JP6094625B2 - Cured film - Google Patents

Description

  The present invention relates to a photocurable composition suitably used for producing an optical apparatus such as an image display device. More specifically, the present invention relates to a photocurable composition suitable for an optical component having a microlens used for a backlight unit or the like.

  For some time, microlenses formed on light guide plates for liquid crystal displays have been formed by injection molding using a mold. This method requires a mold for each product design, and is very costly in the production of a small variety of products. In recent years, a method of forming a microlens by an inkjet method has been proposed as an inexpensive manufacturing method, but there has been a problem that variations in pattern size and pattern height become large. In order to improve this problem, it has been proposed that the substrate is subjected to water repellent treatment by an ink jet method. For this surface treatment, a negative photosensitive composition that forms a surface water-repellent cured film (for example, see JP-A-2008-209739) can be used. Has a problem that the light guide plate becomes yellowish.

  JP 2008-209739 A

  Under the circumstances described above, an object of the present invention is a photocurable composition capable of being subjected to a surface treatment so as to reduce variations in pattern diameter and height when forming a microlens by an inkjet method. An object of the present invention is to provide a photocurable composition in which the film thickness of a water-repellent cured film formed by coating and exposing by a method is 1 μm or less, more preferably 0.5 μm or less.

The inventors have prepared a photocurable composition containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). And found that a photocurable composition having a solvent (A) content of 40 to 98% by weight is useful for forming a water-repellent cured film having a film thickness of 1 μm or less. The present invention has been completed based on the above.
That is, the present invention includes the following items.

[1] A photocurable composition containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). A photocurable composition having a solvent (A) content of 40 to 98% by weight.

[2] The photocurable composition according to item [1], wherein the solvent (A) is an organic solvent having a boiling point of 100 to 300 ° C.

  Here, 1) The photocurable composition according to item [1] or [2], wherein the content of the solvent (A) is 60 to 98% by weight. 2) The photocurable composition according to item [1] or [2], wherein the content of the solvent (A) is 80 to 98% by weight. 3) The photocurable composition according to Item [1] or [2], wherein the content of the solvent (A) is 90 to 98% by weight.

[3] The photocurable composition according to item [1] or [2], wherein the solvent (A) is an organic solvent having hydroxy.

  Here, 1) the solvent (A) is 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 mono Contains 40% by weight or more of a solvent selected from tilether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, and 1,4-butanediol. The photocurable composition according to any one of Items [1] to [3] is preferred.

2) Solvent (A) is propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, dipropylene The photocurable composition according to any one of Items [1] to [3], further containing a solvent selected from glycol monomethyl ether in an amount of 40% by weight or more based on the total amount of the solvent.

[4] The item [1] to [3], wherein the compound (B) having two or more photoreactive functional groups is a polyfunctional (meth) acrylate, a polyfunctional epoxy compound, or a polyfunctional oxetane compound. The photocurable composition of any one of Claims 1.

  1) The compound (B) having two or more photoreactive functional groups is trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, trimethylolpropane propylene oxide-modified tri (Meth) acrylate, glycerin tri (meth) acrylate, ethylene oxide modified glycerin tri (meth) acrylate, propylene oxide modified glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Sa (meth) acrylate is a compound selected from urethane (meth) acrylate, paragraph [1] to the photocurable composition according to any one of [4] are preferred.

  2) The compound (B) having two or more photoreactive functional groups is selected from pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate. The photocurable composition according to any one of Items [1] to [4], which is a compound, is more preferable.

（式中、Ｒ^１は二価の有機基であり、Ｒ^２及びＲ^３はそれぞれ独立に炭素数が１〜２０のアルキレンであり、Ｒ^４及びＲ^５はそれぞれ独立に水素又は炭素数が１〜６のアルキルであり、ｍ及びｎはそれぞれ独立に１〜３の整数である。）[5] In any one of items [1] to [3], the compound (B) having two or more photoreactive functional groups is a compound represented by the formula (B-1): The photocurable composition as described.

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

（式中、Ｒ^１は

からなる二価の基であり、Ｒ^２及びＲ^３はそれぞれ独立に炭素数が１〜１０のアルキレンであり、Ｒ^４及びＲ^５はそれぞれ独立に水素又は炭素数が１〜６のアルキルであり、ｍ及びｎはそれぞれ独立に１〜３の整数である。）[6] In any one of items [1] to [3], the compound (B) having two or more photoreactive functional groups is a compound represented by the formula (B-2): The photocurable composition as described.

(Wherein R ¹ is

R ² and R ³ are each independently alkylene having 1 to 10 carbon atoms, and 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. )

[7] The photocurable composition according to item [3], wherein the compound (B) having two or more photoreactive functional groups contains fluorine.

[8] The photocurable composition according to any one of items [1] to [7], wherein the surfactant (C) is a fluorine-based surfactant or a silicon-based surfactant.

  Here, 1) The photocurable composition according to any one of Items [1] to [8], wherein the weight ratio (B) :( C) is in the range of 1000: 1 to 1: 5. . 2) The photocurable composition according to any one of Items [1] to [8], wherein the weight ratio (B) :( C) is in the range of 100: 1 to 1: 3. 3) The photocurable composition according to any one of [1] to [8], wherein the weight ratio (B) :( C) is in the range of 20: 1 to 1: 2. 4) The photocurable composition according to any one of Items [1] to [8], in which the weight ratio (B) :( C) is in the range of 10: 1 to 1: 1.

[9] The photocurable composition according to any one of items [1] to [8], wherein the surfactant (C) has one photoreactive functional group.

[10] The photocurable composition according to item [9], wherein the photoreactive functional group of the surfactant (C) is any one of (meth) acryloyl, epoxy, and oxetanyl.

[11] The compound (B) having two or more photoreactive functional groups is a polyfunctional (meth) acrylate, and the photoreactive functional group of the surfactant (C) is (meth) acryloyl, Item [9] The photocurable composition according to Item [9], wherein the photopolymerization initiator (D) is a photoradical generator.

[12] The compound (B) having two or more photoreactive functional groups is a polyfunctional epoxy compound or a polyfunctional oxetane compound, and the photoreactive functional group of the surfactant (C) is epoxy or oxetanyl. The photocurable composition according to Item [9], wherein the photopolymerization initiator (D) is a photoacid generator.

[13] The photocurable composition according to any one of items [1] to [12], wherein the viscosity at 25 ° C. is 1.5 to 30 mPa · s.

[14] A surface water-repellent cured film obtained by irradiating with ultraviolet rays after applying the photocurable composition according to any one of items [1] to [13].

[15] A method for forming a surface water-repellent cured film, comprising a step of applying the photocurable composition according to item [13] by an inkjet method.

[16] A microlens formed on the surface water-repellent cured film according to item [14].

[17] A method for forming a microlens, comprising a step of forming a dot pattern by an inkjet method on the surface water-repellent cured film according to the item [14].

[18] An optical component having the microlens according to item [16].

[19] An image display device including the optical component according to item [18].

  When a microlens is formed by an inkjet method on a water-repellent cured film having a film thickness of 1 μm or less obtained from the photocurable composition of the present invention, an optical component such as a light guide plate with little coloring can be produced. Therefore, the present composition is useful for producing a high-quality video display device.

[1. Photocurable composition of the present invention]
The photocurable composition of the present invention contains a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). It is a photocurable composition and is a photocurable composition whose content of a solvent (A) is 40 to 98 weight%.

  The photocurable composition of the present invention may be colorless or colored. Colorless is preferable from the viewpoint of transmittance, but a colored compound may be contained as long as the effects of the invention are not hindered. Further, for example, a colorant may be included in order to facilitate identification from the substrate when the state of the cured film is inspected.

  In this specification, “(meth) acrylate” is used to indicate both or one of acrylate and methacrylate. “Epoxy compound” means an oxirane compound, and “epoxy” means oxiranyl.

  Moreover, the photocurable composition of this invention can contain a polymerization inhibitor, thermosetting compounds other than an epoxy compound, a flame retardant, etc. as needed. First, a preferred embodiment of the present invention will be described.

  The first aspect of the present invention is a light containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). It is a photocurable composition which is a curable composition and the content of the solvent (A) is 40 to 98% by weight. When this photocurable composition is used, the water repellent cured film obtained by light irradiation after coating by the ink jet method has good film thickness uniformity. Furthermore, a thin film having a thickness of 1 μm or less can be formed.

  The second aspect of the present invention is a light containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). A curable composition, which is a photocurable composition having a solvent (A) content of 40 to 98% by weight, wherein the compound (B) having two or more photoreactive functional groups is urethane (meth). It is a photocurable composition containing an acrylate. When this photocurable composition is used, the water repellent cured film obtained by light irradiation after coating by the ink jet method has good film thickness uniformity. Furthermore, a thin film having a thickness of 1 μm or less can be formed.

  The third aspect of the present invention is a light containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). It is a photocurable composition which is a curable composition and the content of the solvent (A) is 40 to 98% by weight, and the surfactant (C) contains a surfactant having a photoreactive functional group It is a photocurable composition. When this photocurable composition is used, the water repellent cured film obtained by light irradiation after coating by the ink jet method has good film thickness uniformity. Furthermore, a thin film having a thickness of 1 μm or less can be formed and cured with a small exposure amount (high sensitivity).

  The fourth aspect of the present invention is a light containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). A curable composition, which is a photocurable composition having a solvent (A) content of 40 to 98% by weight, wherein the compound (B) having two or more photoreactive functional groups is a polyfunctional epoxy compound. Alternatively, a photocurable composition containing a polyfunctional oxetane compound, a surfactant (C) having a photoreactive functional group having epoxy or oxetanyl, and a photopolymerization initiator (D) containing a photoacid generator It is. When this photocurable composition is used, the water repellent cured film obtained by light irradiation after coating by the ink jet method has good film thickness uniformity. Furthermore, a thin film having a thickness of 1 μm or less can be formed.

  The fifth aspect of the present invention is a light containing a solvent (A), a compound (B) having two or more photoreactive functional groups, a surfactant (C), and a photopolymerization initiator (D). A curable composition having a solvent (A) content of 40 to 98% by weight, wherein the compound (B) having two or more photoreactive functional groups contains fluorine. It is a photocurable composition containing a functional acrylate. When this photocurable composition is used, the water repellent cured film obtained by light irradiation after coating by the ink jet method has good film thickness uniformity, and a thin film having a thickness of 1 μm or less can be formed. Furthermore, when this photocurable composition is used, the value of the height / diameter of the dot pattern to be formed increases, which is preferable when used as a microlens.

  Hereinafter, the viscosity of each of the above components and the photocurable composition of the present invention will be described.

<1.1. Viscosity of Photocurable Composition of the Present Invention>
The viscosity of the photocurable composition of the present invention at 25 ° C. measured with an E-type viscometer is preferably 1.0 to 30 mPa · s. When the viscosity is within this range, when the photocurable composition of the present invention is applied by an ink jet method, the ejection property by the ink jet device is good. The viscosity of the photocurable composition of the present invention at 25 ° C. is more preferably 1.2 to 25 mPa · s, and particularly preferably 1.5 to 20 mPa · s.

<1.2. Solvent (A)>
The photocurable composition of the present invention is a photocurable composition containing 40 to 98% by weight of the solvent (A). When the content of the solvent is 40 to 98% by weight, a thin water-repellent cured film can be obtained by irradiating ultraviolet rays after coating by an ink jet method. The content of the solvent is more preferably 60 to 98% by weight, even more preferably 80 to 98% by weight, and even more preferably 90 to 98% by weight.
Further, when the solvent (A) is an organic solvent having a boiling point of 100 to 300 ° C., the wet repellent property to the substrate is good when applied by the ink jet method, and a water repellent cured film having a uniform film thickness can be obtained. Therefore, an organic solvent having hydroxy is even more preferable.

  Specific examples of the organic solvent having a boiling point of 100 to 300 ° C. include butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, Methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 − Ethyl toxipropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, 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, propylene glycol monomethyl ether acetate, propylene glycol Cole monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, anisole, γ-butyrolactone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethyl And the like can be given Midazorijinon.

  Among these, it is preferable that the solvent (A) has hydroxy because clogging of the ink jet head hardly occurs when the ink is applied by the ink jet method. Specific examples of the organic solvent having hydroxy 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 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, dipropiate Glycol monobutyl ether, dipropylene glycol monophenyl ether, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, benzyl alcohol, cyclohexanol, and 1,4-butane diol.

  Among these organic solvents having hydroxy, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, When the solvent selected from dipropylene glycol monomethyl ether contains 40% or more of the entire solvent (A), it is preferable from the standpoint of increasing the film thickness uniformity of the resulting water-repellent cured film.

  The solvent used in the photocurable composition of the present invention may be one type or a mixture of two or more types.

<1.3. Compound (B) having two or more photoreactive functional groups>
The photocurable composition of the present invention is a photocurable composition containing a compound (B) having two or more photoreactive functional groups. It is preferable that the photoreactive functional group is any one of (meth) acryloyl, epoxy, and oxetanyl since the adhesion of the resulting water repellent cured film to the substrate is high.

  Specific examples of the compound having two or more (meth) acryloyl as a photoreactive functional group include trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and trimethylolpropane propylene oxide. Modified tri (meth) acrylate, glycerin tri (meth) acrylate, ethylene oxide modified glycerol tri (meth) acrylate, propylene oxide modified glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, and the like.

  Among these compounds, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable because the resulting water repellent cured film has high photocurability.

（式中、Ｒ^１は炭素数１〜２０である二価の有機基であり、Ｒ^２及びＲ^３はそれぞれ独立に炭素数が１〜２０のアルキレンであり、Ｒ^４及びＲ^５はそれぞれ独立に水素又は炭素数が１〜６のアルキルであり、ｍ及びｎはそれぞれ独立に１〜３の整数である。）
尚、硬化性の面から、ｍ及びｎは２又は３が好ましく、３であることがより好ましい。In addition, when the compound (B) having two or more photoreactive functional groups is urethane (meth) acrylate, the water repellent cured film obtained by light irradiation after applying the photocurable composition of the present invention by an inkjet method. The film thickness uniformity is particularly preferable. Specific examples of the urethane (meth) acrylate include compounds having the following formula (B-1) structure.

(In the formula, R ¹ is a divalent organic group having 1 to 20 carbon atoms, R ² and R ³ are each independently alkylene having 1 to 20 carbon atoms, and R ⁴ and R ⁵ are each independent. And hydrogen or alkyl having 1 to 6 carbon atoms, and m and n are each independently an integer of 1 to 3).
From the viewpoint of curability, m and n are preferably 2 or 3, and more preferably 3.

（式中、Ｒ^１は

からなる二価の基であり、Ｒ^２及びＲ^３はそれぞれ独立に炭素数が１〜１０のアルキレンであり、Ｒ^４及びＲ^５はそれぞれ独立に水素又は炭素数が１〜６のアルキルであり、ｍ及びｎはそれぞれ独立に１〜３の整数である。）
尚、硬化性の面から、ｍ及びｎは２又は３が好ましく、３であることがより好ましい。It is further preferred that the urethane (meth) acrylate has a structure represented by the following formula, since the film thickness uniformity is even better.

(Wherein R ¹ is

R ² and R ³ are each independently alkylene having 1 to 10 carbon atoms, and 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. )
From the viewpoint of curability, m and n are preferably 2 or 3, and more preferably 3.

  Specific examples of compounds having two or more epoxies as photoreactive functional groups include phenol novolac type, cresol novolac type, bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, Bisphenol S type, trisphenol methane type, tetraphenol ethane type, bixylenol type or biphenol type epoxy compound; alicyclic or heterocyclic epoxy compound; epoxy compound having dicyclopentadiene type or naphthalene type structure, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4 ′ -Diaminodiphenylmethane may be mentioned.

  Various commercially available products can be used as these epoxy compounds. TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals), jER828, 834, 1001, and 1004 (trade names; manufactured by Mitsubishi Chemical Corporation) ), Epicron 840, 850, 1050, 1050, 2055 (trade name; manufactured by DIC), Epototo YD-011, YD-013, YD-127, YD-128 (trade name; Nippon Steel Chemical Co., Ltd.) Made by Co., Ltd.) E. R. 317, 331, 661, 664 (trade name; manufactured by Dow Chemical Co., Ltd.), Araldite 6071, 6084, GY250, GY260 (trade name; manufactured by Huntsman Advanced Material Co., Ltd.), Sumi -Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), A.I. E. R. 330, 331, 661, 664 (trade name; manufactured by Asahi Kasei Co., Ltd.) and the like; jER152, 154 (trade name; manufactured by Mitsubishi Chemical Corporation); E. R. 431, 438 (trade name; manufactured by Dow Chemical Co., Ltd.), Epicron N-730, N-770, N-865 (trade name; manufactured by DIC Corporation), Epototo YDCN-701, YDCN- 704 (trade name; manufactured by Nippon Steel Chemical Co., Ltd.), Araldite ECN1235, ECN1273, ECN1299 (trade name; manufactured by Huntsman Advanced Material), XPY307, EPPN-201, EOCN-1025, EOCN- 1020, EOCN-104S, RE-306 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Sumi-Epoxy ESCN-195X, ESCN-220 (trade name; manufactured by Sumitomo Chemical Co., Ltd.), A.I. E. R. Novolak epoxy compounds such as ECN-235 and ECN-299 (trade name; manufactured by ADEKA Corporation); Epicron 830 (trade name; manufactured by DIC Corporation), jER807 (trade name; manufactured by Mitsubishi Chemical Corporation) Bisphenol such as Epototo YDF-170 (trade name; manufactured by Nippon Steel Chemical Co., Ltd.), YDF-175, YDF-2001, YDF-2004, Araldite XPY306 (trade name; manufactured by Huntsman Advanced Material Co., Ltd.) F-type epoxy compounds; hydrogenated bisphenol A-type epoxy compounds such as Epototo ST-2004, ST-2007, and ST-3000 (trade name; manufactured by Nippon Steel Chemical Co., Ltd.); Celoxide 2021 (trade name; Daicel Chemical) Industrial Co., Ltd.), Araldite CY175, CY179 (trade name; Huntsman Advanced) Such as YL-933 (trade name; manufactured by Mitsubishi Chemical Corporation), EPPN-501, EPPN-502 (trade name; manufactured by Dow Chemical Co., Ltd.), etc. Trihydroxyphenylmethane type epoxy compounds; bixylenol type or biphenol type epoxy compounds such as YL-6056, YX-4000, YL-6121 (trade name; manufactured by Mitsubishi Chemical Corporation) or mixtures thereof; EBPS-200 (product) Name: Nippon Kayaku Co., Ltd.), EPX-30 (trade name; manufactured by ADEKA Corporation), EXA-1514 (trade name; manufactured by DIC Corporation), etc .; bisphenol S type epoxy compound; jER157S (trade name) Bisphenol A novolak type epoxy compound such as Mitsubishi Chemical Corporation; YL-931 (trade name; manufactured by Mitsubishi Chemical Corporation), Aral Tetraphenylol ethane type epoxy compounds such as Ito163 (trade name; manufactured by Huntsman Advanced Material Co., Ltd.); Araldite PT810 (trade name; manufactured by Huntsman Advanced Material Co., Ltd.), TEPIC (trade name; Nissan Chemical Co., Ltd.) Heterocyclic epoxy compounds such as HP-4032, EXA-4750, EXA-4700 (trade name; manufactured by DIC Corporation), and the like; HP-7200, HP-7200H, Examples thereof include an epoxy compound having a dicyclopentadiene skeleton such as HP-7200HH (trade name; manufactured by DIC Corporation).

  Among these epoxy compounds, TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.) is preferably used because the adhesion of the film obtained from the photocurable composition of the present invention to various substrates is high.

Specific examples of the compound having two or more oxetanyl as a photoreactive functional group include xylylene bisoxetane (Aron Oxetane OXT-121 (trade name) manufactured by Toagosei Co., Ltd.), 3-ethyl-3 { [(3-Ethyloxetane-3-yl) methoxy] methyl} oxetane (Aron Oxetane OXT-221 (trade name) manufactured by Toagosei Co., Ltd.), di (3-ethyl-3-oxetanyl) methoxyethyladipic acid (Ube) Examples thereof include bisoxetane adipate manufactured by Kosan Co., Ltd. and bis (3-ethyloxetane-3-ylmethyl) carbonate (dioxetane carbonate manufactured by Ube Industries, Ltd.).
Among these compounds having two or more oxetanyls, xylylene bisoxetane (Aron oxetane OXT-121 (trade name) manufactured by Toagosei Co., Ltd.), 3-ethyl-3 {[((3-ethyloxetane- When 3-yl) methoxy] methyl} oxetane (Aron Oxetane OXT-221 (trade name) manufactured by Toagosei Co., Ltd.) is used, the adhesion of the film obtained from the photocurable composition of the present invention to various substrates is improved. It is preferable because it is high.

  In addition, when the compound (B) having two or more photoreactive functional groups has fluorine, the height / diameter value of the dot pattern formed on the cured film obtained increases. It is preferable when used as a microlens. Various commercially available products can be used as the compound having two or more photocurable functional groups having fluorine, such as fluorite FA-16, fluorite FEA-16, fluorite FE-16, Fluorite ART-4 (trade name; manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  The compound (B) having two or more photoreactive functional groups used in the photocurable composition of the present invention may be one type or a mixture of two or more types.

<1.4. Surfactant (C)>
The photocurable composition of the present invention is a photocurable composition containing a surfactant (C). The inclusion of a surfactant is preferable because the water repellency of the resulting water repellent cured film is increased.
Specific examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all are trade names, manufactured by Kyoeisha Chemical Industry Co., Ltd.), Disperbak 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346 (all are trade names, manufactured by BYK Japan KK), KP-341, KP-358, KP-368, KF-96 -50CS, KF-50-100CS (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (all are trade names, manufactured by Seimi Chemical Co., Ltd.), Target 222F, Foot 251, FTX-218 (all are trade names, manufactured by Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 ( All of the above are trade names, manufactured by Mitsubishi Materials Corp.), Mega Fuck F-171, Mega Fuck F-177, Mega Fuck F-475, Mega Fuck R-08, Mega Fuck R-30 (all of these are trade names, DIC Corporation), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl) Polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl Ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan Palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, may be mentioned alkyl benzene sulfonate or an alkyl diphenyl ether disulfonate salt, or the like.

  Moreover, it is preferable that the surfactant (C) is a fluorine-based surfactant or a silicon-based surfactant because the water repellency of the surface of the obtained cured film is further increased. In particular, it is more preferable that the surfactant (C) is a silicon-based surfactant because when the microlenses are formed on the resulting water-repellent cured film by an ink jet method, the variation in lens size is small.

  In the composition of the present invention containing a solvent, it is preferable that the weight ratio (B) :( C) is in the range of 1000: 1 to 1: 5, since both photocurability and water repellency of the cured film surface can be achieved. . Furthermore, the weight ratio (B) :( C) is preferably in the range of 100: 1 to 1: 3, more preferably in the range of 20: 1 to 1: 2, and 16: 1 to 1: 1. It is still more preferable that it is the range of these.

Furthermore, it is preferable that the surfactant has one photoreactive functional group because the photocurability is high even when a large amount of solvent is contained. The photoreactive functional group is preferably (meth) acryloyl, epoxy, or oxetanyl because it has higher photocurability.
Specific examples of the surfactant having (meth) acryl as a photocurable functional group include RS-72K (trade name; manufactured by DIC Corporation), BYK UV 3500, BYK UV 3510, and BYK UV 3570 (all above). Trade names, manufactured by Big Chemie Japan Co., Ltd.), TEGO RAD 2220N, TEGO RAD 2250, TEGO RAD 3500, and TEGO RAD 3570 (all of which are trade names, manufactured by DEGUSSA). Moreover, DIC Corporation RS-212K (brand name) can be mentioned as surfactant which has an epoxy as a photocurable functional group.

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

<1.5. Photopolymerization initiator (D)>
The photocurable composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) is not particularly limited as long as it is a compound capable of generating radicals or acids upon irradiation with ultraviolet rays or visible rays, but is not limited to α-hydroxylalkylphenone, oxyphenylacetate, or acyl. A phosphine oxide photopolymerization initiator is preferred from the viewpoint of photocurability and the transmittance of the resulting cured film.

Specific examples of compounds capable of generating radicals upon irradiation with ultraviolet rays or visible light include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2 , 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phene L] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) Benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3, 4′-di (methoxycarbonyl) -4,3′-di (t-butylperoxycarbonyl) benzophenone, 4,4 ′ Di (methoxycarbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′ , 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2, -(2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophene) ) -S-triazine, 1,3-bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylamino) Styryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5 5 'Tetraphenyl-1,2'-biimidazole,2,2'-bis (2,4,6-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, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2 , 4-Cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide And 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Among these, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) phenylphosphine Fin oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferred, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is most preferred.

Specific examples of compounds capable of generating an acid upon irradiation with ultraviolet rays or visible light include CPI-100P, CPI-100A, CPI-110P, CPI-210S, and CPI-200K (all of which are trade names: San Apro ( Co., Ltd.), Cyracure photocuring initiator UVI-6922, Silacure photocuring initiator UVI-6976 (all are trade names; manufactured by Dow Chemical Japan Co., Ltd.), Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, Adekaoptomer SP-172 (all are trade names; manufactured by ADEKA Corporation), CI-5102, CI-2855 (all are trade names: Nippon Soda ( Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sa Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-180 (all are trade names; manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure 1064, Esacure 1187 (all are trade names; Lamberti Co., Ltd.), Omnicat 550 (trade name; manufactured by IG Resin Co., Ltd.), Irgacure 250 (trade name; manufactured by BASF Japan Ltd.), Rhodesil Photoinitiator 2074 (trade name; Rhodia Japan) For example).
The photopolymerization initiator (D) may be one type or a mixture of two or more types.

  When the content of the photopolymerization initiator (D) is 1 to 100% by weight with respect to the compound (B) having two or more photocurable functional groups, the photocurability against ultraviolet rays is excellent and obtained. The water repellent cured film is preferable because of its high transmittance, more preferably 5 to 60% by weight, and still more preferably 10 to 40% by weight.

<1.6. Polymerization inhibitor>
The photocurable composition of the present invention may contain a polymerization inhibitor in order to improve storage stability. Specific examples of the polymerization inhibitor include 4-methoxyphenol, hydroquinone and phenothiazine. Among these, phenothiazine is preferable because the increase in viscosity is small even during long-term storage.

  The polymerization inhibitor used in the photocurable composition of the present invention may be one type or a mixture of two or more types.

  The content of the polymerization inhibitor is preferably 0.01 to 1% by weight with respect to the compound (B) having two or more photocurable functional groups because the increase in viscosity is small even during long-term storage, Considering the balance with photocurability, it is more preferably 0.01 to 0.5% by weight, and still more preferably 0.01 to 0.1% by weight.

<1.7. Thermosetting compounds other than epoxy compounds>
The photocurable composition of the present invention may contain a thermosetting compound other than the epoxy compound. In the present invention, the thermosetting compound is not particularly limited as long as it is a compound having a functional group that can be thermally cured, and examples thereof include bismaleimide, a phenol resin, a melamine resin, and an epoxy curing agent.
The thermosetting compound used in the curable composition of the present invention may be one type or a mixture of two or more types.

  It is preferable that the content of the thermosetting compound is 2 to 50% by weight based on the compound (B) having two or more photocurable functional groups, since the heat resistance of the resulting cured film is improved, and more preferable. Is 5 to 30% by weight, more preferably 10 to 20% by weight.

1.7.1 Bismaleimide Examples of the bismaleimide include compounds represented by the following general formula (1). The bismaleimide represented by the following general formula (1) is a compound obtained by reacting, for example, a diamine and an acid anhydride.

In formula (1), R ¹⁰ and R ¹² are each independently hydrogen or methyl, and R ¹¹ is a divalent group represented by the following general formula (2).

In formula (2), each of R ¹³ and R ¹⁴ independently represents an alkylene having 1 to 18 carbon atoms in which arbitrary methylene which is not continuous may be replaced by oxygen, or an aromatic ring which may have a substituent. It is a cycloalkylene which may have a valent group or a substituent. Examples of the substituent in the aromatic ring and cycloalkylene include carboxyl, hydroxyl, alkyl having 1 to 5 carbons, and alkoxy having 1 to 5 carbons. From the viewpoint of high heat resistance of the resulting cured film, R ¹³ and R ¹⁴ are each preferably a divalent group represented by any one of the following formulas.

  In formula (2), X is a divalent group represented by any of the following formulas.

The bismaleimide may be one kind or a mixture of two or more kinds.
1.7.2 Phenol Resin As the phenol resin, a novolak resin obtained by a condensation reaction between an aromatic compound having a phenolic hydroxyl group and an aldehyde, a homopolymer of vinyl phenol (including a hydrogenated product), vinyl phenol, A vinylphenol copolymer (including a hydrogenated product) with a compound copolymerizable therewith is preferably used.

  Examples of aromatic compounds having a phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, o-xylenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5 -Trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenol A, bisphenol F, terpene skeleton-containing diphenol, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. I can get lost.

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

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

  Specific examples of the phenol resin include Resitop PSM-6200 (trade name; manufactured by Gunei Chemical Industry Co., Ltd.), Shonor BRG-555 (trade name; manufactured by Showa Denko Co., Ltd.), Marka Linker MS-2P, Marka Examples thereof include linker CST70 and Marca linker PHM-C (trade name; manufactured by Maruzen Petrochemical Co., Ltd.).

  The phenol resin may be one type or a mixture of two or more types.

1.7.3 Melamine Resin Melamine resin is not particularly limited as long as it is a resin produced by polycondensation of melamine and formaldehyde, methylol melamine, etherified methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, and Examples thereof include condensates thereof. Among these, etherified methylol melamine is preferable in that the resulting cured film has good chemical resistance.

Specific examples of the melamine resin include Nicarak MW-30, MW-30HM, MW-390, MW-100LM, MX-750LM (trade names; manufactured by Sanwa Chemical Co., Ltd.).
The melamine resin may be one type or a mixture of two or more types.

1.7.4 Epoxy Curing Agent The photocurable composition of the present invention may contain an epoxy curing agent in order to further improve the chemical resistance of the resulting cured film. As the epoxy curing agent, an acid anhydride curing agent, a polyamine curing agent and the like are preferable.

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

  Examples of polyamine curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, polyamidoamine (polyamide resin), ketimine compound, isophoronediamine, m-xylenediamine, m-phenylenediamine, and 1,3-bis (amino). Methyl) cyclohexane, N-aminoethylpiperazine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, diaminodiphenylsulfone and the like.

  The epoxy curing agent may be one type or a mixture of two or more types.

<1.8. Flame Retardant>
The photocurable composition of the present invention may contain a flame retardant. It is preferable to contain a flame retardant because the resulting cured film has high flame retardancy. Although it will not specifically limit if it is a compound which can provide a flame retardance as a flame retardant, It is preferable to use an organophosphorus flame retardant from a viewpoint of low toxicity, low pollution property, and safety.

  Examples of the organophosphorus flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Etc.

  Among the flame retardants, an organophosphorus flame retardant which is a compound having a structure represented by the following formula (F-1) is used in that there is no bleed out of the flame retardant even when the obtained cured film is exposed to a high temperature state. It is preferable to use it. As a compound having a structure represented by the following formula (F-1), HFA-3003 (trade name; Showa Denko (which is a condensed 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) It is more preferable to use a compound represented by the following general formula (F-2) such as manufactured by

式中、ｍは０〜２の整数であり、ｎは１〜３の整数であり、ｍ＋ｎは３である。好ましくは、ｍは１または２であり、ｎは１または２であり、ｍ＋ｎは３である。

In the formula, 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 may be one type or a mixture of two or more types. In addition, the flame retardant demonstrated above can be manufactured by a well-known method, and is also marketed like HFA-3003 by said Showa Denko KK.

  The flame retardant content is preferably 15 to 30% by weight based on the compound (B) having two or more photocurable functional groups, since the flame retardancy of the resulting cured film is improved, more preferably. 20 to 25% by weight.

<1.9. Method for preparing photocurable composition of the present invention>
The photocurable composition of this invention can be prepared by mixing each component used as a raw material by a well-known method.
In particular, the photocurable composition of the present invention is prepared by mixing the components (A) to (D) and other components as necessary, and filtering and degassing the resulting solution. Is preferred. The photocurable composition of the present invention thus prepared is excellent in dischargeability during ink jet coating. For the filtration, for example, a fluororesin membrane filter is used.

<1.10. Preservation of Photocurable Composition of the Present Invention>
When the photocurable composition of the present invention is stored at -20 to 25 ° C, the increase in viscosity during storage is small, and the storage stability is good.

[2. Application of photocurable composition by inkjet method]
The photocurable composition of the present invention can be applied using a known inkjet coating method. Examples of the ink jet coating method include a piezo method in which mechanical energy is applied to the ink to eject the ink from the ink jet head, and a coating method in which the ink is ejected by applying thermal energy to the ink (so-called bubble jet (registered trademark)). Method).

  By using the inkjet coating method, the photocurable composition can be applied in a predetermined pattern.

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

  The ink jet coating apparatus is not limited to one in which the ink jet head and the ink container are separated, and may be one in which they are integrated so as not to be separated. The ink container is integrated with the ink jet head in a separable or non-separable manner and mounted on the carriage, and is provided at a fixed portion of the apparatus so that the ink is supplied to the ink jet head through an ink supply member, for example, a tube. It may be in the form of supplying.

[3. Formation of cured film]
The cured film of the present invention can be obtained by applying the above-described photocurable composition of the present invention to the substrate surface by an ink jet method and then irradiating it with light such as ultraviolet rays or visible rays.

The amount of light to be irradiated (exposure amount) when irradiating ultraviolet rays, visible rays or the like depends on the composition of the photocurable composition, but the integrated light amount with the receiver UVD-365PD manufactured by USHIO INC. As measured by a total UIT-201, 100 to 5,000 mJ / cm ² is preferable, 200 to 4,000 mJ / cm ² is more preferable, and 300 to 3,000 mJ / cm ² is more preferable. Moreover, 200-500 nm is preferable and, as for wavelengths, such as an ultraviolet-ray and visible light to irradiate, 300-450 nm is more preferable.
In addition, the exposure amount described below is a value measured by an integrated light meter UIT-201 equipped with a photoreceiver UVD-365PD manufactured by USHIO INC.

  The exposure apparatus is not particularly limited as long as it is an apparatus that mounts a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a halogen lamp, or the like and irradiates ultraviolet rays or visible rays in the range of 250 to 500 nm.

  The substrate to which the photocurable composition of the present invention is applied is not particularly limited as long as it can be a target to which the photocurable composition is applied, and the shape is not limited to a flat plate shape, and is a curved surface shape. Also good.

  The material of the substrate is not particularly limited. For example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, fluorine resin, acrylic resin, Plastic film such as polyamide, polycarbonate and polyimide, cellophane, acetate, metal foil, laminated film of polyimide and metal foil, glassine paper, parchment paper with sealing effect, polyethylene, clay binder, polyvinyl alcohol, starch or carboxy Examples thereof include paper and glass treated with methyl cellulose (CMC).

  The substances constituting these substrates may further include an antioxidant, a deterioration inhibitor, a filler, an ultraviolet absorber, an antistatic agent and / or an electromagnetic wave preventing agent as long as the effects of the present invention are not adversely affected. An additive may be contained. Also, part of the surface of the substrate may be subjected to easy adhesion treatment such as water repellent treatment, corona treatment, plasma treatment, or blast treatment if necessary, or the surface may be subjected to an easy adhesion layer, a color filter protective film, or a hard coat film. May be provided.

  Although the thickness of a board | substrate is not specifically limited, Usually, they are 10 micrometers-10 mm, and are suitably adjusted with the objective to use.

  The use of the substrate is not particularly limited, but the cured film obtained from the photocurable composition of the present invention is excellent in adhesion to the substrate and exhibits high transmittance and high strength. It is preferably used for the production of microlenses.

  The dot diameter of the cured film of the present invention that functions as a microlens used in such a backlight unit is not particularly limited, but is usually preferably 10 to 100 μm, more preferably 15 to 60 μm, and particularly preferably 20 to 50 μm. . Moreover, although it does not specifically limit also about the height of a dot, 0.5-30 micrometers is preferable normally, 1-20 micrometers is more preferable, and 2-10 micrometers is especially preferable.

  By mounting the backlight manufactured using the cured film of the present invention as described above, for example, a liquid crystal display for a liquid crystal display element can be manufactured.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by these. Moreover, below, the photocurable composition obtained by the Example or the comparative example may only be called a composition. That is, for example, the photocurable composition 1 may be referred to as the composition 1.

[Example 1] (Example of the first embodiment)
Diethylene glycol methyl ethyl ether (hereinafter abbreviated as EDM) as the solvent (A), pentaerythritol triacrylate (hereinafter abbreviated as M305) as the compound (B) having two or more photoreactive functional groups, and BYK306 as the surfactant (C) (Trade name: manufactured by Big Chemie Japan Co., Ltd., hereinafter abbreviated as BYK306) Irgacure 754 (trade name; manufactured by BASF Japan Co., Ltd., hereinafter abbreviated as I754) as a photopolymerization initiator (D) was mixed in the following composition -After dissolving, it filtered with the membrane filter (1 micrometer) made from PTFE, and prepared the photocurable composition 1. The photocurable composition contains 50.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 7.00 g
(B) M305 5.120 g
(C) BYK306 1.110 g
(D) I754 0.770 g
It was 5.1 mPa · s as a result of measuring the viscosity of the photocurable composition 1 at 25 ° C. using an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd., hereinafter the same).

(Formation of cured film)
A 4 cm square glass substrate (thickness: 0.7 mm) whose surface wettability is improved by ultraviolet irradiation with a low-pressure mercury lamp is prepared, and the photocurable composition 1 is injected into an ink jet cartridge. Mounted on FUJIFILM Digitix Inc. DMP-2831), using a head for 10 pl, discharge voltage (piezo voltage) 16V, head temperature 30 ° C, drive frequency 5 kHz, discharge conditions with one application frequency, printing resolution Was set to 256 dpi and applied to the entire surface. A glass substrate on which a surface water-repellent cured film is formed by irradiating the glass substrate with ultraviolet rays at a UV exposure amount of 2000 mJ / cm ² using a UV irradiation device (J-CURE 1500 manufactured by JATEC Corporation). Obtained. Next, the printing resolution was changed to 512 dpi, and the same operation was performed to obtain a glass substrate on which a surface water-repellent cured film was formed. Furthermore, the printing resolution was changed to 1024 dpi and the same operation was performed to obtain a glass substrate on which a surface water-repellent cured film was formed. The following measurements were performed using the glass substrate on which the surface water-repellent cured film was formed.

(Evaluation of membrane surface)
When the glass substrate was confirmed visually, at a printing resolution of 256 dpi, the film thickness of the cured film was non-uniform and a mottled pattern was observed. At a print printing resolution of 512 dpi, mottled patterns were still observed. A uniform film surface was formed at a printing resolution of 1024 dpi. As evaluation, it was evaluated as “◯” when a uniform film surface was formed, and “X” when the film thickness was non-uniform, such as a mottled pattern observed.

(Film thickness)
A portion of the cured film formed at a printing resolution of 1024 dpi was shaved with a cutter, and the film thickness of the stepped portion was measured using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd. 96 μm. The average value of three measurements was used as the film thickness value.

(Chromaticity b *)
When the chromaticity of this cured film was measured using a transmittance measuring device V-670 (manufactured by JASCO Corporation), the value of b * indicating yellowishness was 0.0589.

(Water contact angle)
The contact angle of water (pure water) on the cured film was measured using DropMaster 500 (manufactured by Kyowa Interface Chemical Co., Ltd.) at a measurement temperature (25 ° C.) and a value after 1 second of water droplet landing was 95 °. there were.

  These results are shown in Table 1.

[Comparative Example 1]
In the same manner as in Example 1, a photocurable composition 2 having the following composition was prepared. The photocurable composition contains 30.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 3000g
(B) M305 5.120 g
(C) BYK306 1.110 g
(D) I754 0.770 g
The viscosity of the photocurable composition 2 was 13.2 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. The results are shown in Table 1.

  In Example 1, which has a higher solvent content than Comparative Example 1, a surface water-repellent cured film with less yellowness (a small value of b *) can be formed by the inkjet method.

[Example 2] (Example of the first embodiment)
In the same manner as in Example 1, a photocurable composition 3 having the following composition was prepared. The photocurable composition contains 95.6% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 15.186 g
(B) M305 0.512g
(C) BYK306 0.111g
(D) I754 0.077g
The resulting photocurable composition 3 had a viscosity of 1.7 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. A comparison with Example 1 is shown in Table 2.

[Example 3] (Example of the first embodiment)
In the same manner as in Example 1, a photocurable composition 4 having the following composition was prepared. However, propylene glycol monomethyl ether (hereinafter abbreviated as PGME), which is a solvent having hydroxy, was used as the solvent (A). The photocurable composition contains 50.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) PGME 7.0000g
(B) M305 5.120 g
(C) BYK306 1.110 g
(D) I754 0.770 g
The obtained photocurable composition 4 had a viscosity of 5.3 mPa · s. This photocurable composition was rolled and the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. A comparison with Example 1 is shown in Table 2.

（Ａ） ＥＤＭ ７．０００ｇ
（Ｂ） Ｍ４０２ ２．５６０ｇ
（Ｂ） Ｕ６ＬＰＡ ２．５６０ｇ
（Ｃ） ＢＹＫ３０６ １．１１０ｇ
（Ｄ） Ｉ７５４ ０．７７０ｇ
得られた光硬化性組成物５の粘度は５．１ｍＰａ・ｓであった。この光硬化性組成物を用いて実施例１と同様の方法で硬化膜表面の観察、膜厚、ｂ＊、水接触角の測定を行なった。実施例１との比較を表２に示す。[Example 4] (Example of the second embodiment)
In the same manner as in Example 1, a photocurable composition 5 having the following composition was prepared. However, the compound (B) having two or more photoreactive functional groups is dipentaerythritol hexaacrylate (hereinafter abbreviated as M402, trade name, manufactured by Toagosei Co., Ltd.) and urethane acrylate having the following structure (hereinafter referred to as U6LPA). U6LPA used a trade name, manufactured by Shin-Nakamura Chemical Co., Ltd. The photocurable composition contains 50.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.

(A) EDM 7.00 g
(B) M402 2.560g
(B) U6LPA 2.560g
(C) BYK306 1.110 g
(D) I754 0.770 g
The viscosity of the obtained photocurable composition 5 was 5.1 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. A comparison with Example 1 is shown in Table 2.

  In Example 2 with a large amount of solvent, a thinner film can be formed by the ink jet method, so that the yellow color of the film is small. In Example 3 using a solvent having hydroxy and Example 4 using urethane acrylate as a compound (B) having two or more photoreactive functional groups, ink jet coating conditions for forming a thinner film (that is, printing) A uniform surface water-repellent cured film could be formed with a resolution of 512 dpi.

  Here, the relationship between the printing resolution and the obtained film thickness in the case of application by the inkjet method will be described. The smaller the print resolution value, the smaller the discharge amount per unit area, and the thinner the coating film. The larger the value of the printing resolution, the greater the amount of discharge per unit area, and the thicker the coating film becomes. In order to reduce the film thickness, it is desired to reduce the printing resolution. In that case, however, the ejected dots are not connected uniformly, and it is difficult to obtain a clean uniform film surface.

[Example 5] (Example of the third embodiment)
In the same manner as in Example 1, a photocurable composition 6 having the following composition was prepared. As the surfactant (C), RS-72K (trade name; hereinafter abbreviated as RS72K) manufactured by DIC Corporation, which is a surfactant having (meth) acryl as a photocurable function, was used. The photocurable composition contains 50.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 7.00 g
(B) M402 2.560g
(B) U6LPA 2.560g
(C) RS72K 1.110 g
(D) I754 0.770 g
The viscosity of the photocurable composition 6 was 5.2 mPa · s.

[Example 6] (Example of the third aspect)
In the same manner as in Example 5, a photocurable composition 7 having the following composition was prepared. However, BYK UV 3500 (trade name; hereinafter abbreviated as BYK3500) manufactured by Big Chemie Japan Co., Ltd., which is a surfactant having (meth) acryl as a photocurable function, was used as the surfactant (C). The photocurable composition contains 53.0% by weight of the solvent (A), the weight ratio (B) :( C) is 15.4: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 7.00 g
(B) M402 2.560g
(B) U6LPA 2.560g
(C) BYK3500 0.330 g
(D) I754 0.770 g
The viscosity of the photocurable composition 7 was 5.3 mPa · s.

A 4 cm square glass substrate (thickness: 0.7 mm) whose surface wettability was improved by performing ultraviolet irradiation with a low-pressure mercury lamp was prepared, and the photocurable composition 5 obtained in Example 4 and Example 5 were used. The obtained photocurable composition 6 and the photocurable composition 7 obtained in Example 6 were each injected into an ink jet cartridge, and this was mounted on an ink jet apparatus (DMP-2831 manufactured by FUJIFILM Dimatix Inc.). Using a 10 pl head, coating was performed on the entire surface with a resolution of 1024 dpi under ejection conditions of a discharge voltage (piezo voltage) of 16 V, a head temperature of 30 ° C., a drive frequency of 5 kHz, and a coating frequency of once. This glass substrate is irradiated with a UV irradiation device (J-CURE 1500, manufactured by JATEC Co., Ltd.) by shaking the irradiation dose of ultraviolet rays at 200 mJ / cm ² , 500 mJ / cm ² , 1000 mJ / cm ² , and 2000 mJ / cm ^2. The photocurability was observed. The case where the coating surface had tackiness was rated as x, the case where tackiness was slightly, Δ, and the case where tackiness was not present as ○. The results are shown in Table 3.

  The composition 6 (Example 5) and the composition 7 (Example 6) using a surfactant having a photocurable functional group in the surfactant (C) are interfaces having no photocurable functional group. It turns out that it is further excellent in photocurability compared with the composition 5 (Example 4) which uses an activator.

[Example 7] (Example of the fourth embodiment)
EDM as the solvent (A), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc., hereinafter abbreviated as VG) as the compound (B) having two or more photoreactive functional groups, and epoxy as the surfactant (C) RS-21K (trade name; manufactured by DIC Corporation, hereinafter abbreviated as RS), CPI-210S ((trade name; San Apro Co., Ltd.), an acid generator as a photopolymerization initiator (D). (Hereinafter, abbreviated as CPI) were mixed and dissolved in the following composition, and then filtered through a PTFE membrane filter (1 μm) to prepare a photocurable composition 7. A solvent was contained in the photocurable composition. (A) contains 50.0% by weight, the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) has two or more photoreactive functional groups. It is 15 weight% of a compound (B).
(A) EDM 7.00 g
(B) VG 5.120 g
(C) RS 1.110g
(D) CPI 0.770g
The resulting photocurable composition 8 had a viscosity of 5.3 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. The results are shown in Table 4.

[Comparative Example 2]
In the same manner as in Example 1, a photocurable composition 9 having the following composition was prepared. The photocurable composition contains 30.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 3000g
(B) VG 5.120 g
(C) RS 1.110g
(D) CPI 0.770g
The viscosity of the photocurable composition 9 was 14.6 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1. The results are shown in Table 4.

  Even if an epoxy compound is used as the compound (B) having two or more photoreactive functional groups and an acid generator is used as the photopolymerization initiator (D), a surface water-repellent cured film with little yellowness is formed by the inkjet method. However, it can be seen that when the content of the solvent is small, a thick film is formed and the yellow color becomes strong.

[Example 8] (Substrate evaluation by microlens formation)
Microlenses were formed on the cured films of Examples and Comparative Examples, and the evaluation of each cured film as a base film was performed.
First, pentaerythritol triacrylate (hereinafter abbreviated as M305. M305 is a trade name, manufactured by Toagosei Co., Ltd.) and n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a monofunctional (meth) acrylate, , DAROCUR TPO (trade name; manufactured by BASF Japan), which is a photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a polymerization inhibitor. Were mixed and dissolved in the following composition, and then filtered through a PTFE membrane filter (1 μm) to prepare an inkjet ink for forming a microlens.
M305 350.00g
n-Butyl methacrylate 200.00g
DAROCUR TPO 55.00g
Phenothiazine 0.28g
As a result of measuring the viscosity at 25 ° C., it was 12.3 mPa · s.

  This microlens forming inkjet ink is injected into an inkjet cartridge, which is mounted on an inkjet apparatus (DMP-2811, manufactured by FUJIFILM Dimatix Co., Ltd.), using a head for 10 pl, an ejection voltage (piezo voltage) of 16 V, On a surface water-repellent cured film formed of the photocurable compositions 1 to 8 on a surface water-repellent cured film formed at a head temperature of 30 ° C., a driving frequency of 5 kHz, and a coating frequency of one time, one dot was ejected at 150 μm intervals.

The glass substrate on which the dot patterns were formed at equal intervals was irradiated with ultraviolet rays at a UV exposure amount of 2000 mJ / cm ^{2 in} the same manner as in Example 1 to obtain a substrate with microlenses. When the shape of the microlens was observed with an optical microscope, the case where the shape was uniform with a clean circle was marked with ◯, and the case where the shape was distorted or the size was uneven was marked with x. The results are shown in Table 5.

Any composition effectively functions as a base film for forming a microlens.
As is clear from the above results, the photocurable composition of the present invention can form a surface water-repellent cured film having a uniform film thickness using an inkjet method. Therefore, the yellowishness of the film can be reduced, and it can be preferably used for the production of a high-quality light guide plate for liquid crystal display.

[Example 9] (Example of the fifth aspect)
In the same manner as in Example 1, a photocurable composition 10 having the following composition was prepared. However, for the compound (B) having two or more photoreactive functional groups, fluorite FA-16 (trade name; manufactured by Kyoeisha Chemical Co., Ltd., hereinafter abbreviated as fluorite) and U6LPA are used. It was. The photocurable composition contains 50.0% by weight of the solvent (A), the weight ratio (B) :( C) is 4.61: 1, and the photopolymerization initiator (D) is light. It is 15% by weight of the compound (B) having two or more reactive functional groups.
(A) EDM 7.00 g
(B) Fluorite 2.560g
(B) U6LPA 2.560g
(C) BYK306 1.110 g
(D) I754 0.770 g
The viscosity of the obtained photocurable composition 10 was 4.2 mPa · s. Using this photocurable composition, the cured film surface was observed and the film thickness, b *, and water contact angle were measured in the same manner as in Example 1.

  Next, a dot pattern was formed on the cured film by the same method as in Example 8, and the pattern shape was observed with an optical microscope. Furthermore, 10 dot patterns were arbitrarily selected, and the diameter and height were measured using a stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., and the average value was calculated. For the dot pattern formed on the cured film obtained from the photocurable composition 5 of Example 8, the diameter and height were calculated by the same method. These results are shown in Tables 6-1 and 6-2.

  The cured film obtained from the composition 10 using fluorite FA-16 having fluorine as the compound (B) having two or more photoreactive functional groups uses a compound having fluorine. Compared to the cured film obtained from the composition 5 (Example 4) having no dot, the ratio of the height / diameter of the dot pattern formed on the cured film is large, which is useful as a microlens for a light guide plate having higher performance. It is.

  As described above, when a microlens is formed by a inkjet method on a cured film obtained from the photocurable composition of the present invention, it is useful for producing a high-quality optical component with little yellowness.

Claims (17)

Solvent (A), compound (B) having two or more photoreactive functional groups, surfactant (C) having one photoreactive functional group , photopolymerization initiator (D) A cured film having a film thickness of 1 μm or less, which is a photocurable composition containing the applied photocurable composition having a solvent (A) content of 40 to 98% by weight by light irradiation. . The cured film of Claim 1 whose solvent (A) is an organic solvent with a boiling point of 100-300 degreeC. The cured film according to claim 1 or 2, wherein the solvent (A) is an organic solvent having hydroxy. The cured film of any one of Claims 1-3 whose compound (B) which has two or more photoreactive functional groups is polyfunctional (meth) acrylate. The cured film according to any one of claims 1 to 3, wherein the compound (B) having two or more photoreactive functional groups is a compound selected from the following structures.

(B-1)
Wherein R ¹ is a divalent organic group having 1 to 20 carbon atoms, R ² and R ³ are each independently alkylene having 1 to 20 carbon atoms, and 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). The cured film according to any one of claims 1 to 3, wherein the compound (B) having two or more photoreactive functional groups is a compound selected from the following structures.

(B-2)
(Wherein R ¹ is

R ² and R ³ are each independently alkylene having 1 to 10 carbon atoms, and 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. )   The cured film according to claim 3, wherein the compound (B) having two or more photoreactive functional groups contains fluorine. The cured film according to any one of claims 1 to 7, wherein the surfactant (C) having one photoreactive functional group is a fluorine-based surfactant or a silicon-based surfactant. Photoreactive functional groups one has to have surfactant photoreactive functional group (C), (meth) acryloyl, cured film according to any one of claims 1-8. The compound (B) having two or more photoreactive functional groups is a polyfunctional (meth) acrylate, and the photoreactivity of the surfactant (C) having one photoreactive functional group The cured film according to any one of claims 1 to 8, wherein the functional group is (meth) acryloyl, and the photopolymerization initiator (D) is a photoradical generator. Viscosity at 25 ° C. of the photocurable composition is 1.5~30mPa · s, the cured film according to any one of claims 1-10. Light irradiation is ultraviolet or visible light, the cured film according to any one of claims 1 to 11. Solvent (A), compound (B) having two or more photoreactive functional groups, surfactant (C) having one photoreactive functional group , photopolymerization initiator (D) A photocurable composition containing a solvent (A) having a content of 40 to 98% by weight and a viscosity at 25 ° C. of 1.5 to 30 mPa · s. A method for forming a cured film, comprising the step of applying in step (b).   A microlens formed on the cured film according to claim 1. Comprising the step of forming a dot pattern by an inkjet method on the hard film of Claim 1, forming a microlens. An optical component having the microlens according to claim 14 . An image display device comprising the optical component according to claim 16 .