility can be obtained. Since the ratio of unsaturated double bonds becomes low, the photocurability at the time of coating film preparation becomes poor, and the hard coat property of the cured film tends to be lowered.

  The amino group-containing photocurable compound can be obtained by reacting the (meth) acrylate compound and the primary or secondary amine in a solvent in which two components can be dissolved. This is a reaction in which an amino group in a primary or secondary amine is Michael-added to an ethylenically unsaturated double bond in a (meth) acrylate compound to introduce an amino group at the end of the molecule.

  Regarding the reaction temperature, 10 to 110 ° C is preferable and 20 to 80 ° C is more preferable because the reaction proceeds rapidly even at room temperature. When the reaction temperature is less than 10 ° C., the solubility of the (meth) acrylate compound as a raw material or the amino group-containing photocurable compound that is a reaction product is lowered and easily precipitated, the reaction rate is lowered, and the reaction time is prolonged. Time is likely to cause problems such as reduced productivity. On the other hand, when the reaction temperature exceeds 110 ° C., the reaction product is colored, which affects the color of the curable composition using the colored amino group-containing photocurable compound and the cured film. .

    The solvent used when the (meth) acrylate compound is reacted with the primary or secondary amine does not have reactivity with the raw material (meth) acrylate compound and primary or secondary amine. If it is a thing, it will not specifically limit. Examples of the solvent include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, xylene, butanol, isopropanol, propylene glycol monomethyl ether, dimethyl adipate, dimethyl succinate, and dimethyl glutarate. Of these, a plurality of types of solvents may be used in combination.

  The weight ratio of the conductive inorganic fine particles to silicon oxide in the curable composition for antistatic of the present invention is preferably 0.5 to 100 parts by weight of silicon oxide with respect to 100 parts by weight of the conductive inorganic fine particles. Furthermore, 1-50 weight part of silicon oxide is more preferable. If the weight ratio of silicon oxide is less than 0.5 parts by weight, the effect of reducing the refractive index and improving the conductivity of the cured film due to the mixed use of silicon oxide is small, and if it exceeds 100 parts by weight, the proportion of conductive inorganic fine particles decreases. As a result, the conductivity of the cured film may be significantly reduced.

  Further, the total content of the inorganic fine particles including the conductive inorganic fine particles and the silicon oxide in the antistatic curable composition is not particularly limited, but is preferably 1 to 80 parts by weight with respect to 100 parts by weight of the solid content. More preferably, it is 10 to 70 parts by weight. When the total content of the inorganic fine particles is less than 1 part by weight, the antistatic property derived from the conductive inorganic fine particles is drastically lowered. When the content exceeds 80 parts by weight, the film forming property is inferior due to the small amount of organic components. There is.

  Although it does not restrict | limit especially as a manufacturing method of the curable composition for antistatics of this invention, Several methods are mentioned. Specifically, the conductive inorganic fine particles, silicon oxide and amino group-containing photocurable compound are first mixed and dispersed in an organic solvent to obtain a stable conductive inorganic fine particle / silicon oxide dispersion, and then various other types. A method of manufacturing by adding and adjusting various additives, first mixing and dispersing conductive inorganic fine particles and amino group-containing photocurable compound in an organic solvent to obtain a stable conductive inorganic fine particle dispersion, while oxidizing A method in which silicon and an amino group-containing photocurable compound are mixed and dispersed in an organic solvent to obtain a stable silicon oxide dispersion, and then the above-mentioned two kinds of dispersions and other various additives are added and prepared. , A method of adding and adjusting the conductive inorganic fine particle dispersion, a commercially available silicon oxide dispersion and other various additives, and a conductive inorganic fine particle, silicon oxide, an amino group-containing photocurable compound, and an organic solvent And other A method of dispersing manufactured in a state in which everything is mixed in the pressurizing agents.

  The antistatic curable composition of the present invention can provide the desired effect even if it is prepared by simply mixing the conductive inorganic fine particle powder, the silicon oxide powder and the amino group-containing photocurable compound. However, it can be mixed mechanically with a kneader, roll, attritor, super mill, dry pulverizer, etc., or it can be suspended with a conductive inorganic fine particle powder and / or silicon oxide powder and an organic solvent. If a solution containing the compound is added and the reaction is carried out in an intimate mixed system such as depositing an amino group-containing photocurable compound on the surface of the conductive inorganic fine particles, a better result can be obtained.

  The silicon oxide dispersion of the present invention can be obtained by mixing and / or dispersing a silicon oxide powder and a commercially available dispersant or surfactant in an organic solvent and / or water by the above method. Examples of commercially available dispersants include, for example, Nippon Lubrizol: Solsparse 3000, Solspers 9000, Solspers 17000, Solspers 24000, Solspers 28000, Solspers 32000, Solspers 35100, Solspers 36000, Solspers 41000, EFKA Additives: EFKA4009, EFKA4046, EFKA 4047, EFKA 4080, EFKA 4010, EFKA 4015, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4330, EFKA 4300, EFKA 7462, Ajispur PB821, Ajispar PB8PA, 111 ORUV20, TEXAPHOUV21, TEXAPHORP61, manufactured by Big Chemie Japan: Disperbyk-101, Disperbyk-103, Disperbyk-106, Disperbyk-110, Disperbyk-111, Disperbyk-161, Disper63D-64-164, Disperbyk-164 , Disperbyk-167, Disperbyk-168, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-182 and the like. In particular, from the viewpoint of dispersibility in an organic solvent and compatibility with an amino group-containing photocurable compound, Disperbyk-110 and Disperbyk-111 are preferable.

  For the dispersion or dissolution of conductive inorganic fine particles and / or silicon oxide, amino group-containing photocurable compound or antistatic curable composition in a non-aqueous vehicle such as an organic solvent, and a mixture thereof, a paint conditioner (Manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homomixer, homogenizer (manufactured by M Technique) Dispersers such as “Cleamix”, wet jet mills (“Genus PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer), microbead mills (“Super Apeck Mill”, “Ultra Apeck Mill” manufactured by Kotobuki Industries) Can be used. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.

  The antistatic curable composition of the present invention contains at least conductive inorganic fine particles, silicon oxide and an amino group-containing photocurable compound, and other components impair the purpose and effect of the present invention. As long as there is no solvent, photopolymerization initiator, photocurable compound, polymerization inhibitor, photosensitizer, leveling agent, surfactant, antibacterial agent, antiblocking agent, plasticizer, ultraviolet absorber, infrared absorption You may add additives, such as an agent, antioxidant, a silane coupling agent, a conductive polymer, a conductive surfactant, an inorganic filler, a pigment, and dye.

  In the case of adding a solvent, the curing process may be performed after the solvent is volatilized. The solvent is not particularly limited, and various known organic solvents can be used. Examples of the organic solvent include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1- Butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl Seteto, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methyl pyrrolidone. These organic solvents may be used in combination of two or more.

  Among them, the hydroxyl group-containing solvent has good wettability with respect to conductive inorganic fine particles and / or silicon oxide having a highly hydrophilic particle surface property. This is preferable because it is very effective in improving the aging stability and also improves the leveling property of the coating process. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to 100% by weight. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol Examples thereof include monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, and propylene glycol monomethyl ether. In particular, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono n-butyl ether are preferable because of better dispersibility and dispersion stability.

  The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

  Specifically, as the monocarbonyl compound, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl -Enetanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4) , 7,10,13-pentaoxotridecyl) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-propenyloxy) Ethyl) metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3 4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

  Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one Polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla Mino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino -Propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

  Examples of aminocarbonyl compounds include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino) benzoate. 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis (4-diethylaminobenzal) cyclopenta Non etc. are mentioned. Examples of commercially available photopolymerization initiators include Irgacure 184, 651, 500, 907, 127, 369, 784, 2959 from Ciba Specialty Chemicals, Lucirin TPO from BASF, Esacure One from Nippon Sebel Hegner, and the like.

  The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular regarding the usage-amount of a photoinitiator, It is preferable to use within the range of 1-20 weight part with respect to 100 weight part of whole quantity of a photocurable compound.

  Moreover, a well-known organic amine etc. can be added as a sensitizer.

  Furthermore, in addition to the radical polymerization initiator, a cationic polymerization initiator may be used in combination.

  In addition to the amino group-containing photocurable compound, other binder resins and photocurable compounds may be added to the antistatic curable composition of the present invention.

  Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin. Etc. These resins may be used alone or in combination of two or more. The binder resin is preferably used within a range of 20 parts by weight or less based on the total amount of solids (components other than the solvent, hereinafter the same) of the curable composition (100 parts by weight).

  As a photocurable compound, for example, a compound having a polymerizable unsaturated double bond group such as a (meth) acrylic compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, and an ethynyl compound is used. Can do. These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group. The photocurable compound other than the amino group-containing photocurable compound is in the range of less than 50 parts by weight, particularly in the range of 5 to 40 parts by weight, based on the total amount of solid content of the curable composition (100 parts by weight). Is preferably used.

  Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, and a hydroxyl group (meta ) Acrylic compounds, nitrogen-containing (meth) acrylic compounds, and the like. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.

  Specific examples of monofunctional (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (medium) ) Acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkylene (meth) acrylate having 1 to 22 carbon atoms such as docosyl (meth) acrylate. For the purpose of adjusting the polarity, it is preferable to use an alkyl group-containing acrylate having a C 2-10 alkyl group, more preferably a C 2-8 alkyl group, or a corresponding methacrylate. For the purpose of adjusting the leveling property, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

  Moreover, as alkylene glycol type (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol mono ( It has a hydroxyl group at the terminal such as (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and polyoxy Monoacrylate having an alkylene chain or the corresponding monomethacrylate, methoxyethylene glycol (meth) acrylate, methoxydiethyle Glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meta ) Acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxy Tetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol ( ) Acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, etc., which has an alkoxy group at the terminal and has a polyoxyalkylene chain or a corresponding monomethacrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, Phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate Polyoxyalkylene-based acrylates having a phenoxy or aryloxy group at the terminal, such as phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene ethylene glycol (meth) acrylate, or corresponding methacrylates Can be mentioned.

  Furthermore, as the compound having a carboxyl group and a polymerizable unsaturated double bond, maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, β- (meth) acryloxyethyl phthalate Examples include monoesters, isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.

  Examples of hydroxyl group-containing (meth) acrylic compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. , 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- ( Monoalkylol (meth) acrylamide such as (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N- Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylaminide, N-ethoxymethyl-N-propoxy Methyl methacrylate N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide unsaturated compounds such as acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide and the like, and dimethylaminoethyl (meth) acrylate , Unsaturated compounds having a dialkylamino group such as diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, and halo such as Cl ⁻ , Br ⁻ and I ⁻ Examples include quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having a gen ion or QSO ₃ ⁻ (Q: an alkyl group having 1 to 12 carbon atoms).

  Furthermore, as other unsaturated compounds, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl ( Perfluoro having 1 to 20 carbon atoms such as (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Perfluoroalkyl (meth) acrylates having an alkyl group can be exemplified.

  In addition, perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkyl group-containing vinyl monomers such as alkylene, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Examples thereof include alkoxysilyl group-containing vinyl compounds such as silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof, and glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

  Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

  Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

  Examples of the vinyl compound include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like. It is done.

  Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like.

  These may be used alone or in combination of two or more.

  From the viewpoint of coating strength and scratch resistance, the photo-curable compound is a poly (meth) acrylate such as polyurethane poly (meth) acrylate or polyepoxy poly (meth) acrylate having at least three functional groups, Polyfunctional acrylates having three or more acryloyl groups can be preferably used.

  Polyepoxy poly (meth) acrylate is an epoxy resin whose ester group is esterified with (meth) acrylic acid and whose functional group is (meth) acryloyl group, and (meth) acrylic acid addition to bisphenol A type epoxy resin Products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  The polyurethane poly (meth) acrylate is obtained by reacting, for example, a diisocyanate and a (meth) acrylate having a hydroxyl group, or an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under an excess of isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

  Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

  Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and ditrimethylolpropane tetraacrylate. .

  Examples of (meth) acrylates having an isocyanate group include 2-methacryloyloxyethyl isocyanate and methacryloyl isocyanate.

Commercially available products of photocurable compounds include Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, Osaka, manufactured by Toa Gosei. Biscoat # 400 from Organic Chemicals, SR-295 from Kayaku Sartomer, DPHA from Daicel UCB, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602, NK Ester K-TM from Shin-Nakamura Chemical Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6, NK Oligo U-4HA, NK Oligo U-6 A, NK Oligo U-324A, BASF LamarerEA81, Sannopco Photomer 3016, Arakawa Chemical Beamset 371, Beamset 575, Beamset 577, Beamset 700, Beamset 710, Negami Industrial Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP-3, Art Resin H61, Nihon Gosei Purple light UV-7600B, purple light UV-7610B, purple light UV-7620EA, purple light UV-7630B, purple light UV-1400B, purple light UV-1700B, purple light UV-6300B, manufactured by Kyoeisha Chemical Co., Ltd. Triacrylate PE-4A, light acrylate DPE-6A, UA-306H, UA-306T, UA-306I, KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, manufactured by Nippon Kayaku Etc.

Next, the cured film and laminated body of the present invention will be described.
The cured film of the present invention is subjected to a curing treatment after coating the curable composition of the present invention on a substrate so that the film thickness is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm. Can be formed.

According to the present invention, a cured film having a surface resistance value of 1 × 10 ¹² Ω / □ or less and a refractive index of 1.5 to 1.8 can be obtained.

  At the time of formation, the cured film may be applied directly to the substrate, or one or more lower layers may exist between the cured film and the substrate.

  Examples of the substrate to which the cured film of the present invention is applied include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

  As a coating method, a known method can be used. For example, a method using a lot or a wire bar, or various coating methods such as microgravure, gravure, die, curtain, lip, slot or spin can be used. it can.

  Moreover, a hardening process can be performed by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, and visible light with a wavelength of 400-500 nm, using a well-known technique. For example, a high-pressure mercury lamp is used as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. An ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.

The active energy dose to be irradiated is preferably in the range of 5 to 2000 mJ / cm ² , and more preferably in the range of 50 to 1000 mJ / cm ² from the viewpoint of easy management in the process.

  In addition, these active energy ray irradiations can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The cured film of the present invention may be formed by applying a curable composition to a substrate and naturally or forcibly drying it, followed by curing treatment, or after coating and curing treatment. Alternatively, forced drying may be performed, but it is more preferable to perform the curing treatment after natural or forced drying.

  In particular, in the case of curing with an electron beam, it is more preferable to carry out the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the remaining organic solvent.

  Moreover, the timing of a hardening process may be simultaneous with coating, and may be after coating.

  Since the cured film of the present invention is excellent in hard coat properties, transparency, light resistance, high refractive index properties, and antistatic properties, it can be suitably used as an optical material. Therefore, the cured film of the curable composition of the present invention is a laminated body, a front panel of various display devices such as a cathode ray tube, a flat display panel (liquid crystal display, plasma display, electrochromic display, light emitting diode display, etc.) or an input thereof. It is also used as a device.

  In addition, it can be widely used for engineering lenses, eyeglass lenses, optical recording disks (compact disks, DVD disks, Blu-ray disks, etc.), light cases, and the like.

  In addition to the cured film and substrate of the present invention, the laminate of the present invention preferably contains one or more films having different refractive indexes, adhesive layers, information recording layers, and the like.

The film (a), the pressure-sensitive adhesive layer (a) or the information recording layer (a) having different refractive indexes may be laminated in a layer configuration / position such as the following (I) to (IX).
(I) Base material / (A) / Curing film (II) Base material / Curing film / (A)
(III) Base material / (A) / Curing film / (A)
(IV) (A) / Substrate / Curing film (V) (A) / Base material / (A) / Curing film (VI) (A) / Base material / Curing film / (A)
(VII) (A) / Base material / (A) / Curing film / (A)
(VIII) (A) / cured film / base material / cured film (IX) cured film / (a) / base material / cured film Other than the function of the cured product of the present invention, the film or information recording layer having a different refractive index The formation method is not particularly limited, and it is formed by a known method.

  For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. There are no limitations on the materials used, and one or more functions such as an information recording function, an antiglare function, a Newton ring prevention function, an adhesive function, a specific wavelength blocking function, an adhesion improvement function, and a color tone correction function can be provided as necessary. .

  The information recording layer is not particularly limited as long as it causes some chemical change by laser light or the like and records information by the change. For example, organic materials include polymethine dyes, Examples include phthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, and triphenylmethane-based metal complex compounds, and the above dyes can be used alone or in combination of two or more. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt, and semimetals can be used alone or in combination of two or more. . The information recording layer may be a laminated layer or the like, and the mode of photochemical change may be any of phase change, bubble, and drilling type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb, or Co, or may be a spiropyran or a fluorinated photochromic material.

  From the viewpoint of antireflection, the cured film having a high refractive index is also preferably used as a laminate provided with a coated film having a low refractive index on the surface layer to provide an antireflection function.

    Further, in a laminate in which reflection interference fringes are a problem, the blending amount of the metal oxide in the curable composition of the present invention is adjusted, and the difference in the refractive index between the cured film and the substrate or the cured film When there is a layer between the substrate and the substrate, the difference in refractive index between the cured film of the present invention and the lower layer in contact with the cured film is preferably within ± 0.02.

  Hereinafter, the present invention will be described in more detail based on production examples and examples. In Production Examples and Examples, parts and% represent parts by weight and% by weight, respectively.

(Production Example 1)
1.16 parts of dibutylamine (ethylenic) in a solution obtained by dissolving 20 parts of an acrylate compound having a pencil hardness of 3H after photocuring (“UN-3320HS” manufactured by Negami Kogyo Co., Ltd.) in 31.74 parts of methyl isobutyl ketone. The number of moles of unsaturated double bonds / number of moles of amine compound = 100/15) was added, and the mixture was stirred at 40 ° C. for 5 hours, then cooled to room temperature, and methyl isobutyl ketone of the amino group-containing photocurable compound (1) A solution (solid content 40%) was obtained.

(Production Example 2)
In a solution prepared by dissolving 20 parts of an acrylate compound having a pencil hardness of 3H after photocuring (“UN-3320HS” manufactured by Negami Kogyo Co., Ltd.) in 30.36 parts of methyl isobutyl ketone, 0.24 part of 1-aminohexane (Number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/10) was added and stirred at 40 ° C. for 5 hours, then cooled to room temperature, and the amino group-containing photocurable compound (2) A methyl isobutyl ketone solution (solid content 40%) was obtained.

(Production Example 3)
A photo-cured pencil hardness of 3H acrylate compound (“UA-306T” manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts was dissolved in methyl isobutyl ketone 35.19 parts in 1,3-diaminopropane 3.46. Parts (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/30), stirred at 40 ° C. for 5 hours, cooled to room temperature, and amino group-containing photocurable compound (3) Of methyl isobutyl ketone was obtained (solid content 40%).

(Production Example 4)
Piperidine 3.59 parts (ethylenically unsaturated) in a solution in which 20 parts of an acrylate compound having a pencil hardness of 2H after photocuring (“Beamset 700” manufactured by Arakawa Chemical Industries, Ltd.) was dissolved in 34.04 parts of cyclohexanone. The number of moles of double bond / number of moles of amine compound = 100/20) was added and stirred at 40 ° C. for 5 hours, then cooled to room temperature, and a cyclohexanone solution of amino group-containing photocurable compound (4) (solid content) 40%).

(Production Example 5)
0.16 parts of dibutylamine (ethylenically unsaturated) was dissolved in 30.24 parts of cyclohexanone in 20 parts of an acrylate compound having a pencil hardness of 2H after photocuring (“UN-9000H” manufactured by Negami Kogyo Co., Ltd.). The number of moles of double bond / number of moles of amine compound = 100/5) was added, and the mixture was stirred at 40 ° C. for 5 hours, then cooled to room temperature, and a cyclohexanone solution of amino group-containing photocurable compound (5) (solid content) 40%).

(Production Example 6)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Osaka Organic Chemistry) Industrial Co., Ltd. product: biscoat # 300) 250.0 parts, hydroquinone 0.16 parts, cyclohexanone 141.2 parts were charged, and the temperature was raised to 85 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (Dow Chemical Japan) is added. 77.3 parts and cyclohexanone 33.9 parts were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and multifunctional (meta ) A cyclohexanone solution of the acrylate compound (a) was obtained. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight (MN) 870, and a weight average molecular weight (MW) 2,830.
A solution obtained by diluting 28.6 parts of cyclohexanone solution (solid content 70%) containing the above polyfunctional (meth) acrylate compound (a) having a pencil hardness of 3H after photocuring with 23.07 parts of cyclohexanone (solid content 40%) ) Is added 1.1 parts of dibutylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, and then cooled to room temperature. A cyclohexanone solution (solid content 40%) of the containing photocurable compound (6) was obtained.

(Production Example 7)
A solution obtained by diluting 28.6 parts of cyclohexanone solution (solid content 70%) containing the above polyfunctional (meth) acrylate compound (a) having a pencil hardness of 3H after photocuring with 22.4 parts of methyl isobutyl ketone (solid content) 40%), 0.65 part of N-methylhexylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/10) was added, and the mixture was stirred at 40 ° C. for 5 hours, and then to room temperature. It cooled and the methyl isobutyl ketone solution (solid content 40%) of the amino-group containing photocurable compound (7) was obtained.

(Production Example 8)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 100.0 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid BT-100), pentaerythritol tri Acrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD PET-30), 463.2 parts, 0.28 part of hydroquinone, and 563.2 parts of cyclohexanone were charged and heated to 85 ° C. Next, 2.82 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (Dow Chemical Japan). 143.4 parts and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and multifunctional (meth). A cyclohexanone solution of the acrylate compound (b) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) 920, and a weight average molecular weight (MW) 2,200.
A solution obtained by diluting 30.0 parts of a cyclohexanone solution (solid content 50%) containing the polyfunctional (meth) acrylate compound (b) having a pencil hardness of 3H after photocuring with 9.1 parts of cyclohexanone (solid content 40%) ) Is added 1.05 parts of dibutylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, cooled to room temperature, A cyclohexanone solution (solid content: 40%) of the photocurable compound (8) was obtained.

(Production Example 9)
To a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (trade name, manufactured by JFE Chemical Co., Ltd.) BPAF) 100.0 parts, pentaerythritol triacrylate (Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat # 300) 200.2 parts, hydroquinone 0.15 parts (manufactured by Wako Pure Chemical Industries, Ltd.), cyclohexanone 200.1 The portion was charged and heated to 85 ° C. Next, 1.50 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.) 62.0 parts by company) and 42.4 parts by cyclohexanone, and then 2.41 parts by weight of dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) is added as a catalyst. The mixture is stirred at 85 ° C. for 6 hours and cooled to room temperature. Thus, a cyclohexanone solution of the polyfunctional (meth) acrylate compound (c) was obtained. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight (MN) 830, and a weight average molecular weight (MW) 2,310.
A solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 60%) containing the above polyfunctional (meth) acrylate compound (c) having a pencil hardness of 3H after photocuring with 10.4 parts of cyclohexanone (solid content 40%) ), 0.3 parts of diethylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/10), stirred at 40 ° C. for 5 hours, cooled to room temperature, amino group-containing A cyclohexanone solution (solid content 40%) of the photocurable compound (9) was obtained.

(Production Example 10)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Nippon Kayaku) Co., Ltd .: KAYARAD PET-30) 124.8 parts, dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 222.8 parts, hydroquinone 0.21 part, cyclohexanone 430.0 parts are charged at 85 ° C. The temperature was raised to. Next, 2.14 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours to give glycidyl methacrylate (Dow Chemical Japan). 77.3 parts and 80.7 parts of cyclohexanone were added, followed by 3.42 parts of dimethylbenzylamine as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and multifunctional (meta ) A cyclohexanone solution of the acrylate compound (d) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,050, and a weight average molecular weight (MW) of 3,830.
A solution obtained by diluting 30.0 parts of cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (d) having a pencil hardness of 3H after photocuring with 9.1 parts of cyclohexanone (solid content 40%) ) 1.05 parts 2-piperidineethanol (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, cooled to room temperature, A cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (10) was obtained.

(Production Example 11)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 100.0 g of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical), dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd.): KAYARAD DPHA) 556.8, hydroquinone 0.33 g, and cyclohexanone 437.8 g were charged and heated to 85 ° C. Next, 3.28 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (manufactured by Dow Chemical Japan) 96. 6 g and 66.8 g of cyclohexanone were added, and then 5.28 g of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to obtain a cyclohexanone solution of polyfunctional (meth) acrylate compound (e). It was. This reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight MN820, and a weight average molecular weight MW2,660.
A solution obtained by diluting 30.0 parts of a cyclohexanone solution (solid content 50%) containing the polyfunctional (meth) acrylate compound (e) having a pencil hardness of 3H after photocuring with 9.1 parts of cyclohexanone (solid content 40%) ) Is added 1.1 parts of dibutylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, and then cooled to room temperature. A cyclohexanone solution (solid content 40%) of the containing photocurable compound (11) was obtained.

(Production Example 12)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 50.0 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), dipentaerythritol penta Acrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 413.4 parts, 0.23 part of hydroquinone, and 463.4 parts of cyclohexanone were charged and heated to 85 ° C. Next, 2.32 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (manufactured by Dow Chemical Japan) 71 7 parts and 74.3 parts of cyclohexanone were added, and then 3.73 g of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and cyclohexanone of polyfunctional (meth) acrylate compound (f) A solution was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight MN900, and a weight average molecular weight MW2,070.
A solution obtained by diluting 30.0 parts of cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (f) having a pencil hardness of 3H after photocuring with 9.1 parts of cyclohexanone (solid content 40%) ) Is added 1.1 parts of dibutylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, and then cooled to room temperature. A cyclohexanone solution (solid content 40%) of the photocurable compound (12) was obtained.

(Production Example 13)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, and 100.0 g of naphthalene dianhydride (trade name NTCDA, manufactured by JFE Chemical Co., Ltd.), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) Product: 342.2 g of KAYARAD PET-30), 0.22 g of hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) and 442.2 g of cyclohexanone were charged and heated to 85 ° C. Next, 2.21 g of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred for 8 hours at 85 ° C., and glycidyl methacrylate (Dow Chemical Japan Co., Ltd.). 105.9 g) and cyclohexanone 108.4 g were added, and then 3.56 g of dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and multifunctional ( A cyclohexanone solution of the (meth) acrylate compound (g) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight MN820, and a weight average molecular weight MW2,440.
A solution obtained by diluting 30.0 parts of cyclohexanone solution (solid content 50%) containing the above polyfunctional (meth) acrylate compound (g) having a pencil hardness of 3H after photocuring with 9.1 parts of cyclohexanone (solid content 40%) ) Is added 1.1 parts of dibutylamine (number of moles of ethylenically unsaturated double bond / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, and then cooled to room temperature. A cyclohexanone solution (solid content 40%) of the containing photocurable compound (13) was obtained.

(Production Example 14)
In a solution obtained by dissolving 20 parts of an acrylate compound having a pencil hardness after photocuring of HB (“Beam Set 750” manufactured by Arakawa Chemical Industries, Ltd.) in 32.27 parts of methyl isobutyl ketone, 1.51 parts of dibutylamine (ethylene Of unsaturated double bonds / number of moles of amine compound = 100/15), stirred at 40 ° C. for 5 hours, cooled to room temperature, methyl isobutyl of amino group-containing photocurable compound (14) A ketone solution (solid content 40%) was obtained.

[Preparation of Conductive Inorganic Fine Particles and Silicon Oxide Dispersed Paste: Production Examples 15 to 33]
Using the amino group-containing photocurable compound prepared in the above production example, conductive inorganic fine particles and / or silicon oxide were dispersed according to the formulation shown in Table 1 to prepare conductive inorganic fine particles and silicon oxide dispersed paste. Dispersion methods are temporary dispersion (dispersion for 1 hour with a paint shaker using zirconia beads (1.25 mm) as a medium) and main dispersion (dispersing machine UAM-015 made using zirconia beads (0.1 mm) as a medium). (Dispersion).

(Combination)

In Table 1,
Sb2O5: “San-Epoch EFR-6N” manufactured by Nissan Chemical Industries (average primary particle size: 20 nm)
ATO: “SN-100P” manufactured by Ishihara Sangyo (average primary particle size: 20 nm)
ITO: “Nanotech ITO” manufactured by CI Kasei (average primary particle size: 30 nm)
PTO: “TL-30S” manufactured by Catalytic Chemical Industry (average primary particle size: 30 nm)
Aluminum-doped zinc oxide: “Pazette CK” (average primary particle size: 30 nm) manufactured by Hakusui Tech Co., Ltd.
SiO2: “AEROSIL 50” manufactured by Nippon Aerosil (average primary particle size: 10 nm)
Commercially available multifunctional monomer: “Beamset 750” manufactured by Arakawa Chemical Industries (bisphenol A ethylene oxide modified acrylate, molecular weight (Mw) 512, pencil hardness HB after photocuring)
MIBK: Methyl isobutyl ketone Metobuta: 3-methoxy-1-butanol

(Production Example 34)
100 parts of commercially available silicon oxide sol (“MEK-ST” manufactured by Nissan Chemical Industries, 30% solids), 1 part of acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.5 parts of water The mixture was heated and stirred at 75 ° C. for 7 hours to obtain an acrylate-based silane coupling agent-treated silicon oxide sol.

(Production Example 35)
Commercially available silicon oxide sol (Nissan Chemical "MIBK-ST", solid content 30%) 100 parts, methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical "KBM-503") 1 part and water 0.5 parts The mixture was heated and stirred at 100 ° C. for 7 hours to obtain a silicon oxide sol treated with a methacrylate silane coupling agent.

(Production Example 36)
Commercially available silicon oxide sol (Nissan Chemical "PMA-ST", solid content 30%) 100 parts, γ-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical "LS5580") 1 part and water 0.5 part Were mixed and heated and stirred at 110 ° C. for 7 hours to obtain a silicon oxide sol treated with an octyl silane coupling agent.

(Production Example 37)
100 parts of commercially available silicon oxide sol (“MEK-ST” manufactured by Nissan Chemical Industries, solid content 30%), 1 part of γ-mercaptopropyltrimethoxysilane (“KBM-1403” manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.5 parts of water Were mixed and heated and stirred at 100 ° C. for 7 hours to obtain a styryl-based silane coupling agent-treated silicon oxide sol.

(Production Example 38)
100 parts of a commercially available silicon oxide sol (“MEK-ST” manufactured by Nissan Chemical Industries, 30% solids), 3 parts of acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 parts of water The mixture was heated and stirred at 75 ° C. for 7 hours to obtain a silicon oxide sol treated with a methacrylate-based silane coupling agent.

[Coating and cured film evaluation: Reference Examples 1, 2, 4, 6, 7, 15, Examples 3, 5, 8-14, 16-19, Comparative Examples 1-4]
Using the conductive inorganic fine particles and / or silicon oxide dispersion paste prepared as described above, a curable composition having the composition shown in Table 2 was prepared, and an easy-adhesion-treated PET film having a thickness of 100 μm (“Cosmo Shine A-4100 manufactured by Toyobo Co., Ltd.) was prepared. After coating with a bar coater so that the film thickness was 5 μm, 400 mJ / cm ² of ultraviolet light was irradiated with a metal halide lamp to form an antistatic hard coat layer (cured film). The resulting antistatic hard coat layer was evaluated for surface resistance, refractive index, scratch resistance, pencil hardness, transparency (haze), and light resistance by the following methods. The results are shown in Table 2.

In Table 2,
Photo-curing compound (1): “Nippon Gosei UV-1700B”
Photo-curable compound (2): “UA-306T” manufactured by Kyoeisha Chemical
Photo-curing compound (3): “KAYARAD DPHA” manufactured by Nippon Kayaku
Commercially available SiO2 dispersion: “MEK-ST” manufactured by Nissan Chemical Industries
Commercially available Sb2O5 dispersion: “ELCOM P-45” (catalyst chemical industry) (silicon oxide treatment on particle surface)
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Solvent: PGME (propylene glycol monomethyl ether)
* 1: Not measured because conductive inorganic fine particle paste was poorly dispersed

[Production and Evaluation of Laminate: Examples 20 to 25]
(Preparation of low refractive index coating liquid)
1,2,9,10-Tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane 50 parts by weight, silica sol 30% dispersion (MEK-ST, Nissan Chemical Industries, Ltd.) 120 parts by weight 2 ′, 2′-bis ((meth) acryloyloxymethyl) propionic acid (2-hydroxy) -4,4,5,5,6,6,7,7,8,8,9,9, 10,10,11,11,11-Nonadecafluoroundecyl 10 parts by weight, butyl alcohol 900 parts by weight Photoinitiator (Nippon Kayaku Co., Ltd. KAYACURE BMS) 5 parts by weight are mixed to prepare a low refractive index coating solution. did.

Using the conductive inorganic fine particles of Production Example 17 and the silicon oxide dispersion of Production Example 34, a curable composition having the composition shown in Table 3 was prepared, and an easy adhesion treatment of 100 micron PET (the refractive index of the easy adhesion layer). = 1.60) Using a bar coater, the coating was applied to a dry film thickness of 6 μm, dried at 100 ° C. for 1 minute, and irradiated with 400 mJ / cm ² of ultraviolet rays with a metal halide lamp. The test specimen obtained here was further coated with a low refractive coating liquid using a spin coater, and the layer thickness was adjusted so that the wavelength of light having a dry film thickness of λ / 4 was about 550 nm. And dried with a metal halide lamp and irradiated with 400 mJ / cm ² of ultraviolet rays to obtain a laminate.

  About the obtained laminated body, surface resistance, scratch resistance, pencil hardness, transparency (haze), light resistance, refractive index, and interference fringes were evaluated by the following methods. The results are shown in Table 3.

In Table 3, photo-curable compound (1): “Nippon Gosei UV-1700B” manufactured by Nippon Synthetic Chemical
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Base material: 100 micron PET (Coating on Toyobo Cosmo Shine A-4100 easy adhesion treated surface (refractive index 1.60))
Solvent: PGME (propylene glycol monomethyl ether)

[Evaluation method]
(1) Surface resistance The surface resistance (Ω / □) of the cured film is
When the surface resistance is 1 × 10 ¹² or less:
When the surface resistance is higher than 1 × 10 ¹² and 1 × 10 ¹⁴ or less: ○
When the surface resistance exceeds 1 × 10 ¹⁴ : ×
(2) Scratch resistance The coated material was set on a Gakushin tester, and was shaken 10 times with a load of 250 g using steel wool No. 0000. About the taken-out coating material, the degree of damage | wound was judged visually by the following five steps. The larger the value, the better the scratch resistance.

5: No scratches 4: Slight scratches 3: Scratches are observed, but the substrate is not visible 2: Scratches are present, and some coated materials are peeled off 1: Coating (3) Pencil hardness In accordance with JISK5600, using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON), variously changing the hardness of the pencil lead, the load The test was conducted 5 times at 500 g. The hardness of the core when the flaw was not scratched once or was flawed only once was defined as the pencil hardness of the coated product. In consideration of practical required physical properties, a pencil with a hardness of 2H or more ○
X lower than 2H
It was determined.
(4) Transparency (Haze value)
Turbidity (Haze value) in the obtained coated product was measured using a Haze meter.

-Light resistance Yellowing over time during continuous light irradiation is very undesirable for application development. Therefore, yellowing during continuous light irradiation was confirmed.
First, the coated material was exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 W / cm ² , black panel temperature: 60 ° C., 60% RH). Thereafter, the coated material was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as L ^* a ^* b ^* , and the standard for yellowing was judged from the b ^* value. The smaller the value of b ^* value, the smaller the degree of yellowing and the better the light resistance. In consideration of practical required physical properties, those with b ^* values of less than 3.5
X 3.5 or more
It was determined.

-Refractive index: The refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd.
-Reflection interference fringes: The reflection interference fringes of the obtained coating were visually evaluated.
Grade: ○: Reflected interference fringes cannot be observed
×: Reflective interference fringes can be observed

Claims (19)

Conductive inorganic fine particles having an average primary particle diameter of 5 to 100 nm;
Silicon oxide having an average primary particle size of 5 to 100 nm;
An amino group-containing photocurable compound;
A antistatic curable composition containing,
The amino group-containing photocurable compound is
An antistatic curable composition, which is obtained by reacting a compound represented by the following general formula (1) with a primary amine or a secondary amine.
General formula (1)


(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group, R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group, and R ⁹ represents a tetravalent aliphatic group or an aromatic group.
  2. The antistatic curable composition according to claim 1, wherein the conductive inorganic fine particles contain at least one element selected from the group consisting of antimony, indium, tin and zinc.   3. The curable composition for antistatic according to claim 1 or 2, wherein the conductive inorganic fine particles are not surface-treated with an insulating metal oxide and / or a hydrolyzable organometallic compound. . The conductive inorganic fine particles are antimony pentoxide, and the relative ratio (D2 / D1) between the average primary particle diameter (D1) of antimony pentoxide and the average primary particle diameter (D2) of silicon oxide is 0.1 to 1.2.
The curable composition for antistatic according to any one of claims 1 to 3, wherein the curable composition is for antistatic.   The antistatic curable composition according to any one of claims 1 to 4, wherein the silicon oxide is treated with a hydrolyzable organometallic compound. Primary amines or secondary amines, claims 1 to 5 or antistatic curable composition according to item 1, wherein the aliphatic monoamine. The curable composition for antistatics according to any one of claims 1 to 6 , further comprising a solvent, and the solvent contains 10 to 100% by weight of a hydroxyl group-containing solvent with respect to the total solvent. Cured film, which is formed by curing the antistatic curable composition according to any one of claims 1 to 7. The cured film according to claim 8 , wherein the surface resistance value is 1 × 10 ¹² Ω / □ or less. The cured film according to claim 8 or 9 , wherein the thickness of the cured film is 0.1 to 30 µm. The cured film according to any one of claims 8 to 10 , wherein the refractive index of the cured film is in a range of 1.5 to 1.8. The laminated body formed by forming the cured film of any one of Claims 8 thru | or 11 on a base material. The laminate according to claim 12 , wherein the substrate is a plastic substrate. The laminate according to claim 12 or 13 , wherein the substrate has a lens shape. The laminate according to any one of claims 12 to 14, wherein a difference in refractive index between the cured film and the substrate is within ± 0.02. 13. The method according to claim 12 , further comprising one or more lower layers between the cured film and the substrate, wherein a difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02. The laminate according to any one of 15 . The laminate according to any one of claims 12 to 16 , comprising an information recording layer. The laminate according to any one of claims 12 to 16, which is an antireflection film. The manufacturing method of the cured film formed by apply | coating the curable composition for antistatic of any one of Claim 1 thru | or 7 to a base material, and irradiating with an active energy ray and hardening.