KR101992154B1 - Photo-curable inkjet ink, cured film with surface liquid repellency, microlens and method for forming the same, optical component and image display device - Google Patents

Abstract

The present invention provides a photo-curable ink-jet ink excellent in wettability to a substrate such as an acrylic resin substrate, and capable of forming a surface liquid-repellent cured film having excellent adhesion to a substrate.
A photocurable inkjet ink (1) containing an organic solvent (A), a bifunctional or less difunctional (meth) acrylate (B), a urethane (meth) acrylate (C), a surfactant (D) and a photopolymerization initiator , And the content of the solvent (A) is 40 to 98% by weight based on 100% by weight of the photocurable inkjet ink.

Description

TECHNICAL FIELD [0001] The present invention relates to a photocurable inkjet ink, a surface liquid-repellent cured film, a microlens, a method of forming the same, an optical component, and an image display device. DISPLAY DEVICE}

TECHNICAL FIELD The present invention relates to a photo-curable ink-jet ink suitably used for producing an optical device such as a video display device. More particularly, the present invention relates to a photo-curable ink-jet ink suitable for manufacturing an optical component having a microlens used in a backlight unit.

Conventionally, a microlens formed on a light guide plate for a video display device is formed by injection molding using a metal mold. This method requires a mold for each product design, and it is a considerable expense when manufacturing a small quantity and a plurality of kinds of microlenses.

In recent years, a method of forming a microlens on the surface of a substrate by an ink-jet method as a manufacturing method with a low cost and a high degree of freedom in design has been proposed. However, microlenses formed by using a conventional composition have a problem of non- Seriously, it became a problem.

In order to solve this problem, it has been proposed that the substrate surface is subjected to liquid repellency treatment by an ink-jet method. For this liquid repellency treatment, a negative type photosensitive composition capable of forming a surface lyophobic cured film (see, for example, Japanese Patent Laid-Open Publication No. 2008-209739 (Patent Document 1)) can be used.

Prior art literature

Patent Document 1: JP-A-2008-209739

However, in the negative photosensitive composition described in Patent Document 1, the wettability to a substrate such as an acrylic resin substrate is sometimes poor, and the cured film obtained may have poor adhesiveness to the substrate.

 The present invention has been made in view of the above problems and provides a photocurable inkjet ink which is excellent in wetting property to a substrate such as an acrylic resin substrate and which can form a surface liquid repellent cured film having excellent adhesion to a substrate The purpose is to do.

The present inventors have found that the above problems can be solved by a photocurable inkjet ink comprising a specific amount of an organic solvent, a specific (meth) acrylate, a urethane (meth) acrylate, a surfactant and a photopolymerization initiator, Thereby completing the present invention.

That is, the present invention includes the following items.

[1] A process for producing a photosensitive resin composition, which comprises the steps of: (1) mixing an organic solvent (A), a difunctional (meth) acrylate (B) having a hydroxyl group, urethane (meth) acrylate (C), a surfactant As Mars inkjet ink,

Wherein the content of the solvent (A) is 40 to 98% by weight based on 100% by weight of the photocurable inkjet ink.

[2] The composition according to any one of [1] to [3], wherein the (meth) acrylate (B) is a compound represented by the following formula (1), glycerin mono (meth) acrylate, glycerin di (meth) Is at least one compound selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

....화학식(1)

(1)

(Wherein R ^a is an alkylene of 2 to 12 carbon atoms which may have a cyclic structure independently, R ^b is alkyl or hydrogen of 1 to 6 carbon atoms, and n is an integer of 1 to 30 to be.)

[3] The composition according to [1], wherein the (meth) acrylate (B) is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono The photo-curable inkjet ink according to [1] or [2], which is at least one kind of compound.

[4] The photocurable inkjet ink according to any one of [1] to [3], wherein the urethane (meth) acrylate (C) is a compound represented by the following formula (2).

....화학식(2)

(2)

(Wherein R ¹ , R ² and R ³ are each independently a divalent organic group having 1 to 20 carbon atoms; R ⁴ and R ⁵ are each independently hydrogen or alkyl having 1 to 6 carbon atoms; and m And n are each independently an integer of 1 to 3.)

[5] The compound according to [4], wherein R ¹ and R ³ in the formula (2) are each independently an alkylene having 1 to 10 carbon atoms and R ² is a bivalent group selected from the following group (a) And the photo-curable inkjet ink described in JP-A-

....그룹(a)

.... Group (a)

[6] The photocurable composition according to any one of [1] to [5], which further comprises (meth) acrylate (F) other than the (meth) acrylate (B) and the urethane (meth) Inkjet ink.

[7] The photocurable inkjet ink according to any one of [1] to [6], wherein the surfactant (D) is at least one compound selected from the group consisting of a fluorochemical surfactant and a silicone surfactant.

[8] The photocurable inkjet ink according to any one of [1] to [7], wherein the surfactant (D) is a compound having at least one reactive group.

[9] The photocurable inkjet ink according to [8], wherein the reactive group of the surfactant (D) is at least one group selected from the group consisting of (meth) acryloyl, epoxy and oxetanyl.

[10] The photocurable inkjet ink according to any one of [1] to [9], wherein the solvent (A) is an organic solvent having a boiling point of 100 to 300 ° C.

[11] The photocurable inkjet ink according to any one of [1] to [10], wherein the solvent (A) is a compound having a hydroxy group.

[12] The photocurable inkjet ink according to any one of [1] to [11], wherein the viscosity at 25 ° C is 1.0 to 30 mPa · s.

[13] A surface liquid-repellent cured film obtained by curing the photo-curable ink-jet ink according to any one of [1] to [12].

[14] A microlens formed by an ink-jet method on the surface liquid-repellent cured film described in [13].

[15] A method of forming a microlens, comprising a step of forming a microlens on the surface liquid-repellent cured film according to [13] by an ink-jet method.

[16] An optical component having a microlens according to [14].

[17] A video display device including the optical component according to [16].

 The photo-curable inkjet ink of the present invention is excellent in wetting property against a substrate such as an acrylic resin substrate. For this reason, the surface-lyophobic cured film having a film thickness of 1 m or less can be easily formed by applying the photocurable ink-jet ink of the present invention onto a substrate such as an acrylic resin substrate by an inkjet method and curing.

 Further, since the surface liquid-repellent cured film obtained by the photo-curable inkjet ink of the present invention can be thinned (film thickness is 1 μm or less) and thus has little coloration and has high surface lyophobicity, A microlens having a large ratio of the pattern height to the pattern diameter can be easily formed, and an optical component such as a light guide plate can be easily manufactured.

 Further, since the surface-lyophobic cured film obtained by the photo-curable inkjet ink of the present invention is excellent in adhesion with a substrate such as an acrylic resin substrate, it is possible to provide a surface relief liquid having excellent reliability, A cured film can be provided.

 Therefore, the photocurable inkjet ink of the present invention is useful for manufacturing a high-quality image display device.

[1. Photocurable inkjet ink]

(A), a bifunctional or less (meth) acrylate (B) having a hydroxyl group, a urethane (meth) acrylate (hereinafter referred to as " C), a surfactant (D) and a photopolymerization initiator (E). The solvent (A) is contained in an amount of 40 to 98% by weight based on 100% by weight of the photocurable inkjet ink.

The ink of the present invention is characterized in that the specific amount of the organic solvent (A), the bifunctional or less (meth) acrylate (B), the urethane (meth) acrylate (C) having a hydroxy group, the surfactant Since the ink contains the initiator (E), it has excellent wetting property to a substrate such as an acrylic resin substrate. The ink is applied to a substrate such as an acrylic resin substrate by the ink jet method and cured, And a surface liquid-repellent cured film having a film thickness of 1 m or less can be easily formed. Further, when a microlens is formed on the surface liquid-repellent cured film obtained by the ink of the present invention by an ink-jet method, a microlens having a large ratio of the pattern height to the pattern diameter (0.18 or more) can be easily formed.

The ink of the present invention may contain (meth) acrylate (F) other than the (meth) acrylate (B) and the urethane (meth) acrylate (C) within the range that does not impair the gist of the present invention, An antioxidant, a thermosetting compound other than the epoxy compound, a flame retardant, a thermal polymerization initiator, an antioxidant, and a silane coupling agent.

The ink of the present invention may be colorless or colored. From the viewpoint of transmittance, colorlessness is preferable, but a small amount of a colored compound may be contained within a range not hindering the effect of the invention. For example, when checking the state of the cured film, a coloring agent may be included in order to facilitate identification with the substrate. In this case, it is preferable that the color of the cured film does not have a yellow color. For example, a blue colorant can be used.

In the present specification, '(meth) acrylate' is used to denote both or one of acrylate and methacrylate. The term "epoxy compound" means a compound having an epoxy group (oxirane).

<1.1. Organic solvent (A)>

The ink of the present invention contains 40 to 98% by weight of the organic solvent (A) based on 100% by weight of the ink. When the content of the solvent (A) is in the above range, an ink excellent in wetting property to the substrate can be obtained, and a surface liquid repellent cured film having a thin film thickness (for example, 1 μm or less) . The content of the solvent (A) is preferably 50 to 90% by weight, more preferably 50 to 70% by weight, based on 100% by weight of the ink of the present invention. On the other hand, if the content of the solvent (A) is less than 40% by weight, the obtained ink tends to have poor wetting characteristics to the substrate, and the cured film obtained tends to be thick and tends to become colored (yellow) .

When the solvent (A) is an organic solvent having a boiling point of 100 to 300 占 폚, the resultant ink has good wetting property to the substrate when it is applied onto a substrate such as an acrylic resin substrate by an inkjet method, , And a surface-lyophobic cured film having a uniform film thickness can be formed. Furthermore, it is preferable to use a compound having a hydroxy group as the solvent (A) to obtain an ink in which clogging of the ink- Point or the like.

Specific examples of the organic solvent having a boiling point of 100 to 300 캜 include butyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, Ethoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetonate, ethyl acetonate, dioxane , 3-methoxybutanol, 3-methoxybutylacetate, methyl 2-hydroxyisobutyrate, i-propyl 2-hydroxyisobutyrate, i-butyl 2-hydroxyisobutyrate, n- Propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl 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 monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monophenyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, 1,4-butanediol, Triethylene glycol, 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 Dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Ethylene 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, Butyrolactone, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

Specific examples of the compound having a hydroxy group include 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 mono Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Diethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, and 1,4-butanediol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, - It may be a shot at Dior.

As the solvent (A), an organic solvent containing at least 40 wt% of the total of the solvent (A) with the compound having a hydroxy group is preferable.

Examples of the solvent (A) include propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, It is preferable to use an organic solvent containing at least 40% by weight of the total of the solvent (A) selected from diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, and dipropylene glycol monomethyl ether, It is preferable in terms of obtaining a highly surface-lyophobic cured film.

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

1.2. Bifunctional (meth) acrylate (B) having a hydroxy group>

The ink of the present invention contains a difunctional (meth) acrylate (B) having a hydroxyl group (hereinafter, also referred to as a 'compound (B)'). When the ink of the present invention contains the compound (B), it is possible to form a surface liquid-repellent cured film having excellent adhesiveness to the substrate, and even when used for a long period of time, I can get a film.

The term "bifunctional (meth) acrylate" refers to (meth) acrylate having two or less (meth) acryloyl groups in one molecule.

Examples of the compound (B) include compounds represented by the above formula (1), glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl Is preferable because it is possible to obtain an excellent surface liquid-repellent cured film by the adhesion with the substrate.

In the above formula (1), for example, when n is 2 or more, the compound has a plurality of R ^a . In this case, any two R ^a may be the same or different. This rule also applies to other expressions.

Examples of the compound (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl , At least one compound selected from the group consisting of 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono And a surface-lyophobic cured film having more excellent adhesion to a substrate can be obtained.

As the compound (B), a compound prepared by a known method may be used, or a commercially available product may be used.

Examples of commercially available products include Blenda GMR (trade name, glycerin dimethacrylate, NOF CORPORATION), 4-hydroxybutyl acrylate (Nippon Kasei Chemical Co., (Manufactured by Nippon Kasei Chemical Co., Ltd.), and 1,4-cyclohexanedimethanol monoacrylate (manufactured by Nippon Kasei Chemical Co., Ltd.).

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

The content of the compound (B) in the ink of the present invention is preferably 10 to 60 wt% based on 100 wt% of the sum of the weight of the compound (B), the weight of the compound (C) %, It is preferably from 12 to 55% by weight, and more preferably from 15 to 50% by weight, because a surface-lyophobic cured film having excellent adhesion to an acrylic resin substrate can be obtained.

1.3. Urethane (meth) acrylate (C) &gt;

The ink of the present invention contains urethane (meth) acrylate (C) (hereinafter also referred to as 'compound (C)'). The compound (C) is a compound other than the compound (B). The surface-lyophobic cured film obtained by the ink containing the compound (C) is excellent in film thickness uniformity, excellent in adhesion to a substrate such as an acrylic resin substrate and further cured at a low exposure amount (high sensitivity) Or less of the thickness of the cured film becomes a thin surface lyophobic cured film.

As the compound (C), use of the compound represented by the above formula (2) is preferable in that an ink excellent in photo-curability can be obtained and the surface liquid-repellent cured film can be easily formed.

In the above formula (2)

Each of R ¹ and R ³ is preferably a divalent organic group having 1 to 20 carbon atoms, independently of each other, having a carbon number of 1 to 10 Lt; / RTI &gt;

R ² is preferably a divalent organic group having 1 to 20 carbon atoms and it is preferable to use a divalent organic group selected from the group (a) selected from the group consisting of a divalent organic group having a carbon number of 1 to 20 and a surface lyophobic cured film having a better film thickness uniformity. Lt;

m and n are each independently an integer of 1 to 3, and preferably 2 or 3, and more preferably 3, in each case for the ink curability and the like.

As the compound (C), it is preferable to use a component containing a compound represented by the following formula (3) to obtain an ink excellent in photo-curability and to obtain a surface-lyophilic cured film having better film thickness uniformity And the like. Examples of the component containing the compound represented by the following formula (3) include NK Oligo U-6LPA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

....화학식(3)

(3)

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

When the content of the compound (C) in the ink of the present invention is 10 to 60% by weight relative to 100% by weight of the sum of the weight of the compound (B), the weight of the compound (C) More preferably 15 to 45% by weight, still more preferably 20 to 35% by weight, in view of obtaining a surface liquid repellent cured film excellent in uniformity of film thickness, to be.

1.4. Surfactant (D)>

The ink of the present invention contains a surfactant (D). When the surfactant (D) is contained, surface lyophobicity of the resultant surface liquid-repellent cured film is increased, which is preferable.

Specific examples of the surfactant (D) include polypropone No. 45, polypropylene KL-245, polypropylene No. 75, polypropylene No. 90, polypropylene No. 95 (trade name, available from Kyoeisha Chemical Co., (Manufactured by KYOEISHA CHEMICAL CO., LTD.), Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, KP-341, KP-358, KP-351, BYK 346, BYK 346 and BYK 346 (trade names, manufactured by BYK Chemie Japan) 368, KF-96-50CS, KF-50-100CS (trade name, produced by Shin-Etsu Chemicla Co., Ltd.), Safuron SC-101 and Safuron KH-40 EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, and EFTOP (trade names, manufactured by Neos Corporation), Futagent 251 and FTX- EF-802 (trade name, manufactured by Mitsubishi Materials Corporation), Mega Park F-171, Mega Park F-177, (Product name, manufactured by DIC), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxyethylene ethers, fluoro (meth) acrylates, Alkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether , Polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene Ethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, Sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, T-butyl ether, alkylbenzenesulfonic acid salts, and alkyl diphenyl ether disulfonic acid salts.

Further, the surfactant (D) is preferably a fluorine-based surfactant or a silicone-based surfactant, because the surface lyophobicity of the resultant surface-lyophilic cured film becomes higher. Particularly, when a microlens is formed on the obtained surface-lyophobic cured film by a surfactant (D) as a surface-active liquid curable film by the ink-jet method, a microlens having a small variation in the size and a large ratio of the pattern height to the pattern diameter is obtained .

If the surfactant (D) is a compound having at least one reactive group, even an ink containing a large amount of the solvent (A) is preferable because the ink has high curability. As the reactive group, at least one group selected from the group consisting of (meth) acryloyl, epoxy and oxetanyl is preferable in that an ink having high curability can be obtained.

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

Examples of the surfactant having an epoxy as a reactive group include RS-211K (trade name, manufactured by DIC Corporation).

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

In the ink of the present invention, the weight ratio of the sum of the weight of the compound (B) and the weight of the compound (C) to the weight of the surfactant (D) (B) + (C) :( D) 1, it is preferable because the balance between the photo-curability of the ink and the lyophobicity of the surface of the resulting cured film is good and excellent. Further, it is more preferable that the weight ratio (B) + (C) :( D) is in the range of 500: 1 to 2: 1, more preferably 200: 1 to 5: : 1 is particularly preferable.

<1.5. Photopolymerization initiator (E)

The ink of the present invention contains a photopolymerization initiator (E). The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of generating radicals upon irradiation with ultraviolet (UV) rays or visible light rays, but may be any one of an? -Hydroxyalkylphenone-based photopolymerization initiator, an acylphosphine oxide- An oxyphenyl acetic acid ester photopolymerization initiator is preferable. Of these, an oxyphenyl acetic acid ester photopolymerization initiator is more preferable in view of the photocurability of the ink, the transmittance of the obtained surface liquid repellent cured film, and the like.

Specific examples of the photopolymerization initiator (E) include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4- 2-methyl-4'-isopropylpropiophenone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, Dimethoxy-1,2-diphenylethan-1-one, camphaquinone, benzanthrone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoyl isoamyl, 4,4'- Butyl peroxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) Phenol, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'- Carbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'- Di (t-butylperoxycarbonyl) benzophenone, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s- triazine, 4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - 2,6- (Trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -Triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis -Diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- -4,4 ', 5,5'-tetra Bis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'- Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholino-propionyl) -9-n- dodecyl carbazole, bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2-hydroxy-2-methyl-1-phenyl-1-propyl) 2-methyl-1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxyphenyl) Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone , 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone, 2- Phenyl) -1-butanone, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl- 2-phenyl-acetoxy-ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] 2-hydroxy-ethoxy] -ethyl ester and a mixture of oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoyl formate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, Tetramethylbenzoyldiphenylphosphinic acid ester, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyl Oxime) and 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime).

Among these, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] 2-phenyl-acetoxy-ethoxy] -ethyl ester and a mixture of oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoyl formate, bis 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable,

Phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, oxy-phenyl- A mixture of 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl acetate and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] , And 4,6-trimethylbenzoyldiphenylphosphine oxide are more preferable.

Examples of commercially available products of the photopolymerization initiator (E) include Irgacure 184, Irgacure 651, Irgacure 127, DAROCUR 1173, Irgacure 500, Irgacure 2959, Irgacure 754, DAROCUR MBF and Lucirin TPO (trade name, product of BASF Japan Ltd.).

Of these, Irgacure 754, DAROCUR MBF and Lucirin TPO (trade name, product of BASF Japan Ltd.) are preferable.

The photopolymerization initiator (E) used in the ink of the present invention may be a single compound or a mixture of two or more compounds.

The content of the photopolymerization initiator (E) in the ink of the present invention is preferably 1 to 50 parts by weight based on 100 parts by weight of the sum of the weight of the compound (B), the weight of the compound (C) More preferably from 1 to 40 parts by weight, still more preferably from 5 to 30 parts by weight, more preferably from 5 to 30 parts by weight, based on the total weight of the ink composition, Wealth.

<1.6. (Meth) acrylate (F) other than the compound (B) and the compound (C)

The ink of the present invention can be prepared by appropriately adjusting the relationship between the solid content concentration and the viscosity in the ink or by adjusting the amount of the compound (B) and the compound (C) for the purpose of improving the applicability (wetting property) (F) (hereinafter abbreviated as 'compound (F)') other than the above-mentioned (meth) acrylate.

Specific examples of the compound (F) include pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, bisphenol F ethylene oxide modified di (meth) (Meth) acrylates such as bisphenol A ethylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, 2-n-butyl- (Meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane tri , Propylene oxide modified trimethylol propane tri (meth) acrylate, epichlorohydrin modified trimethylol propane tri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) , Diglycerin tetra (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate,? -Caprolactone modified tris (acryloxyethyl) isocyanurate, tricyclodecane dimethanol di (Meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (Meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (Meth) acryloyloxyethylketone, 3-ethyl-3- (meth) acryloxyethyloxetane, 2- (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Pentenyl oxyethyl (meth) acrylate, tricyclo (5,2,1,0 ^2.6) decanyl (meth) acrylate, tricyclo (5,2,1,0 ^2.6) decanyl oxyethyl (Meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-phenoxyethyl (meth) acrylate, (meth) acrylate, ethylene oxide adduct of lauryl alcohol, mono [2- (meth) acryloyloxyethyl] maleate mono [2- (Meth) acryloyloxyethyl] and cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

Among them, as the compound (F), an ink excellent in wetting property to a substrate such as an acrylic resin substrate can be obtained when the ink composition is applied by an ink-jet method, and a uniform liquid repellent film having a thin film thickness can be obtained , A polyfunctional (meth) acrylate having at least one kind selected from the group consisting of cycloalkyl and cycloalkylene is preferable, and tricyclodecane dimethanol diacrylate is more preferable.

As the compound (F), a compound prepared by a known method may be used, or a commercially available product may be used.

Examples of commercially available products include IRON214-K (trade name, tricyclodecane dimethanol diacrylate, manufactured by DAICEL-CYTEC Company LTD.), ARONIX M-208, ARONIX M- Manufactured by TOAGOSEI CO., LTD.), And the like.

The compound (F) usable in the ink of the present invention may be a single compound or a mixture of two or more compounds.

When the content of the compound (F) in the ink of the present invention is 0 to 200 parts by weight based on 100 parts by weight of the total amount of the compound (B) and the compound (C) More preferably from 35 to 170 parts by weight, and still more preferably from 70 to 140 parts by weight, because it is possible to obtain a surface-lyophobic cured film excellent in wettability.

<1.7. Polymerization inhibitor>

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

The polymerization inhibitor usable in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

When the content of the polymerization inhibitor in the ink of the present invention is 0.01 to 1 part by weight based on 100 parts by weight of the total amount of the compound (B) and the compound (C), the viscosity increase is small More preferably 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight in view of balance between storage stability and photocurability.

<1.8. Thermosetting compounds other than epoxy compounds>

The ink of the present invention may contain a thermosetting compound other than an epoxy compound. The thermosetting compound is not particularly limited as long as it is a compound having a functional group capable of thermosetting, and includes bismaleimide, a phenol resin, a resin containing a phenolic hydroxyl group, a melamine resin, and an epoxy curing agent.

The thermosetting compound other than the epoxy compound usable in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

In the ink of the present invention, if the content of the thermosetting compound other than the epoxy compound is 2 to 50 parts by weight based on 100 parts by weight of the total amount of the compound (B) and the compound (C) More preferably 5 to 30 parts by weight, still more preferably 10 to 20 parts by weight, because heat resistance is improved.

1.8.1 Bismaleimide

Examples of bismaleimide include compounds represented by the following formula (4). The bismaleimide represented by the following formula (4) is obtained, for example, by reacting a diamine with an acid anhydride.

....화학식(4)

(4)

In the formula (4), R ¹⁰ and R ¹² are each independently hydrogen or methyl, and R ¹¹ is a divalent group represented by the following formula (5).

....화학식(5)

(5)

In the formula (5), R ¹³ and R ¹⁴ each independently represent an alkylene having 1 to 18 carbon atoms in which any methylene which is not adjacent (nonadjacent) may be substituted with oxygen, an aromatic ring which may have a substituent Or a cycloalkylene which may have a substituent. Examples of the substituent include a carboxyl group, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. It is preferable that R ¹³ and R ¹⁴ are each independently a divalent group which is one kind of group selected from the following group (8) in that a surface-lyophobic cured film having high heat resistance can be obtained.

....그룹(8)

.... Groups (8)

In the formula (5), X is a divalent group selected from the following group (9).

....그룹(9)

.... Groups (9)

The bismaleimide usable in the ink of the present invention may be a single compound or a mixture of two or more compounds.

1.8.2 Phenolic resin, or resin containing phenolic hydroxyl group

As the phenol resin, a novolak resin obtained by condensation reaction of an aromatic compound having a phenolic hydroxyl group with an aldehyde is preferably used. As the resin containing a phenolic hydroxyl group, a homopolymer of vinylphenol (including a hydrogenated product) and , Vinylphenol and vinylphenol-based copolymer (including hydrogenated product) of a compound capable of copolymerization with vinylphenol are preferably used.

Examples of the aromatic compound having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, , Gallic acid, gallic acid ester,? -Naphthol,? -Naphthol, and the like.

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

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

Specific examples of the resin containing a phenolic resin or a phenolic hydroxyl group include Redistop PSM-6200 (trade name, manufactured by GUN EI CHEMICAL INDUSTRY CO., LTD.), (Trade name, manufactured by SHOWA DENKO KK), Maruka Linker MS-2P, Maruka Linker CST70, Maruka Linker PHM-C (trade name, Maruzen Petrochemical Co., Manufactured by Maruzen Petrochemical Co., LTD.).

The phenol resin or the resin containing the phenolic hydroxyl group which can be used in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

1.8.3 Melamine resin

The melamine resin is not particularly limited as long as it is a resin produced by the polycondensation of melamine and formaldehyde, and is preferably a resin obtained by polycondensation of melamine with formaldehyde, such as methylolmelamine, etherified methylolmelamine, benzoguanamine, methylolbenzoguanamine, Condensates such as naphthalene and namin. Of these, condensation products of etherified methylol melamine are preferred from the standpoint that the obtained surface lyophobic cured film has good chemical resistance.

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

The melamine resin which can be used in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

1.8.4 Epoxy hardener

The ink of the present invention may contain an epoxy curing agent in order to further improve the chemical resistance of the obtained surface lyophobic cured film. As the epoxy curing agent, an acid anhydride curing agent and a polyamine curing agent are preferred.

Examples of the acid anhydride-based curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic anhydride, and styrene-maleic anhydride copolymer. .

Examples of the polyamine-based vulcanizing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamide amine (polyamide resin), ketimine compound, isophoronediamine, m- Diamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane , Diaminodiphenylsulfone, and the like.

The epoxy curing agent usable in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

<1.9. Flame Retardant>

The ink of the present invention may contain a flame retardant. When the ink of the present invention contains a flame retardant, it is preferable because a surface-lyophobic cured film having high flame retardancy can be obtained. The flame retardant is not particularly limited as far as it is a compound capable of enhancing the flame retardancy, but it is preferable to use an organic phosphorus flame retardant from the viewpoints of low toxicity, low pollution and safety.

Examples of organic phosphorus flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyldiphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene Oxides, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and condensed 9,10-dihydro- 10-phosphaphenanthrene-10-oxide, and the like.

As the flame retardant, it is preferable to use a compound having a structure represented by the following formula (6) in that the flame retardant does not readily bleed out even when the surface-lyophobic cured film obtained is allowed to stand at a high temperature. As the compound having a structure represented by the following formula (6), a compound represented by the following formula (7) is preferable, and a compound represented by the following formula (7) is a condensed 9,10-dihydro-9-oxa- Papenanthrene-10-oxide, and the like. Examples of commercially available compounds represented by the following formula (7) include HFA-3003 (trade name, manufactured by SHOWA DENKO K.K.) (trade name, manufactured by Showa Denko K.K.).

....화학식(6)

(6)

....화학식(7)

(7)

In the formula (7), m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 3. Preferably, m is 1 or 2, n is 1 or 2, and m + n is 3.

The flame retardant which can be used in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

The flame retardant may be a compound prepared by a known method or a commercially available product such as HFA-3003 (trade name) manufactured by SHOWA DENKO K.K.

When the content of the flame retardant used in the ink of the present invention is 15 to 30 parts by weight per 100 parts by weight of the total amount of the compound (B) and the compound (C), the flame retardancy of the surface- And more preferably 20 to 25 parts by weight.

<1.10. Thermal polymerization initiator>

The ink of the present invention may contain a thermal polymerization initiator to improve the curability of the ink by the heating process. Specific examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide and di-t-butyl peroxide . Among these, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) are preferable.

The thermal polymerization initiator usable in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

<1.11. Antioxidants>

The ink of the present invention may contain an antioxidant in order to improve the transparency of the obtained surface lyophobic cured film and to prevent yellowing when it is left at a high temperature. Specific examples of the antioxidant include a hindered amine antioxidant and a hindered phenol antioxidant. Specific examples thereof include IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 and IRGANOX 1520L (trade names, produced by BASF Japan Ltd.).

The antioxidant usable in the ink of the present invention may be a single compound or a mixture of two or more compounds.

<1.12. Silane coupling agent>

The ink of the present invention may contain a silane coupling agent in order to improve the adhesion of the obtained surface liquid-repellent cured film to the substrate.

Specific examples of the silane coupling agent include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

Of these, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane are preferable because they have a reactor and can copolymerize with other components.

The silane coupling agent usable in the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

<1.13. Viscosity of ink>

The viscosity of the ink of the present invention measured at 25 캜 by the E-type viscometer is preferably 1.0 to 30 mPa · s. When the viscosity is within this range, when the ink of the present invention is applied by the ink-jet method, the ejectability by the ink-jet apparatus is improved. The viscosity of the ink of the present invention at 25 占 폚 is more preferably 1.2 to 25 mPa 占 퐏, and particularly preferably 1.5 to 20 mPa 占 퐏.

<1.14. Method of producing ink>

The ink of the present invention can be produced by mixing each component to be a raw material by a known method.

In particular, the ink of the present invention can be produced by mixing the above components (A) to (E) and, if necessary, other components, and filtering the resulting solution by, for example, filtration using a membrane filter made of a fluororesin . The ink thus produced is excellent in dischargeability upon application by the ink-jet method.

<1.15. Preservation of ink>

When the ink of the present invention is stored at -20 to 25 占 폚, the increase in viscosity during storage is small and storage stability becomes good.

[2. Application of ink by inkjet method]

The ink of the present invention can be applied using a known inkjet method. Examples of the ink-jet method include a piezo method in which ink is ejected from an ink-jet head by applying mechanical energy to ink, and a coating method (so-called thermal method) in which ink is ejected by applying heat energy to ink have.

By using the inkjet method, the ink of the present invention can be easily applied in a predetermined pattern shape, and a uniform pattern can be formed on a large substrate.

Examples of the ink-jet head include those having a heat generating portion made of metal and / or metal oxide. Specific examples of the metal and / or metal oxide include metals such as Ta, Zr, Ti, Ni and Al, and oxides of these metals.

As a coating apparatus which is preferably used when applying by using the ink of the present invention, for example, it is possible to apply energy corresponding to a coating signal to ink in an ink jet head having an ink containing section in which ink is contained, And a device for performing coating (drawing) corresponding to the application signal while generating ink droplets (droplets).

The ink-jet applying device is not limited to the one in which the ink-jet head and the ink accommodating portion are separated, but may be integrally formed so that they can not be separated. The ink containing portion may be separated from the ink jet head or may be integrated with the ink jet recording head so that the ink can not be separated from the ink jet head. The ink containing portion may be mounted on the carriage or may be provided on the fixing portion of the apparatus. In the latter case, ink may be supplied to the ink-jet head through an ink supply member, for example, a tube.

[3. Usage of ink]

Since the ink of the present invention is excellent in wettability to a substrate, particularly an acrylic resin substrate, the production of an optical device such as a video display device, the manufacture of an optical component having a microlens used for a backlight unit, Is used suitably for liquid repellent treatment of the surface of the substrate when manufacturing the lens array. Further, according to the ink of the present invention, it is possible to form a surface liquid-repellent cured film having excellent adhesion with a substrate, particularly an acrylic resin substrate, and having excellent reliability in which peeling from the substrate does not occur even in long- It is possible to manufacture an optical component such as a light guide plate and the like, so that the ink is useful for manufacturing a high-quality image display device. Furthermore, according to the ink of the present invention, it is possible to cope with enlargement of optical components and video display devices.

[4. Surface lyophobic cured film]

The surface lyophobic cured film of the present invention is obtained by curing the above-described ink of the present invention, and is preferably a film obtained by coating the surface of a substrate by an inkjet method and then curing by irradiating light such as ultraviolet rays or visible rays .

When irradiated with UV rays or visible rays, the light quantity (exposure dose) of irradiating is suitably adjusted to the composition of the ink, but is 100 to 5,000mJ / cm ^2, and preferably, 200 to a more preferred 4,000mJ / cm ² And more preferably 300 to 3,000 mJ / cm &lt; ² &gt;. The wavelength of ultraviolet light or visible light to be irradiated is preferably 200 to 500 nm, more preferably 200 to 450 nm.

Further, in the present invention, the exposure dose is a value measured with a cumulative light amount meter UIT-201 (trade name) equipped with a light receiving device UVD-365PD (trade name) manufactured by USHIO INC.

A mercury lamp, a high-pressure mercury lamp, a metal-halide lamp, a halogen lamp, or the like is mounted thereon, and an ultraviolet ray or a visible ray And the like.

The substrate to which the ink of the present invention is applied is not particularly limited as long as it can be an object to which ink is applied, and the shape is not limited to a flat plate shape, but may be a curved surface shape.

Examples of the substrate include, but are not limited to, a polyester-based resin substrate made of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); A polyolefin resin substrate made of polyethylene, polypropylene, polystyrene or the like; Organic polymer films composed of polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, and polyimide; cellophane; Metal foil; Laminated films of polyimide and metal foil; Paper peeled with glassine paper, parchment paper, polyethylene, clay binders, polyvinyl alcohol, starch or carboxymethylcellulose (CMC) with a filling effect; And a glass substrate.

Among them, it is preferable to use an acrylic resin substrate.

As the substrate, a substrate containing an additive such as an antioxidant, a deterioration inhibitor, a filler, an ultraviolet absorber, an antistatic agent and / or an electromagnetic wave inhibitor may be used within a range not adversely affecting the effect of the present invention. The substrate may be a substrate which has undergone adhesion (easy adhesion) treatment, such as corona treatment, plasma treatment, or blast treatment, if necessary, on at least a part of the surface of the substrate, Or a substrate on which a hard coat film is set.

The thickness of the substrate is not particularly limited, but is usually 10 μm to 10 mm, and is appropriately adjusted according to the purpose of use.

The film thickness of the surface liquid-repellent cured film of the present invention is not particularly limited, but is preferably 1 m or less, more preferably 0.5 m or less in optical characteristics.

When the thickness of the surface lyophobic cured film of the present invention is within the above range, it becomes a cured film with poor coloration (yellowing), and thus is suitably used for forming a light guide plate requiring a cured film with poor coloration (yellowing).

Since the ink of the present invention is excellent in wetting transferability to a substrate, particularly an acrylic resin substrate, when a film such as a substrate is coated on a substrate, even if the resolution of printing is low, I can get a film. Therefore, the surface liquid-repellent cured film having a thin film thickness can be formed.

On the other hand, conventional ink has poor wetting property to a substrate, particularly an acrylic resin substrate, so that it is difficult to form a film covering the substrate unless the printing resolution is high. Therefore, It is often the case that only a thick cured film can be formed.

The surface lyophobic cured film of the present invention is excellent in adhesion to a substrate such as an acrylic resin substrate and can be formed into a thin film and exhibits high light transmittance and high strength. Therefore, the production of a micro lens used for a backlight unit, Is suitably used for forming the liquid-repellent film provided on the surface of the substrate when manufacturing the microlens array.

[5. Microlens]

The microlens of the present invention is formed by the ink jet method on the surface lyophobic curing film of the present invention. Therefore, it is possible to easily form a microlens having a small non-uniformity in the pattern diameter and the height.

The microlens may be formed using an ink for forming a microlens, and the ink is not particularly limited and conventionally known ink may be used. The method of forming the microlenses is not particularly limited and may be appropriately adjusted according to the ink to be used.

The lens diameter of the microlenses is not particularly limited, but is preferably 10 to 100 占 퐉, more preferably 15 to 60 占 퐉, and particularly preferably 20 to 50 占 퐉. The height of the lens is not particularly limited, but is usually preferably 0.5 to 30 占 퐉, more preferably 1 to 20 占 퐉, and particularly preferably 2 to 15 占 퐉.

The ratio of the lens height to the lens diameter is not particularly limited, but is preferably 0.18 or more, and more preferably 0.2 or more, from the viewpoint of production of an optical component or the like having excellent light extraction efficiency.

[6. Optical components]

The optical component of the present invention has the micro lens. Therefore, it is an optical component having excellent optical characteristics. Examples of the optical component include a light guide plate and the like.

[7. Video display device]

The video display device of the present invention includes the optical component. Therefore, it is an image display device having excellent display characteristics.

[Example]

Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto. In the following, the photo-curable inkjet ink obtained in the embodiment can be simply referred to as an ink. That is, for example, the photo-curable inkjet ink 1 may be referred to as ink 1.

[Example 1]

Propylene glycol monomethyl ether (hereinafter abbreviated as 'PGME') which is a solvent (A) and 4-hydroxybutyl acrylate (trade name: Nippon Kasei Chemical Co., NK Oligo U-6LPA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), which is a component containing urethane (meth) acrylate (C) represented by the above formula (3) (Trade name: BASF) (trade name, manufactured by Evonik Degussa Japan), which is a photopolymerization initiator (E), and TEGO Rad 2200N (Manufactured by BASF Japan Ltd.) was mixed with the following composition to obtain a homogeneous solution, which was then filtered through a membrane filter made of polytetrafluoroethylene (PTFE) (pore size 0.2 μm) to obtain a filtrate Mars inkjet ink 1) was obtained.

(A) PGME: 5.22 g

(B) 4-hydroxybutyl acrylate: 1.50 g

(C) NK Oligomer U-6LPA: 1.50 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

The viscosity of Ink 1 at 25 캜 was measured using an E-type rotational viscometer (TV-22 (trade name), manufactured by TOKI SANGYO CO., LTD. As a result, it was 6.1 mPa · s.

[Example 2]

(Product name, glycerin dimethacrylate, manufactured by NOF CORPORATION) instead of 4-hydroxybutyl acrylate as the (meth) acrylate (B) ) And IRR214-K (trade name: tricyclodecane dimethanol diacrylate, manufactured by DAICEL-CYTEC Company LTD.) Which is further (meth) acrylate (F) A photocurable inkjet ink 2 having the following composition was prepared in the same manner as in Example 1, except that the blending amount was changed as follows.

(A) PGME: 4.25 g

(B) Brena GMR: 1.00 g

(C) NK Oligo U-6LPA: 1.00 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) IRR214-K: 1.00 g

The viscosity of the ink 2 at 25 占 폚 was measured and found to be 5.6 mPa 占 퐏.

[Example 3]

In the same manner as in Example 2 except that 4-hydroxybutyl acrylate was used in place of Brena GMR (trade name) as the (meth) acrylate (B) in Example 2, a photocurable inkjet ink 3 having the following composition .

(A) PGME: 4.25 g

(B) 4-hydroxybutyl acrylate: 1.00 g

(C) NK Oligo U-6LPA: 1.00 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) IRR214-K: 1.00 g

The viscosity of the ink 3 at 25 占 폚 was measured and found to be 5.4 mPa 占 퐏.

[Example 4]

Cyclohexanedimethanol monoacrylate (Nippon Kasei Chemical Co., Ltd.) was used instead of Brena GMR (trade name) as (meth) acrylate (B) The photo-curable inkjet ink 4 of the following composition was prepared in the same manner as in Example 2 except that

(A) PGME: 4.25 g

(B) 1,4-Cyclohexanedimethanol monoacrylate: 1.00 g

(C) NK Oligo U-6LPA: 1.00 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) IRR214-K: 1.00 g

The viscosity of the ink 4 at 25 占 폚 was measured and found to be 5.8 mPa 占 퐏.

[Example 5]

Except that DAROCUR MBF (trade name, product of BASF Japan Ltd.) was used instead of Irgacure 754 (trade name) as the photopolymerization initiator (E) in Example 3, and the blending amount was changed as follows. As in Example 3, a photocurable inkjet ink 5 having the following composition was prepared.

(A) PGME: 4.25 g

(B) 4-hydroxybutyl acrylate: 0.50 g

(C) NK Oligo U-6LPA: 1.25 g

(D) TEGO Rad 2200N: 0.03 g

(E) DAROCUR MBF: 0.45 g

(F) IRR214-K: 1.25 g

The viscosity of the ink 5 at 25 占 폚 was measured and found to be 5.4 mPa 占 퐏.

[Example 6]

(Trade name, bisphenol F ethylene oxide-modified (n? 2) diacrylate, Toagosei (trade name) was used instead of IRR214-K (Manufactured by TOAGOSEI CO., LTD.) Was used, and a photo-curable inkjet ink 6 having the following composition was produced in the same manner as in Example 3, except that the compounding amount was changed as follows.

(A) PGME: 5.22 g

(B) 4-hydroxybutyl acrylate: 1.00 g

(C) NK Oligo U-6LPA: 1.00 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) ARONIX M-208: 1.00 g

The viscosity of the ink 6 at 25 占 폚 was measured and found to be 5.8 mPa 占 퐏.

[Comparative Example 1]

Ink 2 of the following composition was prepared in the same manner as in Example 2 except that (meth) acrylate (B) was not used and the compounding amount was changed as follows.

(A) PGME: 5.22 g

(B) - -

(C) NK Oligomer U-6LPA: 1.50 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) IRR214-K: 1.50 g

The viscosity of the ink 7 at 25 占 폚 was measured and found to be 5.8 mPa 占 퐏.

[Comparative Example 2]

In the same manner as in Example 2 except that Aronix M-305 (trade name: pentaerythritol triacrylate, TOAGOSEI Co., Ltd.) which is a trifunctional acrylate having a hydroxyl group was used instead of (meth) CO., LTD.)) Was used, and in the same manner as in Example 1 except that the compounding amount was changed as follows.

(A) PGME: 5.22 g

(B) - -

(C) NK Oligo U-6LPA: 1.00 g

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure 754: 0.45 g

(F) ARONIX M-305: 1.00 g

(F) IRR214-K: 1.00 g

The viscosity of the ink 8 at 25 占 폚 was measured and found to be 6.0 mPa 占 퐏.

&Lt; Evaluation of Inks 1 to 8 &gt;

The inks 1 to 8 thus prepared were subjected to the following evaluations.

(Formation of surface liquid repellent cured film)

A 4 cm x 4 cm acrylic resin substrate (product of ASAHIKASEI TECHNOPLUS Co., Ltd .; DERGRASS AD999 (trade name)) and a glass substrate were prepared. The ink 1 was injected into an inkjet cartridge and mounted on an inkjet apparatus (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.). The ink 1 was discharged at a discharge voltage (piezo voltage) of 16 V, a head temperature of 30 캜, a driving frequency of 5 kHz, As the ejection conditions, the printing resolution was set to 1250 dpi and the entire surface of each substrate was coated. Thereafter, the substrates were irradiated with ultraviolet rays at an UV exposure amount of 2,000 mJ / cm ² using a UV irradiation apparatus (J-CURE 1500 (trade name) manufactured by JATEC Corporation) , An acrylic resin substrate on which the surface lyophobic cured film was formed, and a glass substrate were obtained. Similarly, a substrate on which the surface lyophobic cured film was formed also for the inks 2 to 8 was obtained.

Furthermore, a microlens was formed on an acrylic resin substrate on which the surface liquid-repellent cured film was formed as follows.

(Formation of microlenses)

The photocurable composition L1 for a microlens was injected into an inkjet cartridge and mounted on an inkjet apparatus (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.), and a discharge voltage (piezo voltage) The ink was applied on the acrylic resin substrate (on the surface liquid-repellent cured film) on the surface lyophobic cured film with the printing resolution set to 512 dpi at a frequency of 5 kHz and a number of application times of 1 time at a time interval of 50 탆. Thereafter, the substrate was irradiated with ultraviolet rays at an UV exposure amount of 1,000 mJ / cm ² using a UV irradiation apparatus (J-CURE 1500 (trade name) manufactured by JATEC Corporation), whereby an acrylic resin To obtain a substrate.

The photocurable composition L1 for a microlens was prepared by mixing Aronix M-305 (trade name, 3.5 g), tetrahydrofurfuryl acrylate (3.5 g) and Irgacure 754 (trade name, 0.49 g) To obtain a solution, which was then filtered through a PTFE membrane filter (pore size 0.2 μm), and the viscosity at 25 ° C. was 16.8 mPa · s.

(Thickness of surface liquid repellent cured film)

A part of the cured film was scraped off with a cutter knife on the glass substrate on which the surface liquid-repellent cured film was formed, and the step was measured with a contact type P-15 (trade name, KLA-Tencor Japan) The film thickness of the cured film was obtained.

A case where the film thickness was less than 1 占 퐉 was evaluated as?, And a case where the film thickness was not less than 1 占 퐉 was evaluated as x. The results are shown in Table 1.

(Transparency of the surface lyophobic cured film)

In the glass substrate on which the surface-lyophobic cured film is formed, the transmittance of the cured film at 400 nm and the angle (b *) at 380 nm to 780 nm were measured by using an infrared ultraviolet spectrophotometer V-670 (trade name, (Manufactured by JEOL Ltd.).

The angle (b *) is an index indicating the yellow color, and means that the color is further yellow when the value is large. The angle b * is preferably less than 0.1.

(Evaluation of adhesion)

A Scotch transparent pressure-sensitive adhesive tape transparent off-white _TM 600 (trade name, product of 3M) having a width of 18 mm was attached to the surface of the acrylic resin substrate on which the microlenses were formed and the micro lenses were formed. Pulled out, and the substrate after peeling off the tape was observed.

A case where there was no abnormality in the surface lyophobic cured film and the microlens (no peeling was observed) was evaluated as &amp; cir &amp;, and a case where peeling occurred in the surface lyophobic cured film or a part of the microlens was evaluated as x.

Further, after the acrylic resin substrate on which the microlenses were formed was subjected to a high temperature and high humidity test (at a temperature of 50 DEG C and a humidity of 90% for 100 hours), the same adhesion evaluation was carried out.

(Evaluation of Micro Lens Diameter (D)) [

The micro lens diameter D formed on the acrylic resin substrate was measured using an optical microscope BX51 (trade name, manufactured by OLYMPUS CO., LTD.). For the value of the micro lens diameter, the average value measured at three places was used.

(Evaluation of Micro Lens Height (H)

The height (H) of the microlenses formed on the acrylic resin substrate was measured in a 3D mode using a stylus film thickness meter P-15, and the average value thereof was calculated. For the height of the microlens, an average value measured at three places was used.

(Evaluation of H / D)

The diameter (D) and the height (H) of the microlens obtained as described above were calculated by H / D.

The results are shown in Table 1.

It was found that the inks of Examples 1 to 6 are superior in adhesion to an acrylic resin substrate as compared with the inks of Comparative Examples 1 and 2. Further, the surface-lyophobic cured films obtained by the inks of Examples 1 to 6 are difficult to be colored (yellow) and excellent in transparency and lyophobicity. When a microlens is formed on a cured film, the height / diameter of the surface- to be. Therefore, the ink of the present invention can be suitably used for manufacturing a light guide plate for a high-quality image display apparatus and the like.

As described above, the ink of the present invention is useful in manufacturing high-quality optical parts.

Claims (17)

A photocurable inkjet ink (1) containing an organic solvent (A), a bifunctional or less difunctional (meth) acrylate (B), a urethane (meth) acrylate (C), a surfactant (D) and a photopolymerization initiator as,
The content of the organic solvent (A) is 40 to 98% by weight based on 100% by weight of the photocurable inkjet ink,
Wherein the surfactant (D) is a compound having at least one reactive group. The method according to claim 1,
Wherein the (meth) acrylate (B) is at least one compound selected from the group consisting of a compound represented by the following chemical formula (1), glycerin mono (meth) acrylate, glycerin di (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl (Meth) acrylate. The photocurable inkjet ink according to claim 1, wherein the at least one compound is selected from the group consisting of (meth) acrylate and (meth) acrylate.

(1)
(Wherein R ^a is an alkylene of 2 to 12 carbon atoms which may have a cyclic structure independently, R ^b is alkyl or hydrogen of 1 to 6 carbon atoms, and n is an integer of 1 to 30 to be.) The method according to claim 1,
Wherein the (meth) acrylate (B) is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono &Lt; / RTI &gt; The method according to claim 1,
Wherein the urethane (meth) acrylate (C) is a compound represented by the following formula (2).

(2)
(Wherein R ¹ , R ² and R ³ are each independently a divalent organic group having 1 to 20 carbon atoms; R ⁴ and R ⁵ are each independently hydrogen or alkyl having 1 to 6 carbon atoms; and m And n are each independently an integer of 1 to 3.) 5. The method of claim 4,
Wherein R ¹ and R ³ in the formula (2) are each independently an alkylene having 1 to 10 carbon atoms and R ² is a bivalent group selected from the following group (a).

.... Group (a) The method according to claim 1,
Further comprising (meth) acrylate (F) other than the (meth) acrylate (B) and the urethane (meth) acrylate (C). The method according to claim 1,
Wherein the surfactant (D) is at least one compound selected from the group consisting of a fluorine-based surfactant and a silicone-based surfactant. The method according to claim 1,
Wherein the reactive group of the surfactant (D) is at least one group selected from the group consisting of (meth) acryloyl, epoxy and oxetanyl. The method according to claim 1,
Wherein the organic solvent (A) is an organic solvent having a boiling point of 100 to 300 占 폚. The method according to claim 1,
Wherein the organic solvent (A) is a compound having a hydroxy group. The method according to claim 1,
And a viscosity at 25 占 폚 of 1.0 to 30 mPa 占 퐏. A surface-lyophobic cured film obtained by curing the photocurable ink-jet ink according to any one of claims 1 to 11. A micro lens formed by the ink jet method on the surface lyophobic curing film according to claim 12. A method of forming a microlens, comprising the step of forming a microlens on the surface liquid-repellent curable film according to claim 12 by an ink-jet method. An optical component having a microlens according to claim 13. A video display device comprising the optical component according to claim 15. delete