JP6303919B2 - Lens forming ink composition - Google Patents

Description

  The present invention relates to a lens forming ink composition that is suitably used for manufacturing a light guide plate that is a member of a backlight unit incorporated in an optical apparatus such as an image display device. More specifically, the present invention relates to a microlens used for manufacturing a light guide plate and a lens-forming ink composition used for a liquid-repellent cured film used for controlling the shape of the microlens.

  For some time, microlenses formed on light guide plates for video display devices have been formed by injection molding using a mold. However, when manufacturing a small amount of various types of microlenses by using this method, it is necessary to remake a mold according to the product design, which increases the number of manufacturing steps.

  In recent years, as a manufacturing method with a high degree of design freedom, a method of directly forming a microlens on a substrate surface using an inkjet method has been proposed. In such a microlens manufacturing method using the ink jet method, patterning can be easily controlled by a personal computer or the like, so that the number of manufacturing steps is not changed even when a small amount of various products are produced, and the manufacturing cost can be suppressed. Is expected from the point of.

  In order to extract light well in the light guide plate, control of the shape of the microlens is important. Because, if the shape of the microlens is not formed with a smooth curved surface, or if the diameter and height of the microlens on the substrate is not as designed, uneven brightness occurs in the surface of the light guide plate, This is because problems such as low light extraction efficiency occur. Therefore, in order to solve these problems, it is necessary to form microlenses as designed without in-plane unevenness.

  For example, a photocurable composition is suitably used as an ink composition for forming a microlens by a printing method such as an inkjet method. In that case, the smaller the cure shrinkage, the easier it is to form a microlens as designed. Therefore, it is conceivable to use a polyfunctional monomer having a small cure shrinkage as a composition raw material.

  However, in order to prepare a photocurable composition so as to be compatible with a printing method such as an ink jet method, it is necessary to adjust the viscosity to be suitable for the printing method. Therefore, a technique for adjusting the viscosity by using a low-viscosity monofunctional monomer or solvent as the composition raw material is taken.

  For example, Patent Document 1 describes a solvent-containing photocurable composition that can be used as a base film for forming a microlens. Patent Document 2 describes a lens-forming ink composition for forming a microlens containing a monofunctional (meth) acrylate.

  However, if a photocurable composition containing a solvent is used as a base film for forming a microlens, the solvent may remain in the film, and the shape of the formed microlens may become distorted and degassing may occur. When used in an image display device, the reliability may decrease.

  Patent Document 3 describes an inkjet curable composition excellent in heat resistance and plating resistance, which contains a radical polymerizable compound having a specific structure. Patent Document 4 describes that a radically polymerizable compound having this specific structure is rapidly cured and excellent in surface curability and thin film curability.

  Furthermore, as described in Patent Document 5, the radical polymerizable compound having the specific structure is used in an optical curable composition.

JP 2012-102314 A JP2013-014740A JP 2013-091788 A JP 2011-137123 A JP 2013-014718 A

  Under such circumstances, there is a need for a photocurable ink composition for forming a microlens that is formed with a smooth curved surface and can be formed as designed with the diameter and height of the microlens on the substrate. It has been.

  As a result of intensive studies, the present inventors have formed a curved surface with a smooth shape by using a radical polymerizable compound having a specific structure, and the diameter and height of the microlens on the substrate are formed as designed. The present inventors have succeeded in developing a microlens-forming ink composition that does not contain a substantial solvent.

  The present invention includes the following items.

（式（１）中、Ｒ^１は水素もしくはアルキルである。） [1] An ink composition for forming a microlens comprising a compound (A) represented by the following formula (1), another radical polymerizable compound (B), and a photopolymerization initiator (C).

(In formula (1), R ¹ is hydrogen or alkyl.)

[2] The microlens-forming ink composition according to [1], further comprising a surfactant (D).

[3] A liquid repellent cured film obtained by applying the microlens-forming ink composition according to [1] or [2] and then curing it.

[4] A microlens obtained by applying the microlens-forming ink composition described in [1] or [2] on a liquid-repellent cured film in a lens shape and then curing it.

[5] A microlens according to [1] or [2] on a liquid-repellent cured film obtained by curing after applying the ink composition for forming a microlens according to [1] or [2]. The microlens according to [4], which is obtained by applying a forming ink composition into a lens shape and then curing the composition.

[6] An optical component having a microlens formed on the liquid repellent cured film according to [3].

[7] An optical component having the microlens according to [4] or [5].

[8] An image display device including the optical component according to [6] or [7].

  The ink composition for forming a microlens of the present invention is excellent in photocurability, and the cured product can be used as a microlens formed with a curved surface having a smooth shape. Moreover, these photocured materials are suitably used as a microlens and a liquid repellent cured film capable of controlling the shape of the microlens.

  In this specification, “(meth) acrylate” is used to indicate both or one of acrylate and methacrylate. The ink composition forming the microlens is called “lens ink”, and the ink composition forming the liquid repellent cured film capable of controlling the shape of the microlens is called “surface treatment agent”. is there.

（式（１）中、Ｒ^１は水素もしくはアルキルである。）
レンズ形状を滑らかにするためや、硬化膜に撥液性をもたせるために界面活性剤（Ｄ）を含ませてもよい。 1. Lens-Forming Ink Composition The lens-forming ink composition of the present invention (hereinafter also referred to as “the ink composition of the present invention” or “the composition of the present invention”) is a radical polymerization represented by the following formula (1). Containing a functional compound (A), other radical polymerizable compound (B), and a photopolymerization initiator (C).

(In formula (1), R ¹ is hydrogen or alkyl.)
A surfactant (D) may be included in order to make the lens shape smooth or to give the cured film liquid repellency.

  The ink composition of the present invention may further contain an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a heat-reactive compound, and the like as necessary.

  The ink composition of the present invention is preferably colorless from the viewpoint of light transmittance, but may contain a colored compound as long as the effects of the invention are not hindered. In this case, since the color of the obtained cured film or the like is not preferred to be yellowish, for example, a blue compound can be used. Further, when inspecting the state of the cured film or the like, a colorant may be included in order to facilitate identification from the substrate.

（式（１）中、Ｒ^１は水素もしくはアルキルである。）
ここで、式（１）におけるアルキルは、炭素数１〜２０の直鎖、炭素数３〜２０の分岐または炭素数５〜２０の環状のアルキルである。好ましくは、炭素数１〜１０の直鎖、炭素数３〜１０の分岐または炭素数３〜１０の環状のアルキルであり、より好ましくは、炭素数１〜５の直鎖または炭素数３〜５の分岐のアルキルであり、さらに好ましくは、炭素数１〜３の直鎖のアルキルである。
好ましいアルキルの具体例は、メチル、エチルが挙げられる。 1-1. Radical polymerizable compound represented by formula (1) (A)
The ink composition of the present invention contains a radical polymerizable compound (A) represented by the following formula (1) (hereinafter also referred to as “compound (A)”).

(In formula (1), R ¹ is hydrogen or alkyl.)
Here, the alkyl in Formula (1) is a C1-C20 linear, C3-C20 branched, or C5-C20 cyclic alkyl. Preferably, it is a C1-C10 straight chain, a C3-C10 branched, or a C3-C10 cyclic alkyl, More preferably, a C1-C5 linear or C3-C5 And more preferably a linear alkyl having 1 to 3 carbon atoms.
Specific examples of preferable alkyl include methyl and ethyl.

  Since such a compound (A) has a low viscosity, it can be suitably used as a dilution monomer in order to adjust the ink composition to a viscosity suitable for coating. In addition, the ink composition containing the compound (A) is very suitable for forming a microlens having a size as designed because the volume shrinkage during curing is small.

  As a production method of such a compound, for example, production method A) production method via 2-halomethylacrylic acid alkyl ester, production method B) 2,2 ′-[oxybis (methylene)] bisacrylic acid alkyl ester Production method, production method C) A method of producing from a lower ester of 2-allyloxymethylacrylic acid such as methyl 2-allyloxymethylacrylate or ethyl 2-allyloxymethylacrylate using an ester exchange reaction, etc. No. 2011-137123 (Patent Document 4).

  When the compound (A) of the present invention is exemplified by compound names, 2-allyloxymethyl acrylic acid, 2-allyloxymethyl acrylate methyl, 2-allyloxymethyl acrylate ethyl, 2-allyloxymethyl acrylate n-butyl , 2-allyloxymethyl acrylate n-pentyl, 2-allyloxymethyl acrylate t-pentyl, 2-allyloxymethyl acrylate neopentyl, 2-allyloxymethyl acrylate n-hexyl, 2-allyloxymethyl acrylate n-heptyl, 2-allyloxymethyl acrylate n-octyl, 2-allyloxymethyl acrylate t-octyl, 2-allyloxymethyl acrylate 2-ethylhexyl, 2-allyloxymethyl acrylate capryl, 2-allyloxy Nonyl methyl acrylate, 2-ant Decyl oxymethyl acrylate, undecyl 2-allyloxymethyl acrylate, lauryl 2-allyloxymethyl acrylate, tridecyl 2-allyloxymethyl acrylate, myristyl 2-allyloxymethyl acrylate, pentadecyl 2-allyloxymethyl acrylate Cetyl 2-allyloxymethyl acrylate, heptadecyl 2-allyloxymethyl acrylate, stearyl 2-allyloxymethyl acrylate, nonadecyl 2-allyloxymethyl acrylate, eicosyl 2-allyloxymethyl acrylate, etc. As mentioned.

  Compound (A) may be a single compound or a mixture of two or more compounds. The compound (A) is 5 to 95% by weight of the total amount of the ink composition, and particularly preferably 5 to 85% by weight of the total amount of the ink composition, since the curability of the ink composition is good.

1.2. Other radical polymerizable compounds (B)
The ink composition of the present invention contains a compound other than the compound (A) as the other radical polymerizable compound (B).

  The compound (B) is not particularly limited as long as it is a radically polymerizable compound other than the compound (A), but is preferably a (meth) acrylate compound because the curability of the ink composition is good.

  The compound (B) is composed of a hydroxyl group, an ester group, an ether group, a carbonyl group, a carboxyl group, and a urethane group in addition to the acryloyl group in terms of adhesion between the cured film and the substrate and adhesion between the cured film and the microlens. It is preferable to have at least one selected group because adhesion is good.

  The (meth) acrylate compound includes a monofunctional (meth) acrylate compound having one (meth) acryloyl group in the molecule and a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule. However, a polyfunctional (meth) acrylate compound is more preferable in terms of high curability of the ink composition, high hardness of the cured film, and high heat resistance.

  Specific examples of the polyfunctional (meth) acrylate compound include the following.

  Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Di (meth) acrylate, bisphenol A alkylene oxide modified di (meth) acrylate, bisphenol F alkylene oxide modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipe Taerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide Addition dipentaerythritol hexa (meth) acrylate, propylene oxide addition trimethylolpropane tri (meth) acrylate, propylene oxide addition ditrimethylolpropane tetra (meth) acrylate, propylene oxide addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipenta Erythritol hexa (meth) acrylate, ε-cap Lolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) acrylate, tri (Acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate, ε-caprolactone-added tri (acryloyloxyethyl) ) Isocyanurate, tolylene diisocyanate, isophorone diisocyanate, xylylene diiso Polyfunctional urethane (meth) acrylate obtained by reaction of polyfunctional isocyanates such as anate with hydroxyl-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate However, the compound (B) of the present invention is not limited thereto.

  Compound (B) may be a single compound or a mixture of two or more compounds. The compound (B) is 5 to 80% by weight of the total amount of the ink composition, and particularly 10 to 70% by weight of the total amount of the ink composition, the film thickness of the cured film applied on the substrate of the ink composition. It is preferable because the uniformity is good and the lens shape when applied to the lens shape is good.

1.3. Photopolymerization initiator (C)
The ink of the present invention contains a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited as long as it is a compound that generates radicals or acids upon irradiation with ultraviolet rays or visible rays, but is not limited to acylphosphine oxide-based initiators, oxyphenylacetate-based initiators, and benzoylformic acid-based initiators. Initiators, oxime ester-based initiators and hydroxyphenyl ketone-based initiators are preferred, and among these, hydroxyphenyl ketone-based initiators are particularly preferred from the viewpoint of photocurability of the ink and light transmittance of the resulting cured film, etc. preferable.

Specific examples of the photopolymerization initiator (C) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2 -Hydroxy-2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 4- Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) ) Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di ( Methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxycarbonyl) benzophenone, 4,4′- Di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′ , 4′-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6- Su (trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl)- 5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2 -(P-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- ( o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tri Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2) -Morpholinopropionyl) -9-n-dodecylcarbazole, bi (Η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propanone, 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- (dimethylamino) -2-[(4-methylphenol L) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl- Acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4 , 6-Trimethylbenzoyldiphenylphosphinate, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxy) ), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 (-2-methylbenzoyl) -9H-carbazole -3-yl]-, 1 (-O-acetyloxime).

  Among these, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- 1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-1-propanone, 2,2-dimethoxy-2-phenyl Acetophenone, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoylformate, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethyl Diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine acid esters are preferred.

  Commercially available products of the photopolymerization initiator (C) include Irgacure 184, Irgacure 651, Irgacure 127, Irgacure 1173, Irgacure 500, Irgacure 2959, Irgacure 754, Irgacure MBF, Irgacure TPO (trade name, BA, etc., manufactured by BA, SPT.

  Among these, Irgacure 1173 and Irgacure 184 are more preferable because of high reactivity and high curability of the (meth) acrylate monomer.

  The photopolymerization initiator (C) used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds. The content of the photopolymerization initiator (C) is preferably 1 to 15% by weight of the total amount of the ink composition, and particularly preferably 5 to 10% by weight of the total amount of the ink composition in consideration of balance with other materials. When it exists, the cured film which is excellent in the photocurability with respect to an ultraviolet-ray, and has high light transmittance is obtained.

1.4. Surfactant (D)
The ink composition of the present invention may further contain a surfactant (D) as necessary for the purpose of controlling the shape of the microlens. When the surfactant (D) is contained, the surface of the resulting cured film has high liquid repellency, and a microlens with a finer pattern size can be formed on the cured film.

  Specific examples of the surfactant (D) include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK344, BYK346 (trade name, manufactured by BYK Japan), KP-341, KP-358, KP-368, KF-96-50CS, KF -50-100CS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (trade name, manufactured by Seimi Chemical Co., Ltd.), Footent 222F, Footage 251, FTX-218, FTX-601AD2 (trade name, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, Mitsubishi) Material Co., Ltd.), Megafuck F-171, Megafuck F-177, Megafuck F-475, Megafuck R-08, Megafuck R-30 (trade name, manufactured by DIC Corporation), Fluoroalkylbenzenesulfone Acid salt, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroal Trimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether , Polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester , Polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polio Shi sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, may be mentioned alkyl benzene sulfonates and alkyl diphenyl ether disulfonate salt.

  Further, when the surfactant (D) is a surfactant having a reactive group, the surfactant is less likely to bleed out from the formed cured film or the like, and variation in the lens diameter of the microlens formed on the surface thereof. Is more preferable because it becomes smaller.

  The reactive group is preferably at least one group selected from the group consisting of a (meth) acryloyl group, an oxirane group, and an oxetanyl group from the viewpoint of obtaining a highly curable ink.

Specific examples of the surfactant having a (meth) acryloyl group as a reactive group include FTX-601AD2 (trade name, manufactured by Neos Corporation), RS-72K (trade name, manufactured by DIC Corporation), BYK UV. 3500, BYK UV 3570 (trade name, manufactured by Big Chemie Japan Co., Ltd.), TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300 and TEGO Rad 2500 (trade name, manufactured by Evonik Degussa Japan Co., Ltd.) .
Examples of the surfactant having an oxirane group as a reactive group include RS-211 (trade name, manufactured by DIC Corporation).

  The surfactant (D) used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

  In the ink composition of the present invention, the content of the surfactant (D) is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, further based on the total amount of the ink composition. When the content is preferably 0.1 to 5% by weight, the photocurability of the ink composition and the liquid repellency of the surface of the resulting cured film are more excellent.

  The ink composition of the present invention may further contain a compound selected from an organic solvent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a thermally reactive compound, and a thermal polymerization initiator, as necessary.

1.5. Organic Solvent The ink composition of the present invention may contain an organic solvent for the purpose of adjusting the viscosity of the ink composition and the wettability to the substrate. When an organic solvent is used, fine adjustment of the viscosity and surface tension of the ink can be easily performed.
Although it does not restrict | limit especially as an organic solvent, It is preferable that it is an organic solvent whose boiling point is 100 to 300 degreeC.

  Specific examples of the organic solvent having a boiling point of 100 to 300 ° C. include butyl acetate, isobutyl acetate, butyl propionate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropion Methyl acetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-hydroxyisobutyrate I-propyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, propyl lactate, dioxane, 3-methoxybutanol, 3-methoxybutyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono Phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol Propylene glycol, dipropylene glycol, benzyl alcohol, cyclohexanol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tripropylene glycol methyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, Cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, toluene, xylene, anisole, γ-butyrolactone, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

  The organic solvent that can be used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

1.6. Ultraviolet Absorber The ink composition of the present invention may contain an ultraviolet absorber in order to prevent the obtained cured film and the like from being deteriorated by light such as a backlight.

  Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di Benzotriazole compounds such as -t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (4,6- Triazine compounds such as diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone compounds such as 2-hydroxy-4-n-octyloxybenzophenone, and 2-ethoxy Oxalic acid anilide compounds such as -2'-ethyloxalic acid bisanilide.

  The ultraviolet absorber that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

1.7. Antioxidant The ink composition for lens formation of the present invention may contain an antioxidant in order to prevent oxidation of the resulting cured film and the like.

  Antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis- [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t -Butyl-4-hydroxyphenyl) hindered phenol compounds such as propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, n-butylamine, triethylamine, diethylaminomethyl methacrylate, 2,2, methacrylate 6,6-tetramethyl-4-piperidyl, metac Le acid 1,2,2,6,6-tetramethyl-4-piperidyl, sebacic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl) amine compound, and the like.

  The antioxidant that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

1.8. Polymerization inhibitor The ink composition of the present invention may contain a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone and phenothiazine. Among these, phenothiazine is preferable because an ink composition having a small increase in viscosity can be obtained even during long-term storage.

  The polymerization inhibitor that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

1.9. Thermally Reactive Compound The ink composition of the present invention improves strength in a range that does not affect the light transmittance and refractive index of a cured film obtained from the ink composition, or improves adhesion to a substrate. Therefore, a thermally reactive compound may be included. The heat-reactive compound is not particularly limited as long as it has a functional group that can be reacted with heat, and an epoxy compound, an epoxy curing agent, a bismaleimide, a phenol resin, a resin containing a phenolic hydroxyl group, Examples include melamine resins and silane coupling agents.
The heat-reactive compound may be a single compound or a mixture of two or more compounds.

  In the ink composition of the present invention, the content of the heat-reactive compound is preferably 1 to 10% by weight, more preferably 1 to 8% by weight, and further preferably 1 to 8% by weight with respect to the total amount of the ink composition. It is preferable that it is 6% by weight because a cured film with higher strength can be obtained.

(1) Epoxy compound The ink composition of the present invention may contain an epoxy compound in order to improve the strength of a cured film or the like obtained from the ink composition.
The epoxy compound is not particularly limited as long as it has at least one structure represented by the following formula (11-1) or formula (11-2) in one molecule.

  Specific examples of the epoxy compound include novolak type (phenol novolak type and cresol novolak type), bisphenol A type, bisphenol F type, trisphenol methane type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, bisphenol S type, and tetrapheny. Roll ethane type, bixylenol type and biphenol type epoxy resins, alicyclic and heterocyclic epoxy resins, and epoxy resins having dicyclopentadiene skeleton or naphthalene skeleton, preferably novolak type, bisphenol A type, bisphenol F type and trisphenol methane type epoxy resins.

  As the epoxy compound, an epoxy resin produced by a known method may be used, or a commercially available product may be used.

Examples of commercially available products are jER828, 834, 1001, and 1004 (all trade names: manufactured by Mitsubishi Chemical Corporation), Epicron 840, 850, 1050, 1050, and 2055 (all trade names: DIC). Co., Ltd.), Epototo YD-011, YD-013, YD-127, YD-128 (all trade names: Nippon Steel Chemical Co., Ltd.), D.E.R. 317, 331, 661, 664 (both trade names: Dow Chemical Japan Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (both trade names: Huntsman Japan Co., Ltd.), Sumi-Epoxy ESA- 011, ESA-014, ELA-115, ELA-115, ELA-128 (all trade names: Sumitomo Chemical Co., Ltd.), AER 330, 331, 661, and 664 Trade names: Asahi Kasei E-materials Corp.) Bisphenol A type epoxy resins and the like;
jER152, 154 (all trade names: Mitsubishi Chemical Corporation), D.E.R.431, 438 (all trade names: Dow Chemical Japan Co., Ltd.), Epicron N-730, N-770 N-865 (all trade names: DIC Corporation), Epototo YDCN-701, YDCN-704 (all trade names: Nippon Steel Chemical Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 ( All are trade names: Huntsman Japan Co., Ltd.), XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 (all trade names: Nippon Kayaku Co., Ltd.), Sumi- Epoxy ESCN-195X, ESCN-220 (both trade names: Sumitomo Chemical Co., Ltd.), A.E.R.ECN-235 and E N-299 (trade names: Asahi Kasei E-Materials Co., Ltd.) novolak type such as an epoxy resin;
Epicron 830 (trade name: DIC Corporation), jER807 (trade name: Mitsubishi Chemical Corporation), Epototo YDF-170 (trade name: Nippon Steel Chemical Co., Ltd.), YDF-175, YDF-2001, YDF -Bisphenol F type epoxy resins such as 2004 and Araldite XPY306 (both trade names: Huntsman Japan K.K.);
Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (all trade names: Nippon Steel Chemical Co., Ltd.);
An alicyclic epoxy resin such as Celoxide 2021P (trade name: Daicel Corporation), Araldite CY175 and CY179 (all trade names: Huntsman Japan Co., Ltd.);
Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 (all trade names: manufactured by Mitsubishi Chemical Corporation) or mixtures thereof;
Bisphenol S type epoxy resins such as EBPS-200 (trade name: Nippon Kayaku Co., Ltd.), EPX-30 (trade name: ADEKA Corp.) and EXA-1514 (trade name: DIC Corp.);
bisphenol A novolac epoxy resin such as jER157S (trade name: Mitsubishi Chemical Corporation);
Tetraphenylolethane type epoxy resins such as YL-931 (trade name: Mitsubishi Chemical Corporation) and Araldite 163 (trade name: Huntsman Japan Co., Ltd.);
Heterocyclic epoxy resins such as Araldite PT810 (trade name: Huntsman Japan Co., Ltd.) and TEPIC (trade name: Nissan Chemical Industries, Ltd.);
Epoxy resins having a naphthalene skeleton such as HP-4032, EXA-4750, and EXA-4700 (all trade names: DIC Corporation);
Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200, HP-7200H and HP-7200HH (all trade names: DIC Corporation);
Tris such as Techmore VG3101L (trade name: Mitsui Chemicals), YL-933 (trade name: Mitsubishi Chemical), EPPN-501 and EPPN-502 (all trade names: Nippon Kayaku Co., Ltd.) A phenol methane type epoxy resin is mentioned.

Among these, jER828, 834, 1001 and 1004 (all trade names: Mitsubishi Chemical Corporation), TECHMORE VG3101L (trade name: Mitsui Chemicals), EPPN-501 and EPPN-502 (all When using a trade name: Nippon Kayaku Co., Ltd.), a cured film obtained from the ink composition is preferable because it has high strength.
The epoxy resin that can be used in the ink composition of the present invention may be one type or two or more types.

(2) Epoxy curing agent The ink composition of the present invention may contain an epoxy curing agent in order to further improve the strength of the resulting cured film. As the epoxy curing agent, an acid anhydride curing agent and a polyamine curing agent are preferable.

  Acid anhydride curing agents include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellit Examples thereof include acid anhydrides and styrene-maleic anhydride copolymers.

Examples of polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, and 1,3-bis (amino). Methyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and diaminodiphenylsulfone.
The epoxy curing agent that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

(3) Bismaleimide The ink composition of the present invention may contain a bismaleimide compound in order to further improve the strength of the resulting cured film. Although it does not restrict | limit especially as a bismaleimide compound, For example, the compound represented by following formula (12) is preferable. The bismaleimide compound represented by the following formula (12) can be obtained, for example, by reacting a diamine with an acid anhydride.

In the formula (12), R ⁶³ and R ⁶⁵ are each independently hydrogen or methyl, and R ⁶⁴ is a divalent group represented by the following formula (13).

In formula (13), R ⁶⁶ and R ⁶⁷ are each independently an alkylene having 1 to 18 carbon atoms or a substituent that may be substituted for any arbitrary methylene that is not continuous (not adjacent) with oxygen. It is a divalent group having a good aromatic ring, or an optionally substituted cycloalkylene. Examples of the substituent include carboxyl, hydroxy, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. In view of obtaining a cured film having high heat resistance, it is preferable that R ⁶⁶ and R ⁶⁷ are each independently one divalent group selected from the following group (14).

  In formula (13), X is a divalent group selected from the following group (15).

  The bismaleimide may be one kind or a mixture of two or more kinds.

(4) Phenol resin or resin containing phenolic hydroxyl group The ink composition of the present invention may contain a phenol resin or a resin containing a phenolic hydroxyl group in order to further improve the strength of the cured film obtained. As the phenol resin, a novolak resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde is preferably used. As the resin containing a phenolic hydroxyl group, a vinylphenol homopolymer (hydrogenated product) is used. And vinylphenol copolymers (including hydrogenated products) of vinylphenol and a compound copolymerizable therewith are preferably used.

  Specific examples of the aromatic compound having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-butylphenol. P-butylphenol, o-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, terpene skeleton-containing diphenol, gallic acid, gallic acid ester, α-naphthol and β-naphthol For example.

  Specific examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde.

  Specific examples of the compound copolymerizable with vinylphenol include (meth) acrylic acid or a derivative thereof, styrene or a derivative thereof, maleic anhydride, vinyl acetate and acrylonitrile.

  Specific examples of phenolic resins include Resitop PSM-6200 (trade name; Gunei Chemical Co., Ltd.), Shonor BRG-555 (trade name; Showa Denko Co., Ltd.), and specific resins containing phenolic hydroxyl groups. Specific examples include Marca Linker MS-2G, Marca Linker CST70, and Marca Linker PHM-C (all trade names: Maruzen Petrochemical Co., Ltd.).

  The phenol resin or the resin containing a phenolic hydroxyl group used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

(5) Melamine resin The ink composition of the present invention may contain a melamine resin in order to further improve the strength of the resulting cured film. The melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, and examples thereof include condensates such as methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, and etherified methylol benzoguanamine. . Among these, a condensate of etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.

  Specific examples of the melamine resin include Nicalac MW-30, MW-30HM, MW-390, MW-100LM, and MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.).

  The melamine resin that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

(6) Silane coupling agent The ink composition of the present invention may contain a silane coupling agent in order to improve the adhesion of the resulting cured film to the substrate. Specific examples of the silane coupling agent include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Mention may be made of aminopropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. Among these, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane have a reactive group and can be copolymerized with other components. preferable.

  The silane coupling agent that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

1.10. Thermal polymerization initiator The ink composition of the present invention may contain a thermal polymerization initiator in order to improve the curability of the ink composition by the heating step. Specific examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide and di-t-butyl peroxide. Can be mentioned. Among these, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable.

  The thermal polymerization initiator that can be used in the ink composition of the present invention may be a single compound or a mixture of two or more compounds.

1.11. Viscosity of Ink Composition When the viscosity of the ink composition of the present invention at 25 ° C. measured with an E-type viscometer is 1.0 to 30 mPa · s, the ink composition of the present invention is applied by, for example, an inkjet method. In addition, the discharge property is improved. The viscosity of the ink composition of the present invention at 25 ° C. is more preferably 2.0 to 25 mPa · s, and further preferably 4.0 to 20 mPa · s.

1.12. Method for Preparing Ink Composition The ink composition of the present invention can be prepared by mixing each component as a raw material by a known method.
In particular, the ink composition of the present invention comprises the components (A) to (C) and, if necessary, the component (D), a solvent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a thermally reactive compound, and thermal polymerization. It is preferable to prepare by mixing an initiator etc., filtering the obtained solution, for example using the membrane filter made from ultra high molecular weight polyethylene (UPE), and deaerating it. The ink composition prepared in this way is excellent in dischargeability at the time of application by, for example, an ink jet method.

1.13. Storage of Ink Composition When the ink composition of the present invention is stored at 5 to 30 ° C., the increase in viscosity during storage is small and the storage stability is good.

1.14. Application of Ink Composition by Inkjet Method The ink composition of the present invention can be applied using a known inkjet method. Examples of the ink jet method include a piezo method in which mechanical energy is applied to ink to eject the ink from the ink jet head, and a thermal method in which thermal energy is applied to the ink to eject ink.

  As a preferable coating apparatus used when coating using the ink composition of the present invention, for example, energy corresponding to a coating signal is given to ink in an ink jet head having an ink storage section in which ink is stored, An apparatus that performs application (drawing) corresponding to the application signal while generating ink droplets by energy can be used.

The ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are inseparably integrated. Further, the ink storage unit may be integrated with the ink jet head so as to be separable or non-separable and mounted on the carriage, or may be provided at a fixed portion of the apparatus. In the latter case, ink may be supplied to the ink jet head via an ink supply member, for example, a tube.
The ink jet head may be heated, and the heating temperature is preferably 80 ° C. or less, and more preferably 50 ° C. or less. The viscosity of the ink composition of the present invention at the heating temperature is preferably 1.0 to 30 mPa · s.

1.15. Use of ink composition The ink composition of the present invention is excellent in photocurability, can form a cured film having high adhesion to the substrate, high transparency, etc., and is formed with a smooth curved surface. Since the diameter and height of the microlens can be formed on the substrate as designed, the microlens is preferably used for manufacturing a light guide plate used in a backlight device or the like.

2. Cured film, etc. The cured film for optical material of the present invention (also referred to simply as “cured film” in the present invention) and the microlens are obtained by curing the ink composition of the present invention described above. A cured film or a microlens obtained by applying the ink composition of the present invention described above by, for example, an ink jet method and then curing the ink composition by irradiating the ink composition with light such as ultraviolet rays or visible light is preferable.

  When the thickness of the cured film and microlens obtained from the ink composition of the present invention is 0.5 μm, the light transmittance at a wavelength of 400 nm is preferably 95% or more, more preferably 97% or more.

The amount of light to be irradiated (exposure amount) when the ink composition of the present invention is irradiated with ultraviolet rays, visible light, or the like depends on the composition of the ink composition of the present invention, but is a photo detector manufactured by Ushio Electric Co., Ltd. UVD-365PD measured by integrating actinometer UIT-201 fitted with, preferably 100~5,000mJ / cm ^2, more preferably ^{300~4,000mJ / cm 2, 500~3,000mJ / cm} 2 and more preferable. Moreover, 200-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray and visible light to irradiate, 250-450 nm is more preferable.
In addition, the exposure amount described below is a value measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.

  In addition, as an exposure machine, an electrodeless lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a halogen lamp, an ultraviolet light-emitting diode, etc. are mounted. If it is an apparatus which irradiates, it will not specifically limit.

  Although the lens diameter of the microlens is not particularly limited, it is preferably 10 to 100 μm and more preferably 20 to 60 μm. Moreover, although it does not specifically limit about lens height, Usually, 0.5-20 micrometers is preferable and 2-15 micrometers is more preferable.

3. Laminate The cured film and microlens obtained from the ink composition of the present invention are usually formed on a substrate and constitute a laminate of the substrate and the cured film. Further, a microlens is preferably formed on the cured film obtained from the ink composition of the present invention, and constitutes a laminate of the cured film and the microlens. Furthermore, in the light guide plate in which the cured film obtained from the ink composition of the present invention is suitably used, a cured film obtained from the ink composition of the present invention is formed on a substrate, and a microlens is formed on the cured film. It is the formed laminated body.
3.1. Substrate The substrate is not particularly limited as long as it can be an object to which the ink composition is applied, and the shape is not limited to a flat plate shape, and may be a curved surface shape.

The substrate is not particularly limited. For example, a polyester resin substrate made of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), a polyolefin resin substrate made of polyethylene and polypropylene, a polyvinyl chloride resin substrate, Examples thereof include a fluorine resin substrate, a PMMA substrate, a PC substrate, a PS substrate, an MS substrate, an organic polymer film made of polyamide, polycarbonate, polyimide, and the like, a substrate made of cellophane, and a glass substrate.
Although the thickness of a board | substrate is not specifically limited, Usually, it is 10 micrometers-10 mm, and is suitably adjusted with the objective to use.

3.2. Light guide plate As the light guide plate, a liquid repellent cured film obtained from the ink composition of the present invention is formed on a substrate, and a microlens obtained from the ink composition of the present invention is formed on the cured film. It is preferable that it is a laminated body. Reducing the refractive index difference at the interface between the substrate and the liquid repellent cured film and the interface between the liquid repellent cured film and the microlens can suppress reflection of light incident on the light guide plate at each interface. And can extract light efficiently.

4). Optical component The optical component of the present invention is not particularly limited as long as a liquid-repellent cured film obtained from the ink composition of the present invention is formed, but from the viewpoint of light extraction efficiency and luminance, A light plate is preferred.

5. Video display device The video display device of the present invention includes the optical component. For this reason, it can be suitably used for a video display device having excellent display characteristics such as a liquid crystal display.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these.
In the following, the lens-forming ink compositions obtained in Examples and Comparative Examples are divided into uses and referred to as lens ink and surface treatment agent.

  The names of reaction raw materials and solvents used in Examples and Comparative Examples are indicated by abbreviations. This abbreviation is used in the following description.

Ingredient (A)
AMM: 2-allyloxymethyl acrylate methyl component (B)
TB: t-butyl methacrylate CH: cyclohexyl acrylate HEMA: 2-hydroxyethyl methacrylate DEAA: diethyl acrylamide THFA: tetrahydrofurfuryl acrylate 4HBA: 4-hydroxybutyl acrylate BzMA: benzyl methacrylate LA: lauryl acrylate M-305 (Aronix M-305 , Trade name: manufactured by Toagosei Co., Ltd.): mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate M-309 (Aronix M-309, trade name: manufactured by Toagosei Co., Ltd.): trimethylolpropane triacrylate M- 315 (Aronix M-315, trade name: manufactured by Toagosei Co., Ltd.): isocyanuric acid ethylene oxide modified diacrylate and isocyanuric Mixture of ethylene oxide-modified triacrylate M-402 (Aronix M-402, trade name: manufactured by Toagosei Co., Ltd.): Mixture M-450 of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-450, product) Name: manufactured by Toagosei Co., Ltd.): A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate PE3A-MS (trade name: manufactured by Kyoeisha Chemical Co., Ltd.): pentaerythritol triacrylate succinic acid modified product and pentaerythritol triacrylate DPCA -20 (KAYARAD DPCA-20, trade name: manufactured by Nippon Kayaku Co., Ltd.): caprolactone-modified dipentaerythritol hexaacrylate DPCA-60 (KAYARAD DPCA-60, quotient) Name: Nippon Kayaku Co., Ltd.): Caprolactone-modified dipentaerythritol hexaacrylate V # 1000 (Biscoat V # 1000, trade name: Osaka Organic Chemical Industry Co., Ltd.): Branched polyester polyol terminal acrylate CN2302 (trade name) : Arkema Co., Ltd.): Hyperbranched polyester acrylate oligomer CN2304 (trade name: Arkema Co., Ltd.): Hyperbranched polyester acrylate oligomer A-9550 (NK ester A-9550, trade name: Shin Nakamura Chemical Co., Ltd.) Co., Ltd.): Dipentaerythritol polyacrylate A-9300-1CL (NK ester A-9300-1CL, trade name: Shin-Nakamura Chemical Co., Ltd.): ε-caprolactone-modified tris- (2-acryloxyethyl) Isocyanurate I XA (light acrylate IB-XA, trade name: manufactured by Kyoeisha Chemical Co., Ltd.): isobornyl acrylate U-6LPA (NK oligo U-6LPA, trade name: manufactured by Shin-Nakamura Chemical Co., Ltd.): urethane acrylate and penta Erythritol tetraacrylate UA-306H (UA-306H, trade name: manufactured by Kyoeisha Chemical Co., Ltd.): Reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate UA-510H (UA-510H, trade name: manufactured by Kyoeisha Chemical Co., Ltd.) ): Reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate DPHA-40H (KAYARAD DPHA-40H, trade name: Nippon Kayaku Co., Ltd.): Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Reaction product R-1214 (New Frontier R-1214, trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): Urethane acrylate R-1304 (New Frontier R-1304, trade name: Daiichi Manufactured by Kogyo Seiyaku Co., Ltd.): Mixture of urethane acrylate, alkanediol diacrylate and 2-hydroxypropyl acrylate GX-8810A (New Frontier GX-8810A, trade name: Daiichi Kogyo Seiyaku Co., Ltd.): Urethane acrylate SIU100 (MIRAMER SIU100, product name: manufactured by MIWON): Silicone urethane acrylate oligomer SIU700 (MIRAMER SIU700, product name: manufactured by MIWON): Silicone urethane acrylate oligomer EA2280 (MIRA ER EA2280, trade name: miwon Inc.): modified epoxy diacrylate IRR-214K: manufactured (trade name manufactured by Daicel-Cytec Co.): dimethylol dicyclopentane diacrylate component (C)
Irg754 (Irgacure 754, trade name: manufactured by BASF): oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy]- Mixture with ethyl ester Irg184 (Irgacure 184, trade name: manufactured by BASF): 1-hydroxy-cyclohexyl-phenyl-ketone Irg1173 (Irgacure 1173, trade name: manufactured by BASF): 2-hydroxy-2-methyl-1-phenyl-propane- 1-one component (D)
2200N (TEGO Rad 2200N, trade name: manufactured by Evonik Degussa Japan Co., Ltd.): reactive surfactant having acryloyl group RS-72K (trade name, manufactured by DIC Corporation): reactive surfactant having acryloyl group FTX-601AD2 (trade name, manufactured by Neos Co., Ltd.): Reactive surfactant organic solvent having acryloyl group PGME: Propylene glycol monomethyl ether

Example 1-Preparation of Lens Ink 1 As compound (A) represented by formula (1), AMM, as compound (B), M-305, as photopolymerization initiator (C), Irg 1173, As the surfactant (D), 2200N was mixed in the following composition ratio, and filtered through a UPE membrane filter (0.2 μm) to obtain a filtrate (lens ink 1).
(A) AMM 4.7g
(B) 5.3 g of M-305
(C) Irg1173 0.7g
(D) 2200N 0.0214g

  It was 10.0 mPa · s as a result of measuring the viscosity of the lens ink 1 at 25 ° C. using an E-type viscometer (trade name: TV-22, manufactured by Toki Sangyo Co., Ltd.).

(Examples 2 to 22) -Preparation of lens inks 2 to 22 Lens inks 2 to 22 were prepared in the same manner as in Example 1 except that the ratios of the respective compounds were changed as shown below. The viscosity measured in the same manner as in Example 1 is shown below.

Example 2-Preparation of Lens Ink 2 (A) AMM 3.0 g
(B) M-309 7.0 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 2 was 12.2 mPa · s.

Example 3-Preparation of Lens Ink 3 (A) 5.7 g of AMM
(B) 4.3 g of M-402
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 3 was 9.5 mPa · s.

Example 4-Preparation of lens ink 4 (A) 5.5 g AMM
(B) DPCA-20 4.3 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 4 was 10.1 mPa · s.

Example 5-Preparation of lens ink 5 (A) 5.5 g of AMM
(B) V # 1000 4.5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 5 was 10.5 mPa · s.

Example 6-Preparation of Lens Ink 6 (A) 5.5 g AMM
(B) A-9550 4.5 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 6 was 10.0 mPa · s.

Example 7-Preparation of Lens Ink 7 (A) AMM 5g
(B) CN2302 5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 7 was 10.2 mPa · s.

(Example 8)-Preparation of lens ink 8 (A) 5.3 g of AMM
(B) 4.7 g of CN2304
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 8 was 10.5 mPa · s.

Example 9-Preparation of Lens Ink 9 (A) AMM 7.4g
(B) SIU100 2.6g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 9 was 10.1 mPa · s.

Example 10-Preparation of Lens Ink 10 (A) AMM 6.6 g
(B) SIU700 3.4g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 10 was 11.4 mPa · s.

Example 11-Preparation of Lens Ink 11 (A) AMM 5.8g
(B) A-9300-1CL 4.2g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 11 was 11.3 mPa · s.

(Example 12)-Preparation of lens ink 12 (A) 5.2 g of AMM
(B) M-315 4.8 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 12 was 11.0 mPa · s.

Example 13 Preparation of Lens Ink 13 (A) AMM 4.5 g
(B) 5.5 g of M-450
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 13 was 10.6 mPa · s.

Example 14 Preparation of Lens Ink 14 (A) 6.0 g AMM
(B) UA-510H 4.0g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 14 was 10.7 mPa · s.

Example 15-Preparation of Lens Ink 15 (A) 6.0 g AMM
(B) UA-306H 4.0g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 15 was 9.6 mPa · s.

Example 16-Preparation of Lens Ink 16 (A) AMM 7.8g
(B) EA2280 3.2 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 16 was 10.6 mPa · s.

Example 17-Preparation of Lens Ink 17 (A) 6.0 g AMM
(B) DPCA-60 4.0 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 17 was 10.6 mPa · s.

(Example 18)-Preparation of lens ink 18 (A) 5.2 g of AMM
(B) DPHA-40H 3.8 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 18 was 9.5 mPa · s.

Example 19-Preparation of Lens Ink 19 (A) 6.0 g AMM
(B) R-1304 4.0 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 19 was 9.8 mPa · s.

Example 20-Preparation of Lens Ink 20 (A) AMM 5.6 g
(B) R-1214 4.4g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 20 was 9.8 mPa · s.

Example 21-Preparation of Lens Ink 21 (A) AMM 6.5g
(B) GX-8801A 3.5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 21 was 10.2 mPa · s.

(Example 22)-Preparation of lens ink 22 (A) 5.5 g of AMM
(B) PE3A-MS 4.5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 22 was 10.4 mPa · s.

(Comparative Examples 1 to 9)-Preparation of Lens Inks 23 to 30 Lens inks 23 to 30 were prepared in the same manner as in Example 1 except that the ratios of the respective compounds were changed as shown below. The viscosity measured in the same manner as in Example 1 is shown below.

(Comparative Example 1)-Preparation of lens ink 23 (B) TB 3.8 g
(B) 5.2 g of M-305
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 23 was 9.9 mPa · s.

Comparative Example 2 Preparation of Lens Ink 24 (B) CH 5.8 g
(B) M-305 4.2 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 24 was 9.8 mPa · s.

(Comparative Example 3)-Preparation of lens ink 25 (B) 7.5 g of HEMA
(B) M-305 2.5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 25 was 10.5 mPa · s.

(Comparative Example 4)-Preparation of lens ink 26 (B) DEAA 5.4 g
(B) 4.6 g of M-305
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 26 was 10.6 mPa · s.

(Comparative Example 5) -Preparation of lens ink 27 (B) THFA 6.0 g
(B) M-305 4.0 g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 27 was 10.1 mPa · s.

Comparative Example 6 Preparation of Lens Ink 28 (B) 4HBA 8.8 g
(B) M-305 1.2g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 28 was 11.6 mPa · s.

Comparative Example 7-Preparation of lens ink 28 (B) 5.5 g of BzMA
(B) M-305 4.5g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 28 was 10.4 mPa · s.

(Comparative Example 8)-Preparation of lens ink 29 (B) IBXA 8.8 g
(B) M-305 1.2g
(C) Irg1173 0.7g
(D) 2200N 0.0214g
The viscosity of the lens ink 29 was 10.4 mPa · s.

(Comparative Example 9)-Preparation of lens ink 30 (B) LA 6.6 g
(B) 3.4 g of M-305
(C) Irg1173 0.7g
(D) 2200N 0.0214g
Since the lens ink 30 became cloudy, the viscosity was not measured.

(Example 23)-Preparation of surface treating agent 1 As compound (A) represented by formula (1), AMM, M-305 as compound (B), and Irg184 as photopolymerization initiator (C) As a surfactant (D), RS-72K was mixed at the following composition ratio, and filtered through a UPE membrane filter (0.2 μm) to obtain a filtrate (surface treatment agent 1).
(A) AMM 4.7g
(B) 5.3 g of M-305
(C) Irg184 0.9g
(D) RS-72K 0.0214 g

  As a result of measuring the viscosity of the surface treating agent 1 at 25 ° C. using an E-type viscometer, it was 10.0 mPa · s.

(Example 24)-Preparation of surface treating agent 2 Surface treating agent 2 was prepared in the same manner as in Example 23 except that each compound was used in the respective proportions as shown below. The viscosity measured in the same manner as in Example 23 is shown below.
(A) AMM 4.7g
(B) 5.3 g of M-305
(C) Irg184 0.9g
(D) RS-72K 0.0428g
(D) 2200N 0.0214g
The viscosity of the surface treatment agent 2 was 10.0 mPa · s.

Example 25-Preparation of surface treating agent 3 (A) 4.7 g of AMM
(B) 5.3 g of M-305
(C) Irg184 0.9g
(D) FTX-601AD2 0.1g
The viscosity of the surface treatment agent 3 was 10.0 mPa · s.

(Comparative Examples 10 to 11)-Preparation of Surface Treatment Agents 4 to 5 Surface treatment agents 4 to 5 were prepared in the same manner as in Example 23, except that the ratios of the respective compounds were changed as shown below. The viscosity measured in the same manner as in Example 23 is shown below.

(Comparative Example 10) -Preparation of surface treating agent 4 (B) THFA 3.5 g
(B) M-305 3.5g
(C) Irg754 0.45g
(D) RS-72K 0.015 g
The viscosity of the surface treatment agent 4 was 13.0 mPa · s.

(Comparative example 11)-Preparation of surface treating agent 5 (B) U-6LPA 1.5g
(B) IRR-214K 1.5g
(C) Irg754 0.9g
(D) 2200N 0.024g
(Organic solvent) PGME 5.22 g
The viscosity of the surface treatment agent 5 was 5.7 mPa · s.

(Production of laminate)
A 4 cm square acrylic resin substrate (trade name: manufactured by Asahi Kasei Techno Plus Co., Ltd., Delaglass AD999) was prepared. A surface treatment agent is injected into an ink jet cartridge, and this is mounted on an ink jet apparatus (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.), and a discharge voltage (piezo voltage) is applied using an ink jet head for 10 pl. Under the discharge conditions of 16 V, head temperature of 30 ° C., drive frequency of 5 kHz, and number of coatings of 1, the printing resolution was set to 256 dpi, and coating was performed on the entire surface of the prepared substrate. This substrate was irradiated with light having an integrated exposure of 1,000 mJ / cm ² using a UV irradiation device (J-CURE 1500 (trade name) manufactured by JATEC Corporation) to cure the coating film of the surface treatment agent, thereby repelling the surface. A liquid substrate was obtained.

The lens ink is injected into an ink jet cartridge, mounted on an ink jet apparatus, and using a 10 pl ink jet head, a discharge voltage (piezo voltage) of 20 V, a head temperature of 31 ° C., a drive frequency of 5 kHz, and a discharge condition of one application. Then, one dot was discharged onto the surface liquid repellent substrate at intervals of 150 μm. A substrate (hereinafter referred to as a microlens) formed by irradiating a surface liquid-repellent substrate on which dot patterns are formed at equal intervals with light having an integrated exposure amount of 2,000 mJ / cm ² and curing the applied dot pattern of lens ink Sometimes referred to as a microlens forming substrate). Table 1 shows the laminates prepared with the lens inks and surface treatment agents of the examples and comparative examples and the evaluation results.

  The shape of the microlens was observed with an optical microscope BX51 (trade name) manufactured by OLYMPUS. When the shape of the microlens seen from above is almost a perfect circle (circular), “○”, when it is slightly circular to distorted (slightly distorted), “△”, bulges and waves are seen. The case where the shape was greatly deviated from the circle (bite) was designated as “x”. Further, the lens curved surface shape was measured using a stylus type film thickness meter P-15 (trade name) manufactured by KLA-Tencor Japan Co., Ltd. The case where the shape of the curved surface of the microlens was smooth from the edge toward the center was “◯”, and the case where there was a step at the edge of the lens was “x”.

Table 1

  As shown in Table 1, in the microlens forming substrate formed using the lens ink of the present invention on the surface liquid repellent substrate formed using the surface treating agent of the present invention, a good microlens is obtained. It has been. On the other hand, when a conventional surface treatment agent is used or when a conventional lens ink is used, a good microlens is not obtained. Thus, the usefulness of the present invention was proved.

  The present invention is suitably used for manufacturing a light guide plate that is a member of a backlight unit incorporated in an optical apparatus such as an image display device.

Claims (5)

A microlens-forming ink composition comprising a compound (A) represented by the following formula (1), another radical polymerizable compound (B), and a photopolymerization initiator (C) on a liquid repellent cured film. Is a microlens obtained by curing after applying to a lens shape.

(In formula (1), R ¹ is hydrogen or alkyl.) A microlens forming ink composition further contains a surfactant (D), the micro-lens according to claim 1. The ink composition for forming a microlens according to claim 1 or 2 is formed on a liquid-repellent cured film obtained by curing after applying the ink composition for forming a microlens according to claim 1 or 2. The microlens according to claim 1 , wherein the microlens is obtained by curing after being applied to a shape. The optical component which has a microlens of any one of Claims 1-3 . An image display device comprising the optical component according to claim 4 .