KR20120137258A - Photocurable inkjet ink - Google Patents

Abstract

PURPOSE: A photocurable inkjet ink is provided have excellent wettability to an acryl resin substrate, and to form excellent liquid-proof surface cured film with excellent adhesion to a substrate. CONSTITUTION: A photocurable inkjet ink comprises an organic solvent, bifunctional or less (meth)acrylate having a hydroxy group, urethane(meth)acrylate, a surfactant, and a photopolymerization initiator. The content of the solvent is 40-98 weight% based on 100.0 weight%. The (meth)acrylate is one or more compounds selected from a compound represented by chemical formula 1, glycerine mono(meth)acrylate, glycerine di(meth)acrylate, and 2-hydroxy-3-acryloyl-oxypropyl(meth)acrylate.

Description

Photocurable Inkjet Inks {PHOTOCURABLE INKJET INK}

The present invention relates to a photocurable inkjet ink suitably used for producing optical equipment such as an image display device. More specifically, the present invention relates to a photocurable inkjet ink suitable for the manufacture of an optical component having a microlens used in a backlight unit.

Background Art Conventionally, microlenses formed on a light guide plate for an image display device are formed by injection molding using a mold. In this method, a mold is required for each product design, and it is a method that requires a considerable cost when manufacturing a small quantity and a large variety of microlenses.

Recently, a method of forming a microlens on the surface of a substrate by the inkjet method has been proposed as a low cost and high degree of freedom in design. However, microlenses formed using a conventional composition have a nonuniformity in pattern size and pattern height. Seriously, it became a problem.

In order to improve this problem, it has been proposed to perform liquid repellent treatment on the surface of the substrate by the inkjet method. In this liquid repellent treatment, a negative photosensitive composition (for example, see Japanese Patent Laid-Open No. 2008-209739 (Patent Document 1)) and the like which can form a surface liquid repellent cured film can be used.

Prior art literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-209739

However, the negative photosensitive composition of patent document 1 may be inferior to wet development property with respect to board | substrates, such as an acrylic resin substrate, and the cured film obtained may be inferior to adhesiveness to a board | substrate.

 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a photocurable inkjet ink capable of forming a surface-repellent cured film having excellent wettability to a substrate such as an acrylic resin substrate and having excellent adhesion to the substrate. It is aimed at.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject can be solved by the photocurable inkjet ink containing a specific amount of organic solvent, a specific (meth) acrylate, a urethane (meth) acrylate, surfactant, and a photoinitiator, and based on this, The present invention was completed.

That is, the present invention includes the following terms.

[1] A sight containing an organic solvent (A), a bifunctional or less (meth) acrylate (B) having a hydroxy group, a urethane (meth) acrylate (C), a surfactant (D), and a photopolymerization initiator (E) As a chemical inkjet ink,

Photocurable inkjet ink whose content of the said solvent (A) is 40-98 weight% with respect to 100 weight% of photocurable inkjet inks.

[2] The compound (meth) acrylate (B) represented by the following general formula (1), glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and 2-hydroxy-3-acryloyl- The photocurable inkjet ink according to [1], which is at least one compound selected from the group consisting of oxypropyl (meth) acrylate.

....화학식(1)

.... Formula (1)

(In formula (1), n R ^<a> is ^a C2-C12 alkylene which may each independently have a cyclic structure, R <^b> is a C1-C6 alkyl or hydrogen, n is an integer of 1-30. to be.)

[3] The (meth) acrylate (B) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydride. Selected from the group consisting of hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate The photocurable inkjet ink according to [1] or [2], which is at least one 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 general formula (2).

....화학식(2)

.... Formula (2)

(In formula (2), 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, m And n are each independently an integer of 1 to 3.)

[5] R ¹ and R ³ in Formula (2) are each independently alkylene having 1 to 10 carbon atoms, and R ² is a divalent group which is one kind selected from the following group (a): [4] The photocurable inkjet ink described in.

....그룹(a)

.... Group (a)

[6] The photocurable according to any one of [1] to [5], further comprising (meth) acrylate (F) other than the (meth) acrylate (B) and the urethane (meth) acrylate (C). 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 fluorine-based surfactant and a silicone-based 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], in which 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 photocurable inkjet ink according to any one of [1] to [12].

[14] A microlens formed on the surface liquid repellent cured film according to [13] by an inkjet method.

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

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

[17] An image display device comprising the optical component according to [16].

 The photocurable inkjet ink of the present invention is excellent in wet spreadability with respect to substrates such as acrylic resin substrates. For this reason, by apply | coating the photocurable inkjet ink of this invention to board | substrates, such as an acrylic resin substrate, and hardening by the inkjet method, the surface liquid repellent cured film whose film thickness is 1 micrometer or less can be formed easily.

 In addition, since the surface liquid repellent cured film obtained by the photocurable inkjet ink of the present invention can be thinned (film thickness is 1 μm or less), since there is little coloring and the surface liquid repellency is high, the microlens is formed on the cured film by an inkjet method. By forming the microlenses, a large ratio of the pattern height to the pattern diameter can be easily formed, and an optical part such as a light guide plate can be easily manufactured.

 Furthermore, since the surface liquid repellent cured film obtained by the photocurable inkjet ink of this invention is excellent in adhesiveness with board | substrates, such as an acrylic resin substrate, surface liquid repellency excellent in the reliability which is hard to produce peeling from a board | substrate also in long-term use. A cured film can be provided.

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

[1.Photocurable Inkjet Ink]

The photocurable inkjet ink (hereinafter also referred to as 'ink of the present invention') of the present invention is an organic solvent (A), a bifunctional or less (meth) acrylate (B) having a hydroxy group, or a urethane (meth) acrylate ( C), surfactant (D) and photopolymerization initiator (E), and the solvent (A) is included 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 the above-described organic solvent (A), bifunctional or less (meth) acrylate (B), urethane (meth) acrylate (C), surfactant (D), and photopolymerization having a hydroxyl group. Since it contains an initiator (E), it is excellent in wet development property with respect to board | substrates, such as an acrylic resin substrate, and is excellent in adhesiveness with a board | substrate by apply | coating this ink to board | substrates, such as an acrylic resin substrate, and hardening | curing by the inkjet method. And the surface liquid repellent cured film whose film thickness is 1 micrometer or less can be formed easily. In addition, when a microlens is formed by the inkjet method on the surface liquid repellent cured film obtained by the ink of this invention, a microlens with a large ratio of the pattern height with respect to a pattern diameter (0.18 or more) can be easily formed.

The ink of this invention is a (meth) acrylate (F) other than (meth) acrylate (B) and urethane (meth) acrylate (C), superposition | polymerization as needed within the range which does not impair the summary of this invention. Other components, such as a inhibitor, thermosetting compounds other than an epoxy compound, a flame retardant, a thermal polymerization initiator, antioxidant, a silane coupling agent, may also be included.

The ink of the present invention may be colorless or colored. Although colorless is preferable from a viewpoint of transmittance | permeability, you may contain a trace amount of colored compounds in the range which does not inhibit the effect of this invention. For example, a colorant may be included in order to facilitate identification with the substrate when inspecting the state of the cured film. In this case, it is preferable that the color of a cured film does not have a yellowish feeling, For example, a blue coloring agent can be used.

In this specification, "(meth) acrylate" is used in order to show both or one side of an acrylate and a methacrylate. "Epoxy compound" means the compound which has an epoxy group (oxirane).

<1.1. Organic Solvents (A)>

The ink of this invention contains 40-98 weight% of organic solvents (A) with respect to 100 weight% of this ink. When the content of the solvent (A) is in the above range, an ink excellent in wet development property to a substrate can be obtained, and by the inkjet method, a surface liquid-repellent cured film having a thin film thickness (for example, 1 μm or less) can be formed. Can be. It is preferable that it is 50-90 weight% with respect to 100 weight% of the ink of this invention, and, as for content of the said solvent (A), it is more preferable that it is 50-70 weight%. On the other hand, when the content of the solvent (A) is less than 40% by weight, the obtained ink tends to have poor wet developability to the substrate, and the resulting cured film tends to be thickened and easily colored (yellowed). .

When the solvent (A) is an organic solvent having a boiling point of 100 to 300 ° C., when the ink obtained is applied onto a substrate such as an acrylic resin substrate by an inkjet method, the wet development property to the substrate becomes good. Since the surface liquid repellent cured film of a uniform film thickness can be formed, it is preferable. Furthermore, using the compound which has a hydroxyl group as said solvent (A) can obtain the ink which clogging of an inkjet head does not produce easily It is more preferable for reasons such as a point.

Specific examples of the organic solvent having a boiling point of 100 to 300 ° C. include butyl acetate, butyl propionate, ethyl lactate, methyl methoxy acetate, ethyl methoxy acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate and 3-meth Methyl oxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, dioxane , 3-methoxybutanol, 3-methoxybutyl acetate, 2-hydroxyisobutyrate methyl, 2-hydroxyisobutyric acid i-propyl, 2-hydroxyisobutyric acid i-butyl, 2-hydroxyisobutyrate n- Butyl, 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 monophenyl 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, glycerin, 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 Cetate, 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 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, γ- Butyrolactone, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone.

Moreover, as a specific example of the compound which has the said hydroxyl group, 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 Phenyl 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 monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, and 1,4 - It may be a shot at Dior.

As said solvent (A), the organic solvent which contains 40 weight% or more of the compound which has these hydroxyl groups in the whole solvent (A) is preferable.

As said solvent (A), among these organic solvents, 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 uniform in film thickness to use an organic solvent containing 40% by weight or more of the solvent (A) as a compound selected from diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, and dipropylene glycol monomethyl ether. It is preferable at the point etc. which obtain the high surface liquid repellent cured film.

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

<1.2. Bifunctional or less (meth) acrylate (B) which has a hydroxyl group>

The ink of this invention contains the bifunctional or less (meth) acrylate (B) which has a hydroxyl group (henceforth a "compound (B)."). When the ink of the present invention contains the compound (B), it is possible to form a surface-repellent cured film excellent in adhesion to the substrate, and even in long-term use, excellent surface-repellent curing which does not easily peel off from the substrate. You can get a film.

In addition, "(meth) acrylate below bifunctional" means the (meth) acrylate which has two or less (meth) acryloyl groups in 1 molecule.

As said compound (B), the compound represented by the said General formula (1), glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and 2-hydroxy-3-acryloyl-oxypropyl (meth) acrylate It is preferable that it is at least 1 sort (s) of compound chosen from the group which consists of the point which can obtain the excellent surface liquid repellent cured film by adhesiveness with a board | 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 and may differ. This rule also applies to other formulas.

As said compound (B), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate At least one compound selected from the group consisting of 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate. It is preferable at the point which can obtain the surface liquid repellent cured film which was more excellent in adhesiveness with a board | substrate.

As said compound (B), the compound manufactured by a well-known method may be used, and a commercial item may be used.

As a commercial item, Brenma GMR (brand name, glycerin dimethacrylate, Nichiyu Co., Ltd. product), 4-hydroxybutyl acrylate (Nippon Kasei Chemical Co., Ltd.) ., Ltd.), and 1, 4- cyclohexane dimethanol monoacrylate (made by Nippon Kasei Chemical Co., Ltd.), etc. are mentioned.

The compound (B) used 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, the sum of the content of the compound (B), the weight of the compound (B), the weight of the compound (C), and the weight of the compound (F) is 10 to 60 weight based on 100% by weight. If it is%, since the surface liquid repellent cured film excellent in the adhesiveness with respect to an acrylic resin substrate can be obtained, it is preferable, More preferably, it is 12 to 55 weight%, More preferably, it is 15 to 50 weight%.

<1.3. Urethane (meth) acrylate (C)>

The ink of this invention contains urethane (meth) acrylate (C) (henceforth a "compound (C)."). In addition, a compound (C) is compounds other than the said compound (B). The surface-repellent cured film obtained by the ink containing the compound (C) has good uniformity in film thickness, excellent adhesion to substrates such as acrylic resin substrates, and further cures with a small exposure amount (high sensitivity), and 1 μm. Since the following film thickness turns into a thin surface liquid repellent cured film, it is preferable.

As a compound (C), it is preferable to use the compound represented by the said General formula (2) in the point which can obtain the ink excellent in photocurability, and can form a surface liquid repellent cured film easily.

In the above formula (2),

R ¹ and R ³ are each independently a divalent organic group having 1 to 20 carbon atoms, and in terms of obtaining a surface-repellent cured film having a more uniform film thickness, preferably each independently having 1 to 10 carbon atoms. Alkylene,

R ² is a divalent organic group having 1 to 20 carbon atoms, and in view of obtaining a surface liquid-repellent cured film having better uniformity in film thickness, etc., preferably one kind of divalent groups selected from the group (a) ,

m and n are the integers of 1-3 each independently, In curability of an ink etc., 2 or 3 is respectively independently preferable, and it is more preferable that it is three.

As said compound (C), using the component containing the compound represented by following General formula (3) can obtain the ink excellent by photocurability, and can obtain the surface liquid repellent cured film with more uniformity of film thickness. It is preferable at the point which exists. As a component containing the compound represented by following General formula (3), NK oligo U-6LPA (brand name, the product made by Shin-Nakamura Chemical Co., Ltd.) etc. are mentioned.

....화학식(3)

.... Formula (3)

The compound (C) used 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, the content of the compound (C) is 10 to 60% by weight based on 100% by weight of the total weight of the compound (B), the weight of the compound (C) and the weight of the compound (F). Since the ink excellent in photocurability can be obtained and the surface liquid repellent cured film excellent in the uniformity of film thickness can be obtained, it is preferable, More preferably, it is 15 to 45 weight%, More preferably, it is 20 to 35 weight% to be.

<1.4. Surfactant (D)>

The ink of this invention contains surfactant (D). If it contains surfactant (D), since the surface liquid repellency of the surface liquid repellent cured film obtained becomes high, it is preferable.

As a specific example of surfactant (D), Polypro No.45, Polypro KL-245, Polypro No.75, Polypro No.90, Polypro No.95 (brand name, Kyoeisha Chemical) (Products from KYOEISHA CHEMICAL CO., LTD.), Disperbyk 161, Disperbeek 162, Disperbeek163, Disperbeek164, Disperbeek166, Disperbeek170, Disperbeek 180, Dispervik 181, Dispervik 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (brand name, product made by BYK Kemi Japan Co., Ltd.), KP-341, KP-358, KP- 368, KF-96-50CS, KF-50-100CS (brand name, product of Shin-Etsu Chemicla Co., Ltd.), Safron SC-101, Safron KH-40 (brand name, three Already Chemical Co., Ltd., Futagent 222F, Futagent 251, FTX-218 (trade name, Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (trade name, manufactured by Mitsubishi Materials Corporation), Mega Park F-171, Mega Park F-177, Mega Park F-475, Mega Park R-08, Mega Park R-30 (trade name, manufactured by DIC Corporation), fluoroalkyl benzenesulfonates, fluoroalkyl carbonates, fluoroalkyl polyoxyethylene ethers, fluoro Alkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethylammonium salt, fluoroalkyl aminosulfonate, polyoxyethylene nonylphenyl ether , Polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxy Ethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, small Non-stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene nap Tyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate are mentioned.

Moreover, since surfactant (D) is fluorine-type surfactant or silicone type surfactant, since the surface liquid repellency of the obtained surface liquid repellent cured film becomes higher, it is preferable. In particular, when the surfactant (D) is a silicone-based surfactant, when the microlenses are formed on the obtained surface liquid repellent cured film by the inkjet method, the microlenses are small in size and have a large ratio of pattern height to pattern diameter. It is more preferable because there is.

If surfactant (D) is a compound which has at least one reactive group further, even if it is an ink containing many solvents (A), since it becomes an ink with high hardenability, it is preferable. As said reactive group, at least 1 group chosen from the group which consists of (meth) acryloyl, an epoxy, and oxetanyl is preferable at the point which can obtain the ink with high curability.

As a specific example of surfactant which has (meth) acryloyl as a reactive group, RS-72K (brand name, the product made by DIC Corporation), BYK UV 3500, BYK UV 3570 (brand name, the product made by BYK Chemi Japan Co., Ltd.) ), TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500 (trade name, product of Evonik Degussa Japan Co., Ltd.).

Moreover, RS-211K (brand name, the product made by DIC Corporation) etc. are mentioned as surfactant which has an epoxy as a reactive group.

The surfactant (D) used 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, the weight ratio ((B) + (C) :( D)) of the sum of the weight of the compound (B) and the weight of the compound (C) to the surfactant (D) is 1000: 1 to 1: The range of 1 is preferable because the balance is good and excellent in the photocurability of the ink and the liquid repellency of the resulting cured film surface. Furthermore, the weight ratio (B) + (C) :( D) is more preferably in the range of 500: 1 to 2: 1, still more preferably in the range of 200: 1 to 5: 1, and 100: 1 to 10 It is especially preferable that it is the range of: 1.

<1.5. Photoinitiator (E)>

The ink of this invention contains a photoinitiator (E). The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of generating radicals by irradiation with ultraviolet (UV) light or visible light, but is not limited to α-hydroxyalkylphenone-based photoinitiator, acylphosphine oxide-based photoinitiator, and An oxyphenyl acetate ester photoinitiator is preferable, and especially an oxyphenyl acetate ester photoinitiator is more preferable from a viewpoint of the photocurability of an ink, the transmittance | permeability of the obtained surface liquid repellent cured film, etc.

As a specific example of a photoinitiator (E), benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4- diethyl thioxane Ton, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, camphorquinone, benzanthrone, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4,4'-di (t- Butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxy Carbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methock Carbonyl) -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- Bis (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'-tet Kis (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-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) Carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-1-prop Panon, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane, 2-hydroxy-1- {4- [4- (2-hydroxy Roxy-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- (dimethyl Mino) -2-[(4-methylphenyl) 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, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-e A mixture of oxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoyl formate, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinic acid ester, 1- [4- (phenylthio) phenyl] -1,2-octanedione2- (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- propane, 2-hydroxy-2-methyl-4'-isopropyl propiophenone, 1-hydroxycyclohexylphenyl ketone, and oxy- Phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2 A mixture of-[2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoyl formate, bis (2, 4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable,

Oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, oxy-phenyl- A mixture of 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, methyl benzoyl formate, and 2 More preferred is 4,6-trimethylbenzoyldiphenylphosphine oxide.

As a commercial item of a photoinitiator (E), Irgacure184, Irgacure651, Irgacure127, DAROCUR1173, Irgacure500, Irgacure2959, Irgacure754, DAROCUR MBF, LucirinTPO (brand name, BASF Japan Ltd. make) are mentioned.

Among these, Irgacure754, DAROCUR MBF, and Lucirin TPO (trade name, product of BASF Japan Co., Ltd.) are preferable.

1 type of compounds may be sufficient as the photoinitiator (E) used for the ink of this invention, and a mixture of 2 or more types of compounds may be sufficient as it.

In the ink of the present invention, the content of the photopolymerization initiator (E) is 1 to 50 parts by weight based on 100 parts by weight of the total of the weight of the compound (B), the weight of the compound (C) and the weight of the compound (F), Since the ink excellent in the photocurability with respect to an ultraviolet-ray can be obtained, and the surface liquid repellent cured film of a high light transmittance can be obtained, it is preferable, More preferably, it is 1-40 weight part, More preferably, it is 5-30 weight It is wealth.

<1.6. (Meth) acrylates (F) other than a compound (B) and a compound (C)>

The ink of the present invention is the compound (B) and the compound (C) for the purpose of appropriately adjusting the relationship between the solid content concentration and the viscosity in the ink or to improve the applicability (wet developability) to various substrates, particularly acrylic resin substrates. (Meth) acrylate (F) (hereinafter abbreviated as "compound (F)") other than) may be contained.

Specific examples of the compound (F) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, bisphenol Fethylene oxide modified di (meth) acrylate, Bisphenol Aethylene oxide modified di (meth) acrylate, polyethyleneglycol di (meth) acrylate, polypropylene glycoldi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, 1,4-cyclohexanedimethanoldi (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propane Oldi (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate , Propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate , Diglycerin tetra (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ε-caprolactone modified tris (acroxyethyl) isocyanurate, tricyclodecane dimethanol di ( Meta) acrylate, alkoxylated cyclohexanedimethanoldi (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth Ta) acrylate, methylglycidyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 3-methyl-3 -(Meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxymethyl oxetane, 2-trifluoromethyl-3- ( Meta) acryloxymethyl oxetane, 4-trifluoromethyl-2- (meth) acryloxymethyl oxetane, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) Acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl ( Meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclophene 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, phenyl (meth) acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylic (Meth) acrylate which is an ethylene oxide addition product of the rate, 2-phenoxyethyl (meth) acrylate, lauryl alcohol, monosuccinate [2- (meth) acryloyloxyethyl], monomaleic acid [2- (meth) ) Acryloyloxyethyl] and cyclohexene-3,4-dicarboxylic acid mono [2- (meth) acryloyloxyethyl].

Among these, when the said compound (F) is apply | coated by the inkjet method, the ink excellent in the wet development property to board | substrates, such as an acrylic resin substrate, can be obtained, and the surface liquid repellent cured film which is uniform and thin is obtained can be obtained. Etc., polyfunctional (meth) acrylates having at least one selected from the group consisting of cycloalkyl and cycloalkylene are preferred, and tricyclodecane dimethanol diacrylate is more preferred.

As said compound (F), the compound manufactured by a well-known method may be used, and a commercial item may be used.

As a commercial item, IRR214-K (brand name, tricyclodecane dimethanol diacrylate, the product of DAICEL-CYTEC Company LTD.), Aronix M-208, an aronix M-305 (brand name, Toagosei Co., Ltd. product (TOAGOSEI CO., LTD.) Etc. are mentioned.

The compound (F) which can be used for 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 compound (F) is 0 to 200 parts by weight based on 100 parts by weight of the total amount of the weight of the compound (B) and the weight of the compound (C), it is directed to a substrate such as an acrylic resin substrate. Since the surface liquid repellent cured film excellent in wet developability can be obtained, it is preferable, More preferably, it is 35-170 weight part, More preferably, it is 70-140 weight part.

<1.7. Polymerization inhibitor>

The ink of this invention may contain a polymerization inhibitor, in order to improve storage stability. As a specific example of a polymerization inhibitor, 4-methoxy phenol, hydroquinone, and phenothiazine are mentioned. Among these, the use of phenothiazine is preferable because an ink having a small increase in viscosity can be obtained even in long-term storage.

The polymerization inhibitor which can be used for 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 polymerization inhibitor is 0.01 to 1 part by weight relative to 100 parts by weight of the total amount of the weight of the compound (B) and the weight of the compound (C), the increase in viscosity is small even in long-term storage. Since an ink is obtained, it is preferable, and considering the balance of storage stability and photocurability, More preferably, it is 0.01-0.5 weight part, More preferably, it is 0.01-0.1 weight part.

<1.8. Thermosetting Compounds other than Epoxy Compounds>

The ink of this invention may also contain thermosetting compounds other than an epoxy compound. It will not specifically limit, if it is a compound which has a functional group which can be thermosetted as said thermosetting compound, Bismaleimide, a phenol resin, resin containing a phenolic hydroxyl group, a melamine resin, an epoxy hardening agent, etc. are mentioned.

One type of compound may be sufficient as thermosetting compounds other than the epoxy compound which can be used for the ink of this invention, and the mixture of 2 or more types of compounds may be sufficient as it.

In the ink of the present invention, the content of thermosetting compounds other than the epoxy compound is 2 to 50 parts by weight based on 100 parts by weight of the total amount of the weight of the compound (B) and the weight of the compound (C). Since heat resistance improves, it is preferable, More preferably, it is 5-30 weight part, More preferably, it is 10-20 weight part.

1.8.1 Bismaleimide

As bismaleimide, the compound represented by following General formula (4) is mentioned, for example. Bismaleimide represented by following General formula (4) is obtained by making diamine and an acid anhydride react, for example.

....화학식(4)

.... Formula (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)

.... Formula (5)

In formula (5), R ¹³ and R ¹⁴ each independently represent an alkylene having 1 to 18 carbon atoms in which any methylene (non-contiguous) non-contiguous (non-adjacent) substituent may be substituted with oxygen, and an aromatic ring which may have a substituent. It is a divalent group which has, or cycloalkylene which may have a substituent. Examples of the substituent include carboxyl, hydroxy, alkyl having 1 to 5 carbon atoms and alkoxy having 1 to 5 carbon atoms. In that the heat resistance can be obtained a cured film high-component surface foot, R ¹³ and R ¹⁴ preferably each independently represent a divalent group to one member selected from the group (8).

....그룹(8)

.... Group (8)

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

....그룹(9)

.... Group (9)

Bismaleimide which can be used for the ink of this invention may be 1 type of compounds, or the mixture of 2 or more types of compounds may be sufficient as it.

1.8.2 Phenolic resins or resins containing phenolic hydroxyl groups

As a phenol resin, the novolak resin obtained by the condensation reaction of the aromatic compound and aldehydes which have a phenolic hydroxyl group is used preferably, As resin containing a phenolic hydroxyl group, the homopolymer of vinylphenol (including a hydrogenated substance), and And vinylphenol copolymers (including hydrogen additives) of vinylphenol and a compound copolymerizable therewith 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, p-ethylphenol, o-butylphenol, m-butylphenol and p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogarol, bisphenol A, bisphenol F, terpene skeleton-containing diphenol , A molded asset, a molded asset ester, (alpha)-naphthol, (beta) -naphthol, etc. are mentioned.

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

As a compound which can be copolymerized with vinylphenol, (meth) acrylic acid or its derivative (s), styrene or its derivative (s), maleic anhydride, vinyl acetate, acrylonitrile, etc. are mentioned.

Specific examples of the phenol resin or the resin containing a phenolic hydroxyl group include ready top PSM-6200 (trade name, manufactured by GUN EI CHEMICAL INDUSTRY CO., LTD.), Shool BRG-555 (trade name, product of SHOWA DENKO KK), Maruka Linker MS-2P, Maruka Linker CST70, Maruka Linker PHM-C (brand name, Maruzen Petrochemical ( (Manufactured by Maruzen Petrochemical Co., LTD.)).

The resin containing phenol resin or phenolic hydroxyl group which can be used for the ink of this invention may be 1 type of compounds, or the mixture of 2 or more types of compounds may be sufficient as it.

1.8.3 melamine resin

The melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, and may be methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, and etherified methylol benzoguar. Condensates, such as namin, etc. are mentioned. Among these, the condensate of etherified methylol melamine is preferable at the point that the chemical-resistance of the obtained surface liquid repellent cured film becomes favorable.

As a specific example of a melamine resin, Nikarak MW-30, MW-30HM, MW-390, MW-100LM, MX-750LM (brand name, the product made by Sanwa Chemical Co., Ltd.) is mentioned. .

Melamine resin which can be used for the ink of this invention may be 1 type of compounds, or the mixture of 2 or more types of compounds may be sufficient as it.

1.8.4 Epoxy Curing Agent

The ink of this invention may contain an epoxy hardening agent in order to improve the chemical-resistance of the obtained surface liquid repellent cured film further. As an epoxy hardening | curing agent, an acid anhydride type hardening | curing agent, a polyamine type hardening | curing agent, etc. are preferable.

Examples of the acid anhydride curing agent include maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrotrimeric anhydride, phthalic anhydride, trimellitic anhydride, and styrene-maleic anhydride copolymers. Can be.

Examples of the polyamine-based curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamideamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, and m-phenylene Diamine, 1,3-bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane And diaminodiphenyl sulfone.

The epoxy hardener which can be used for 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. If the ink of this invention contains a flame retardant, since a flame-retardant high surface liquid repellent cured film can be obtained, it is preferable. The flame retardant is not particularly limited as long as it is a compound capable of expanding flame retardancy, but it is preferable to use an organophosphorus flame retardant from the viewpoint of low toxicity, low pollution and safety.

As an organophosphorus flame retardant, a triphenyl phosphate, a tricresyl phosphate, a trixylenyl phosphate, a cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, 9,10- dihydro-9-oxa-10- phosphazanthrene -10 oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and condensation 9,10-dihydro-9-oxa-10 Phosphazphenanthrene-10 oxide and the like.

As a flame retardant, it is preferable to use the compound which has a structure represented by following General formula (6) in that the bleed out of a flame retardant does not occur easily even if the obtained surface-repellent cured film is left to stand at high temperature. As a compound which has a structure represented by following General formula (6), the compound represented by following General formula (7) is preferable, As a compound represented by following General formula (7), condensation 9,10-dihydro-9-oxa-10-force Pafenanthrene-10 oxide etc. are mentioned. As a commercial item of the compound represented by following General formula (7), HFA-3003 (brand name, the Showa Denko Co., Ltd. product) is mentioned.

....화학식(6)

... (6)

....화학식(7)

.... Formula (7)

In formula (7), m is an integer of 0 to 2, n is an integer of 1 to 3, 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 for the ink of the present invention may be one kind of compound or a mixture of two or more kinds of compounds.

In addition, the said flame retardant may use the compound manufactured by a well-known method, and may use the commercial item, such as HFA-3003 (brand name) by the Showa Denko Co., Ltd. product.

Since the flame retardance of the obtained surface liquid-repellent cured film improves that content of the flame retardant used for the ink of this invention is 15-30 weight part with respect to 100 weight part of total amounts of the weight of a compound (B) and the weight of a compound (C), it is preferable. More preferably, it is 20-25 weight part.

<1.10. Thermal Polymerization Initiator>

The ink of the present invention may contain a thermal polymerization initiator in order to improve the curability of the ink 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. . Among these, 2,2'- azobisisobutyronitrile and 2,2'- azobis (2, 4- dimethylvaleronitrile) are preferable.

One type of compound may be sufficient as the thermal polymerization initiator which can be used for the ink of this invention, and the mixture of 2 or more types of compounds may be sufficient as it.

<1.11. Antioxidant ＞

The ink of the present invention may contain an antioxidant from the viewpoint of improving the transparency of the obtained surface-repellent cured film and preventing yellowing when left at a high temperature. Specific examples of the antioxidant include hindered amine antioxidants and hindered phenol antioxidants. Specifically, IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (brand name, product made from BASF Japan Ltd.), etc. are mentioned.

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

<1.12. Silane Coupling Agents>

The ink of this invention may contain a silane coupling agent in order to improve the adhesiveness to the board | substrate of the obtained surface liquid repellent cured film.

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

Among these, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-glycidoxy propyl trimethoxysilane are preferable because they have a reactor and can copolymerize with other components.

The silane coupling agent which can be used for the ink of this invention may be 1 type of compounds, or the mixture of 2 or more types of compounds may be sufficient as it.

<1.13. Viscosity of Ink>

It is preferable that the viscosity at 25 degrees C of the ink of this invention measured with the E-type viscosity meter is 1.0-30 mPa * s. When viscosity is this range, when apply | coating the ink of this invention by the inkjet method, discharge property by an inkjet apparatus will become favorable. The viscosity of the ink of this invention at 25 degreeC becomes like this. More preferably, it is 1.2-25 mPa * s, Especially preferably, it is 1.5-20 mPa * s.

<1.14. Ink Manufacturing Method>

The ink of this invention can be manufactured by mixing each component used as a raw material by a well-known method.

In particular, the ink of this invention is manufactured by mixing the said (A)-(E) component and other components as needed, and filtering and degassing the obtained solution using a fluororesin membrane filter, for example. It is preferable to be. The ink prepared in this way is excellent in discharge property at the time of application | coating by the inkjet method.

<1.15. Preservation of the ink ＞

When the ink of this invention is stored at -20-25 degreeC, the viscosity increase in storage will be small, and storage stability will become favorable.

[2. Application of Ink by Ink Jet Method]

The ink of this invention can be apply | coated using a well-known inkjet method. As the inkjet method, for example, a piezoelectric method for discharging ink from the inkjet head by applying mechanical energy to the ink, and a coating method (so-called thermal method) for discharging ink by applying thermal energy to the ink can be cited. have.

By using the inkjet method, the ink of this invention can be apply | coated easily in a predetermined pattern shape, and a uniform pattern can be formed on a big board | substrate.

As an inkjet head, what has a heat generating part which consists of metals and / or a metal oxide, etc. is mentioned, for example. Specific examples of metals and / or metal oxides include metals such as Ta, Zr, Ti, Ni, Al, and oxides of these metals.

As a coating apparatus which is preferably used when applying with the ink of the present invention, for example, energy corresponding to an application signal is applied to ink in an inkjet head having an ink containing portion in which ink is accommodated, The apparatus which performs application | coating (drawing) corresponding to the said application | coating signal, generating ink droplets is mentioned.

The inkjet coating apparatus is not limited to the one where the inkjet head and the ink receiving portion are separated, but may be one that is integrally formed so that they cannot be separated. In addition, the ink containing portion may be integrated with or separated from the inkjet head so as to be mounted on a carriage or may be provided at a fixed portion of the apparatus. In the latter case, it may be in the form of supplying ink to the inkjet head through an ink supply member, for example, a tube.

[3. Use of Ink]

Since the ink of the present invention is excellent in wet development property on substrates, especially acrylic resin substrates, the production of optical components having microlenses used for the production of optical devices such as image display devices, backlight units, and the like, specifically, micro It is suitably used for performing liquid repellent treatment on the surface of the substrate when manufacturing the lens array. Moreover, according to the ink of this invention, it is excellent in adhesiveness with a board | substrate, especially an acrylic resin board | substrate, and can form the surface liquid repellent cured film excellent in the reliability which does not produce peeling from a board | substrate even in long-term use, and coloring Since the optical parts, such as a light guide plate, can be manufactured few, this ink is useful for manufacturing a high quality image display apparatus. Further, according to the ink of the present invention, it is possible to cope with an increase in size of an optical component or an image display device.

[4. Surface-repellent cured film]

The surface liquid repellent cured film of the present invention is obtained by curing the ink of the present invention described above, and after being applied to the substrate surface by the inkjet method, a film obtained by irradiating and curing light such as ultraviolet rays or visible light is preferable. .

When irradiating ultraviolet rays or visible rays, the amount of light to be irradiated (exposure amount) may be appropriately adjusted according to the composition of the ink, but 100 to 5,000 mJ / cm ² is preferable, and 200 to 4,000 mJ / cm ² is more preferable. More preferably 300 to 3,000 mJ / cm ² . Moreover, 200-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray to be irradiated and visible light, 200-450 nm is more preferable.

In addition, in this invention, exposure amount is the value measured with the integrated light quantity meter UIT-201 (brand name) with the light receiver UVD-365PD (brand name) which is a product made by Ushio Electric Co., Ltd. (USHIO INC.).

When irradiating light, an exposure apparatus may be used, and as an exposure apparatus, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp or a halogen lamp, etc., is mounted, and ultraviolet rays or visible rays range from 200 to 500 nm. If it is an apparatus which irradiates etc., it will not specifically limit.

The board | substrate to which the ink of this invention is apply | coated will not be specifically limited if it can become the object to which ink is apply | coated, The shape is not limited to a flat plate shape, A curved surface shape may be sufficient.

Although it does not specifically limit as said board | substrate, For example, Polyester-type resin substrate which consists of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc .; Polyolefin resin substrates made of polyethylene, polypropylene and polystyrene; Organic polymer films made of polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, polyimide and the like; cellophane; Metal foil; Laminated film of polyimide and metal foil; Paper which has been filled with glassine paper, parchment paper, polyethylene, clay binder, polyvinyl alcohol, starch or carboxymethyl cellulose (CMC) having a filling effect; And glass substrates.

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

As said board | substrate, you may use the board | substrate containing additives, such as antioxidant, an antiaging agent, a filler, a ultraviolet absorber, an antistatic agent, and / or an electromagnetic wave inhibitor, in the range which does not adversely affect the effect of this invention. The substrate may be a substrate which has been subjected to an easy adhesion treatment such as a corona treatment, a plasma treatment, or a blast treatment on at least a part of the surface of the substrate, if necessary, and an easy adhesion layer on the surface. Or a substrate on which a hard coat film is set.

Although the thickness of a board | substrate is not specifically limited, Usually, it is 10 micrometers-10 mm, and it adjusts suitably according to a use purpose.

Although the film thickness of the surface liquid repellent cured film of this invention is not specifically limited, On an optical characteristic, Preferably it is 1 micrometer or less, More preferably, it is 0.5 micrometer or less.

When the film thickness of the surface liquid-repellent cured film of this invention becomes a cured film with poor coloring (yellowing), it is used suitably for formation of the light guide plate in which the cured film with poor coloring (yellowing) is calculated | required.

Since the ink of the present invention is excellent in wet spreadability with respect to a substrate, especially an acrylic resin substrate, when forming a film such as covering the substrate on the substrate, even if the resolution of printing is low, the surface liquid-repellent curing of the film surface is uniform. You can get a film. For this reason, a surface liquid repellent cured film with a thin film thickness can be formed.

On the other hand, with conventional inks, the wet development property of a substrate, especially an acrylic resin substrate, is bad, so that if the resolution of printing is not high, it is difficult to form a film such as covering the substrate. In many cases, only thick cured films were formed.

Since the surface liquid-repellent cured film of the present invention has excellent adhesion to substrates such as acrylic resin substrates, can be thinned, and exhibits high light transmittance and high strength, in particular, the manufacture of microlenses used for backlight units, It is suitably used for formation of a liquid-repellent film provided on the surface of a substrate at the time of manufacturing a microlens array.

[5. Microlens]

The microlens of the present invention is formed on the surface liquid repellent cured film of the present invention by an inkjet method. For this reason, the microlens with small nonuniformity of a pattern diameter and a height can be formed easily.

The microlens-forming ink may be used for formation of the microlens, and the ink is not particularly limited, and a conventionally known one can be used. In addition, the formation method of a microlens is not specifically limited, What is necessary is just to adjust suitably according to the ink to be used.

The lens diameter of the microlens is not particularly limited, but is usually 10 to 100 µm, more preferably 15 to 60 µm, particularly preferably 20 to 50 µm. Although it does not specifically limit also about the height of a lens, Usually, 0.5-30 micrometers is preferable, 1-20 micrometers is more preferable, 2-15 micrometers is especially preferable.

The ratio of the lens height to the lens diameter is not particularly limited, but is preferably 0.18 or more, more preferably 0.2 or more in that an optical component or the like having excellent light extraction efficiency can be produced.

[6. Optical components]

The optical part of this invention has the said microlens. For this reason, it is an optical component excellent in the optical characteristic. A light guide plate etc. are mentioned as said optical component.

[7. Video display device]

The video display device of the present invention includes the optical component. For this reason, it is a video display device excellent in display characteristics.

[Example]

Hereinafter, although an Example further demonstrates this invention, this invention is not limited by these. In addition, below, the photocurable inkjet ink obtained by the Example can only be called ink. That is, for example, the photocurable inkjet ink 1 may be referred to as ink 1.

Example 1

Propylene glycol monomethyl ether (hereinafter, abbreviated as 'PGME') and 4-hydroxybutyl acrylate (trade name, Nippon Kasei Chemical Co., Ltd.) (meth) acrylate (B) Co., Ltd.) and NK oligo U-6LPA (brand name, Shin-Nakamura Chemical Co., Ltd.) (Shin-Nakamura) which is a component containing the urethane (meth) acrylate (C) represented by the said General formula (3) Chemical Co., Ltd.), TEGO Rad 2200N (trade name, manufactured by Evonik Degussa Japan), a surfactant (D), and Irgacure754 (trade name, BASF, a photopolymerization initiator (E)) Japan (BASF Japan Ltd.) was mixed with the following composition, and a uniform solution was obtained, and it filtered with the membrane filter (0.2 micrometer of pore diameter) made from polytetrafluoroethylene (PTFE), and filtered the filtrate (a sight Chemical inkjet ink 1) was obtained.

(A) PGME: 5.22 g

(B) 4-hydroxybutyl acrylate: 1.50 g

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

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure754: 0.45 g

The viscosity of the ink 1 at 25 ° C. was measured using an E-type rotational viscometer (TV-22 (trade name) manufactured by TOKI SANGYO CO., LTD., Hereafter identical). As a result, it was 6.1 mPa? S.

[Example 2]

In Example 1, as (meth) acrylate (B), instead of 4-hydroxybutyl acrylate, Brenmar GMR (trade name, glycerin dimethacrylate, Nichiyu Co., Ltd. product) ), Further using (meth) acrylate (F) IRR214-K (trade name, tricyclodecane dimethanol diacrylate, manufactured by DAICEL-CYTEC Company LTD.), Except having changed the compounding quantity as follows, like Example 1, the photocurable inkjet ink 2 of the following composition was manufactured.

(A) PGME: 4.25 g

(B) Brenma GMR: 1.00 g

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

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure754: 0.45 g

(F) IRR214-K: 1.00 g

It was 5.6 mPa * s when the viscosity of the ink 2 in 25 degreeC was measured.

[Example 3]

In Example 2, photocurable inkjet ink 3 of the following composition was prepared in the same manner as in Example 2 except that 4-hydroxybutylacrylate was used instead of Brenma GMR (trade name) as the (meth) acrylate (B). Prepared.

(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) Irgacure754: 0.45 g

(F) IRR214-K: 1.00 g

It was 5.4 mPa * s when the viscosity of the ink 3 in 25 degreeC was measured.

Example 4

In Example 2, 1,4-cyclohexane dimethanol monoacrylate (Nippon Kasei Chemical Co., Ltd.) instead of Brenma GMR (brand name) as (meth) acrylate (B). A photocurable inkjet ink 4 having the following composition was produced in the same manner as in Example 2 except that the product was used).

(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) Irgacure754: 0.45 g

(F) IRR214-K: 1.00 g

It was 5.8 mPa * s when the viscosity of the ink 4 in 25 degreeC was measured.

[Example 5]

In Example 3, the compounding amount was changed as follows using DAROCUR MBF (trade name, manufactured by BASF Japan Ltd.) instead of Irgacure754 (trade name) as the photopolymerization initiator (E). As in Example 3, 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

It was 5.4 mPa * s when the viscosity of the ink 5 in 25 degreeC was measured.

[Example 6]

In Example 3, as (meth) acrylate (F), instead of IRR214-K (brand name), Aronix M-208 (brand name, bisphenol F ethylene oxide modified (n ≒ 2) diacrylate, Toagosei) Photocurable inkjet ink 6 of the following composition was produced in the same manner as in Example 3, except that the compounding amount was changed as follows using the product of TOAGOSEI CO., LTD.

(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) Irgacure754: 0.45 g

(F) Aaronics M-208: 1.00 g

It was 5.8 mPa * s when the viscosity of the ink 6 in 25 degreeC was measured.

Comparative Example 1

In Example 2, the ink 7 of the following composition was manufactured like Example 2 except having changed the compounding quantity as follows without using (meth) acrylate (B).

(A) PGME: 5.22 g

(B)--

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

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure754: 0.45 g

(F) IRR214-K: 1.50 g

It was 5.8 mPa * s when the viscosity of the ink 7 in 25 degreeC was measured.

Comparative Example 2

Aronics M-305 (brand name, pentaerythritol triacrylate, Toagosei Co., Ltd.) which is a trifunctional acrylate which has a hydroxyl group instead of (meth) acrylate (B) in Example 2 (TOAGOSEI) CO., LTD.)), And the ink 8 of the following composition was manufactured like Example 1 except having changed the compounding quantity as follows.

(A) PGME: 5.22 g

(B)--

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

(D) TEGO Rad 2200N: 0.03 g

(E) Irgacure754: 0.45 g

(F) Aaronics M-305: 1.00 g

(F) IRR214-K: 1.00 g

It was 6.0 mPa * s when the viscosity of the ink 8 in 25 degreeC was measured.

<Evaluation of Inks 1-8>

The following evaluation was performed about the inks 1-8 manufactured in this way.

(Formation of surface liquid repellent cured film)

A 4 cm * 4 cm acrylic resin substrate (ASAHIKASEI TECHNOPLUS Co., Ltd. product, Dera Glass AD999 (trade name)) and a glass substrate were prepared. Ink 1 is injected into an inkjet cartridge and mounted on an inkjet device (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.), and the discharge voltage (piezo voltage) is 16V, the head temperature is 30 ° C, the driving frequency is 5kHz, and the number of coatings is applied once. As the discharge conditions, the print resolution was set at 1250 dpi and applied to the entire surface of each substrate. Subsequently, the substrate 1 was irradiated with ultraviolet light at a UV exposure amount of 2,000 mJ / cm ² using a UV irradiation apparatus (J-CURE1500 manufactured by JATEC Co., Ltd.). And an acrylic resin substrate and a glass substrate on which a surface repellent cured film was formed. Similarly, the board | substrate with which the surface liquid repellent cured film was formed also about the ink 2-8 was obtained.

Furthermore, the microlenses were formed on the acrylic resin substrate in which the surface liquid repellent cured film was formed as follows.

(Formation of Micro Lens)

A photocurable composition (L1) for microlenses is injected into an inkjet cartridge, mounted on an inkjet device (DMP-2831 (trade name) manufactured by FUJIFILM Dimatix Inc.), and discharge voltage (piezo voltage) 22 V, head temperature 34 DEG C, and drive The printing resolution was set to 512 dpi at the frequency of 5 kHz and the number of application times, and was applied in a dot pattern on an acrylic resin substrate (on the surface liquid repellent cured film) on which the surface liquid repellent cured film was formed at 50 μm intervals. Subsequently, the substrate was irradiated with ultraviolet light at a UV exposure amount of 1,000 mJ / cm ² using a UV irradiation apparatus (J-CURE1500 (trade name) manufactured by JATEC Co., Ltd.). A substrate was obtained.

Further, the photocurable composition (L1) for microlens was uniformly mixed with Aaronic M-305 (trade name, 3.5 g), tetrahydrofurfuryl acrylate (3.5 g), and Irgacure754 (trade name, 0.49 g). After obtaining one solution, it was a filtrate obtained by filtration with a PTFE membrane filter (pore diameter 0.2 micrometer), and the viscosity in 25 degreeC was 16.8 mPa * s.

(Film thickness of surface liquid repellent cured film)

In the glass substrate on which the surface liquid repellent cured film was formed, a part of the cured film was scraped off with a cutter knife, and the step was measured by a stylus type film thickness gauge P-15 (trade name, manufactured by KLA-Tencor Japan Co., Ltd.). The film thickness of the cured film was calculated | required.

(Circle) and the case of 1 micrometer or more were made into the case where the film thickness is less than 1 micrometer, and x. The results are shown in Table 1.

(Transparency of surface liquid repellent cured film)

In the glass substrate on which the surface liquid repellent cured film was formed, the transmittance at 400 nm and the angle (b *) at 380 nm to 780 nm of the cured film were determined using an ultraviolet-visible near-infrared spectrophotometer V-670 (trade name, Nippon Electronics Co., Ltd.) (JEOL Ltd.).

Angle b * is an index which shows a yellowish sense, and when a numerical value becomes large, it means that it is colored more yellow. The angle b * is preferably less than 0.1.

(Evaluation of adhesiveness)

After attaching 18mm wide Scotch clear adhesive tape, Transparent Off White _TM 600 (trade name, 3M product) to the surface where the microlens is formed on the acrylic resin substrate on which the microlens is formed, apply the tape 90 degrees to the surface on which the microlens of the substrate is formed. The board | substrate after pulling out was removed and the tape was removed.

(Circle) and the case where peeling generate | occur | produced also in a part of surface liquid repellent cured film or a micro lens were made into x when the surface liquid repellent cured film and a microlens have no abnormality (no peeling is seen).

Furthermore, after performing the high temperature and high humidity test (50 hours of standing at the temperature of 50 degreeC, and 90% of humidity for 100 hours), the same adhesive evaluation was performed.

(Evaluation of Microlens Diameter (D))

The microlens diameter D formed on the acrylic resin substrate was measured using an optical microscope BX51 (trade name, manufactured by OLYMPUS Co., Ltd.). The average value which measured three places was used for the value of a microlens diameter.

(Evaluation of Microlens Height (H))

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

(Evaluation of H / D)

H / D was calculated | required by calculation to the diameter (D) and height (H) of the microlens obtained by making it above.

These results are shown in Table 1.

It was found that the inks of Examples 1 to 6 were superior in adhesion to the acrylic resin substrate as compared with the inks of Comparative Examples 1 and 2. In addition, the surface liquid repellent cured film obtained by the ink of Examples 1 to 6 is difficult to be colored (yellowed), has excellent transparency and liquid repellency, and has a height / diameter of 0.2 or more when a microlens is formed on the cured film. to be. Therefore, the ink of this invention can be used suitably for manufacture of light guide plates, such as for high quality image display apparatuses.

As described above, the ink of the present invention is useful for producing high quality optical parts.

Claims (17)

Photocurable inkjet ink containing an organic solvent (A), a bifunctional or less (meth) acrylate (B) which has a hydroxyl group, a urethane (meth) acrylate (C), surfactant (D), and a photoinitiator (E) as,
Photocurable inkjet ink whose content of the said solvent (A) is 40-98 weight% with respect to 100 weight% of photocurable inkjet inks. The method of claim 1,
The (meth) acrylate (B) is a compound represented by the following general formula (1), glycerin mono (meth) acrylate, glycerin di (meth) acrylate, and 2-hydroxy-3-acryloyl-oxypropyl ( Photocurable inkjet ink which is at least 1 sort (s) of compound chosen from the group which consists of a meta) acrylate.

.... Formula (1)
(In formula (1), n R ^<a> is ^a C2-C12 alkylene which may each independently have a cyclic structure, R <^b> is a C1-C6 alkyl or hydrogen, n is an integer of 1-30. to be.) The method of claim 1,
The said (meth) acrylate (B) is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( At least one selected from the group consisting of meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate The photocurable inkjet ink which is a compound of. The method of claim 1,
Photocurable inkjet ink whose said urethane (meth) acrylate (C) is a compound represented by following General formula (2).

.... Formula (2)
(In formula (2), 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, m And n are each independently an integer of 1 to 3.) 5. The method of claim 4,
The photocurable inkjet ink in which R <^1> and R <^3> in the said General formula (2) are respectively independently C1-C10 alkylene, and R <^2> is a divalent group which is 1 type chosen from the following group (a).

.... Group (a) The method of claim 1,
The photocurable inkjet ink which further contains (meth) acrylate (F) other than the said (meth) acrylate (B) and urethane (meth) acrylate (C). The method of claim 1,
The photocurable inkjet ink of which the said surfactant (D) is at least 1 sort (s) of compound chosen from the group which consists of a fluorine-type surfactant and a silicone type surfactant. The method of claim 1,
The photocurable inkjet ink wherein the surfactant (D) is a compound having at least one reactive group. 9. The method of claim 8,
Photocurable inkjet ink, 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 of claim 1,
The photocurable inkjet ink whose said solvent (A) is an organic solvent with a boiling point of 100-300 degreeC. The method of claim 1,
The photocurable inkjet ink whose said solvent (A) is a compound which has a hydroxyl group. The method of claim 1,
The photocurable inkjet ink whose viscosity in 25 degreeC is 1.0-30 mPa * s. The surface liquid repellent cured film obtained by hardening | curing the photocurable inkjet ink in any one of Claims 1-12. The microlens formed by the inkjet method on the surface liquid repellent cured film of Claim 13. A method of forming a microlens, comprising the step of forming a microlens by an inkjet method on the surface liquid repellent cured film according to claim 13. An optical component having the microlens according to claim 14. An image display device comprising the optical component according to claim 16.