JP2015007166A - Photocurable resin composition, and photocurable light-shielding coating material, light leakage preventing material, liquid crystal display panel and liquid crystal display device using the composition, and photocuring method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, first, a photocurable resin composition suitable for curing by use of an LED light source, particularly, curing by irradiation with UV rays of a wavelength of 365 nm by LED, and to provide, second, a photocurable resin composition, a photocurable light-shielding coating material and a light leakage preventing agent useful for shielding against light, and a liquid crystal panel using these materials.SOLUTION: The photocurable resin composition comprises (A) a resin having a number average molecular weight of 900 to 10,000 and having a polymerizable unsaturated group, (B) a monomer having a polymerizable unsaturated group, and (C) a photopolymerization initiator in an amount of 1 to 10 parts by mass with respect to total 100 parts by mass of (A) and (B). The photocurable light-shielding coating material comprises the photocurable resin composition further containing (D) a thiol compound, (E) a filler having light-shielding property, and (F) a leuco compound. The liquid crystal panel suppresses leakage of light by applying the above photocurable light-shielding coating material on a panel side face.

Description

  The present invention relates to a photocurable resin composition, a photocurable light-shielding coating material using the same, a light leakage prevention material, a liquid crystal display panel and a liquid crystal display device, and a photocuring method. More specifically, the present invention relates to a photocurable resin composition suitable for curing by light irradiation based on an LED light source, a photocurable light-shielding paint and a light leakage preventing material using the same, a liquid crystal display panel and a liquid crystal display device using these, And a photocuring method.

  The photocurable resin composition is used in various fields. The composition effect naturally requires light irradiation, but recently, as part of energy saving, there is a demand for labor saving of the light source. Therefore, attention is focused on LED light sources, and in particular, irradiation of light with an ultraviolet wavelength of 365 nm by LEDs has been attracting attention, and it is an urgent need to provide a photocurable resin composition suitable for it.

  For example, as an application of a photocurable resin composition, there is use as a protective coating in a field where moisture resistance and heat cycle properties are required, as described in Patent Document 1, and applied to a liquid crystal display or a module thereof. Use is planned.

  The liquid crystal display device includes a liquid crystal display panel and a backlight that illuminates the liquid crystal display panel from the back surface. When these are incorporated into the housing, the illumination light of the backlight is transmitted only from the image display area of the liquid crystal display panel, and is prevented from leaking from, for example, a gap between the liquid crystal display panel and the housing. It is necessary. In addition, in the liquid crystal display device, since there is a demand for a narrow frame for the screen frame of the liquid crystal display device, light leakage from the gap between the casing and the liquid crystal display panel at the frame portion is likely to occur.

  Therefore, as a countermeasure against light leakage, as disclosed in Patent Document 2, a light-shielding double-sided adhesive sheet is disposed in the peripheral portion between the backlight and the liquid crystal display panel, and as disclosed in Patent Document 3, a light reflection preventing film or There has been proposed a method of arranging a light leakage prevention material (light shielding material) such as a black paint sprayed with a light reflection preventing tape or a spray between a case for housing a backlight and a liquid crystal display panel.

  However, in these methods, when the width of the light-shielding sheet becomes narrow, the work of arranging becomes complicated, and there arises a problem that it takes time for dimensional accuracy and work. In the case of a method of applying a light-shielding paint, a solvent drying type or The heat-curing type requires high-temperature treatment and long-time treatment in order to completely dry and cure the paint. On the other hand, photo-curable light-shielding coatings that can be cured in a short time, for example, several seconds to several minutes, have been developed, but photo-curable light-shielding that cures the film thickness necessary for light shielding (for example, about several hundred μm). The material is not available.

International Publication WO2012 / 090298 JP 2002-98945 A JP 2006-154870 A

  The present invention provides, firstly, a photocurable resin composition suitable for curing by an LED light source, in particular, curing by irradiation with light having an ultraviolet wavelength of 365 nm by an LED, and secondly, useful for light shielding. The present invention provides a photocurable resin composition, a photocurable light-shielding coating material, and a light leakage preventing agent, and further provides a liquid crystal panel and a liquid crystal display device using these, and a photocuring method.

The present invention relates to the following.
1. (A) A resin having a polymerizable unsaturated group having a number average molecular weight of 900 to 10,000, (B) a monomer having a polymerizable unsaturated group, and (C) a photopolymerization initiator, (A) and (B The photocurable resin composition containing 1 to 10 parts by mass with respect to 100 parts by mass in total.
2. Item 2. The photocurable resin composition according to Item 1, wherein the component (B) contains 1 to 50 parts by mass with respect to 50 parts by mass of the component (A).
3. Furthermore, (D) The photocurable resin composition in any one of the term 1 or 2 which contains 5-20 mass parts with respect to the total of 100 mass parts of said (A) and (B) thiol compound.
4). Further, any one of Items 1-3, wherein (E) an average particle diameter of 10 μm or less and a light-shielding filler is contained in an amount of 1 to 50 parts by mass relative to a total of 100 parts by mass of the component (A) and the component (B). A photocurable resin composition according to claim 1.
5. Furthermore, the photocurability in any one of claim | item 1-4 which contains 0.1-3.0 mass parts of (F) leuco compounds with respect to a total of 100 mass parts of (A) component and (B) component. Resin composition.
6). Item 6. A photocurable light-shielding coating material comprising the photocurable resin composition according to any one of Items 4 and 5.
7). Item 6. A light leakage preventing material comprising the photocurable resin composition according to Item 4 or 5.
8). Item 7. A liquid crystal display panel that is shielded by applying the photocurable light-shielding coating material according to Item 6 or the light leakage preventing material according to Item 7 to the outer periphery of the panel.
9. Item 9. A liquid crystal display device using the liquid crystal display panel according to item 8.
10. Item 6. The photocurable resin composition according to items 1-5, the photocurable light-shielding coating material according to item 6, and the light leakage prevention material according to item 7, wherein ultraviolet rays mainly containing wavelengths near 365 nm based on LED light sources are used. Irradiating, a photocuring method.

  The photocurable resin composition according to the present invention is suitable for curing by an LED light source, particularly curing by irradiation with light having an ultraviolet wavelength of 365 nm by an LED, and exhibits excellent curability. In particular, by including the component (D) [thiol compound], it is excellent in surface curability, and further, by including the component (E) [filler for light shielding], it is necessary for light shielding in a short time with an LED light source. It is possible to cure the film thickness. Moreover, it can be set as the photocurable resin composition which can confirm having hardened | cured by changing a color by irradiating an ultraviolet-ray by containing (F) component [leuco compound]. By applying such a resin composition to the side surface of the liquid crystal panel as a light-shielding paint or a light leakage preventing agent, a liquid crystal display device in which light leakage is suppressed can be provided. Moreover, according to the photocuring method of the present invention, it is possible to effect photocuring effectively using an LED light source.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
Specific examples of the resin having a polymerizable unsaturated group having a number average molecular weight of 900 to 10,000 as the component (A) include urethane oligomers such as (meth) acrylate compounds having a urethane bond. . These can be used individually by 1 type or in combination of 2 or more types.

  Examples of urethane oligomers include (meth) acrylic monomers having an OH group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction products, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO or PO-modified urethane di (meth) acrylate, carboxyl group-containing urethane (meth) acrylate, etc. It is done. These can be used individually by 1 type or in combination of 2 or more types.

  As the monomer having a polymerizable unsaturated group (B) used in the present invention, styrene, vinyltoluene, α-methylstyrene, p-tertiarybutylstyrene, chlorostyrene, divinylbenzene, diallyl phthalate, 2-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate, methacrylic acid and Cardura E-10 (manufactured by Shell Chemical Co., Ltd., trade name of glycidyl ester of higher fatty acid), etc. Monofunctional methacrylate ester, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, bifunctional methacrylate ester such as 1,6-hexanediol dimethacrylate, trimethylolpropane trime Monofunctional methacrylates such as acrylate, methyl acrylate, ethyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and a reaction product of acrylic acid and Cardura E-10. Bifunctional acrylic esters such as acrylic ester, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, trifunctional acrylic ester such as trimethylolpropane triacrylate, pentaerythritol triacrylate, For example, tetrafunctional acrylic esters such as pentaerythritol tetraacrylate, hexafunctional acrylic esters such as pentaerythritol hexaacrylate, etc. These can be used in combination of two or more.

  The blending ratio of the monomer (B) having a polymerizable unsaturated group is 1 with respect to 50 parts by mass of the component (A) from the viewpoints of the curing speed, the viscosity of the coating material, and the flexibility of the coating film. The range of -50 mass parts is preferable, and the range of 20-50 mass parts is more preferable.

  Among the monomers having a polymerizable unsaturated group (B), a monomer (B-1) having 3 or more polymerizable double bonds and a single monomer having 2 or less polymerizable double bonds. It is preferable to use the monomer (B-2) in combination. The blending ratio of the component (B-1) / component (b-2) is preferably in the range of 10/90 to 75/25 by weight ratio. If this ratio is too small, the strength of the cured product tends to be small, and if this ratio is too large, the cured product tends to be brittle.

  The photopolymerization initiator which is the component (C) includes what is called a sensitizer. Specific examples of such a photopolymerization initiator include acridine or an acridine compound having at least one acridinyl group in the molecule, benzophenone, N, such as N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), and the like. , N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl ] Aromatic ketones such as 2-morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (O-chlorophenyl) -4 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole dimers such as-(o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer N-phenylglycine, N-phenylglycine derivatives, coumarin compounds, onium salts and the like. These can be used alone or in combination of two or more. The blending ratio of these (C) photopolymerization initiators is 0 with respect to 100 parts by mass of the total amount of the above-mentioned components (A) and (B) from the viewpoints of curing speed, film-forming property, and coating flexibility. 0.1-15 mass parts is preferable, and the range of 0.1-10 mass parts is more preferable. If the blending ratio is less than 0.1 parts by mass, photocuring tends to be insufficient, and if it exceeds 15 parts by mass, the properties of the resulting cured product (deep part curability, flexibility, adhesion, etc.) ) Generally tends to decrease.

In the photocurable resin composition according to the present invention, a thiol compound is preferably blended as the component (D). By blending this, the surface curability of the cured product is excellent particularly when the photocurable resin composition is cured. As specific examples of the component (D) [thiol compound], various compounds can be used as long as they have two or more thiol groups. Specific examples include thioglycolic acid derivatives and mercaptopropionic acid derivatives in addition to simple thiols. Simple thiols include o-, m- or p-xylenedithiol. Examples of the thioglycolic acid derivative include ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, and the like. Mercaptopropionic acid derivatives include ethylene glycol bisthiopropionate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and trihydroxyethyl triisocyanurate tristhioproate. Pionate etc. are mentioned.
As the component (D), a compound having two or more thiol groups is preferable because of excellent curability.

  The blending amount of the component (D) is preferably 5 to 20 parts by mass, particularly preferably 5 to 15 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B). If the amount of component (D) is too small, the effect of improving the surface curability will be small, and if it is too large, the cured product tends to be brittle.

In order to impart light-shielding properties to the photocurable resin composition according to the present invention, it is preferable to blend a light-shielding filler as the component (E). Specific examples of the filler include silicone resin powder, silicone rubber powder, composite powder in which the surface of silicone rubber powder is coated with silicone resin, alumina, zirconia, ceramic fine powder, talc, mica, boron nitride, kaolin, barium sulfate, etc. Can be used.

From the viewpoint of light shielding properties, the component (E) used in the present invention preferably has an average particle size of 10 μm or less, and more preferably has an average particle size of 5 μm or less. When the average particle diameter exceeds 10 μm, the light shielding property is deteriorated. The “average particle diameter” described in the present specification is a value obtained by measurement by a light scattering method. The blending ratio of the component (E) is 100 parts by mass of the total amount of the components (A) and (B). 1 to 50 parts by mass, preferably 1 to 20 parts by mass. If the blending ratio is less than 1 part by mass, the light-shielding effect tends to be small, and even if it exceeds 50 parts by mass, no further effect on the light-shielding property is observed, and the viscosity tends to increase and handling becomes difficult. is there.

  Examples of the leuco compound as the component (F) used for confirming that it has been cured or irradiated with light for curing include tris (4-dimethylaminophenyl) methane [leuco crystal violet], tris ( 4-diethylamino-2-methylphenyl) methane, leucomalachite green, leucoaniline, leucomethyl violet and the like. The blending ratio of the (F) leuco compound is 0.1 to 3.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). It is preferable. If the blending ratio is less than 0.1 parts by mass, the color after photocuring becomes thin and the effect of shading is small, and even if it exceeds 3.0 parts by mass, no effect is seen.

  The photocurable light-shielding paint or light leakage preventive agent of the present invention is obtained by blending the components (A), (B), (C), (D) and (E), preferably further (F) A component is mix | blended.

  In addition, a coupling agent, a polymerization inhibitor, a colorant, and the like can be added to the photocurable resin composition, the photocurable light-shielding coating material, or the light leakage preventing agent according to the present invention as necessary.

  The coupling agent includes a titanate coupling agent and a silane coupling agent. The titanate coupling agent includes a titanate coupling agent having an alkylate group having at least 1 to 60 carbon atoms and an alkyl phosphite group. And titanate coupling agents having an alkyl phosphate group, titanate coupling agents having an alkyl phosphate group, and titanate coupling agents having an alkyl phosphate group. Specifically, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, Examples include tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, and the like.

  Silane coupling agents include amino silane coupling agents, ureido silane coupling agents, vinyl silane coupling agents, methacrylic silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents and An isocyanate silane coupling agent etc. are mentioned. Specifically, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltri Ethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane, which are used alone or in combination of two or more. It can be used Te.

  Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, quinones such as 2,6-di-tert-butyl-4-methylphenol, pyrogallol, and other commonly used ones. Used.

  Examples of the antifoaming agent include those commonly used such as silicone oil, fluorine oil, and polycarboxylic acid polymer.

  When a black dye [for example, OPLAS Black 833 (manufactured by Orient Chemical Co., Ltd.)] is blended as a colorant, there is a possibility that curing may be insufficient even if the photocurable resin composition is irradiated with light. Need attention.

  The photocurable resin composition, the photocurable light-shielding paint, or the light leakage preventing agent according to the present invention is applied to the side surface of the liquid crystal display panel with a dispenser device or the like, and is used according to each purpose. At this time, in order to cure the resin composition, it is possible to cure by irradiating a necessary amount of ultraviolet rays using a lamp type or LED type UV irradiation apparatus using a high pressure mercury lamp, a metal halide lamp or the like as a light source.

  The photocurable resin composition, the photocurable light-shielding paint or the light leakage preventive agent according to the present invention is preferably suitably irradiated with light from an LED light source, and in particular, may be irradiated mainly with light having a wavelength of 365 nm. Preferably suitable. The light mainly having a wavelength of 365 nm is not only light having a single wavelength of 365 nm but also light having a center of 365 nm. For example, light having a wavelength of 350 nm to 380 nm accounts for 90% or more of the total light amount. It is.

The amount of light to be irradiated is such that it cures sufficiently in consideration of the formulation (especially the type and amount of photopolymerization initiator, the presence or absence of fillers and dyes, the type and amount of fillers and dyes when used, etc.). For example, when it is appropriately determined from the range of 50 to 3000 mJ / cm ² per 300 μm thickness of the photocurable resin composition, the photocurable light-shielding paint or the light leakage preventing agent, and contains a filler or a dye is preferably to more eyes light quantity, for example, is a 300 mJ / cm ² or more, and is preferably in consideration of the energy cost and moderate degree of curing and 1500 mJ / cm ² or less.

  Hereinafter, the present invention will be described in detail with reference to examples. The following examples are illustrations for suitably explaining the present invention, and do not limit the present invention.

  TA37-248A (Hitachi Chemical Polymer Co., Ltd., urethane acrylate resin, number average molecular weight of about 1,800) 35 parts by mass as component (A-1), UN-3320HA (manufactured by Negami Kogyo Co., Ltd.) as component (A-2) , Urethane acrylate resin, number average molecular weight of about 1,000) 25 parts by mass (B-1) component 10 parts by mass of dipentaerythritol hexaacrylate, (B-2) 30 parts by mass of isobornyl acrylate, (C- 1) 4 parts by mass of 1-hydroxycyclohexylphenyl-ketone as component, 1.0 part by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as component (C-2), component (D) 10 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) as component (E) 8 parts by mass of MP-605 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone composite powder, average particle size 2 μm) and 1.0 part by mass of leuco crystal violet as component (F) were mixed and heated and stirred at 60 ° C. A photocurable resin composition (light-shielding paint or light leakage prevention material) was obtained.

  Except for changing 35 parts by mass of TA37-248A of Example 1 to 35 parts by mass of TE-2000 (manufactured by Nippon Soda Co., Ltd., acrylic-modified polybutadiene resin, number average molecular weight: about 1,000), the same as Example 1 did.

  10 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) of Example 1 was replaced with 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione The procedure was the same as Example 1 except that the amount was changed to 10 parts by mass.

  The same procedure as in Example 1 was performed except that 20 parts by mass of KMP-605 of Example 1 was changed to 8 parts by mass of KMP-600 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone composite powder, average particle size 5 μm).

  The procedure was the same as Example 1 except that 1.0 part by mass of leuco crystal violet of Example 1 was changed to 1.0 part by mass of 3-dibutylamino-6-methyl-7-anilinofluorane.

  The procedure was the same as Example 1 except that 1.0 part by mass of leuco crystal violet of Example 1 was not added.

  The same procedure as in Example 1 was conducted except that 10 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) in Example 1 was not added.

  The same procedure as in Example 1 was conducted except that 8 parts by mass of KMP-605 in Example 1 was not added.

  The same procedure as in Example 1 was carried out except that 8 parts by mass of KMP-605 of Example 1, 1.0 part by mass of leucocrystal violet, and 10 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) were not added.

  Example 1 was carried out in the same manner as in Example 1 except that 1.0 part by mass of leuco crystal violet and 10 parts by mass of pentaerythritol tetrakis (3-mercaptobutyrate) in Example 1 were not added.

  Except for changing 8 parts by mass of KMP-605 of Example 1 to 8 parts by mass of Tospearl 1110 (manufactured by Momentive Performance Materials Japan GK, silicone powder, average particle size 11 μm), the same as Example 1 was performed. .

  About the photocurable resin composition obtained above, deep part curability, surface curability, color change, and transmittance were evaluated as follows. The results are shown in Table 1 together with the formulation.

[Deep part curability]
The photocurable resin composition obtained in Examples 1 to 11 was poured into a mold having a depth of 5 mm, and a bandpass filter was used at around 365 nm with an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., UV-0308). The light having a wavelength of 365 nm was removed by removing light other than the above and irradiated so that the total irradiation amount was 500 mJ / cm ² at an irradiation output of 100 mW / cm ² , and the thickness of the cured product was measured with a micrometer (Mittoyo Corporation). Manufactured by MDC-MJ).

[Surface curing]
The photocurable resin composition obtained in Examples 1 to 11 was applied to a glass plate so as to have a thickness of 300 μm, and the obtained coating film was banded with an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., UV-0308). Using a pass filter, light other than around 365 nm is removed and light having a peak at a wavelength of 365 nm is irradiated so that the total irradiation amount is 500 mJ / cm ² at an irradiation output of 100 mW / cm ² , and a test piece is prepared. The touch of the surface of the coating film was evaluated. Evaluations were made as “O” for those without stickiness, and “X” for those with stickiness and paint on fingers.

[Transmissivity]
Similarly to the evaluation of the surface curability, the photocurable resin composition obtained in Examples 1 to 11 was applied to a glass plate so as to have a thickness of 300 μm, and an ultraviolet irradiation device (Nippon Battery Co., Ltd.) was applied to the obtained coating film. Company-manufactured, UV-0308) using a bandpass filter to remove light other than around 365 nm and peaking at a wavelength of 365 nm so that the total irradiation amount is 500 mJ / cm ² at an irradiation output of 100 mW / cm ^2. A test piece was prepared by irradiation, and the average light transmittance at 400 to 700 nm was measured using a spectrophotometer (trade name “U-3310” manufactured by Hitachi High-Technologies Corporation).

Claims (10)

  (A) A resin having a polymerizable unsaturated group having a number average molecular weight of 900 to 10,000, (B) a monomer having a polymerizable unsaturated group, and (C) a photopolymerization initiator, (A) and (B The photocurable resin composition containing 1 to 10 parts by mass with respect to 100 parts by mass in total.   (B) The photocurable resin composition of Claim 1 in which a component contains 1-50 mass parts with respect to 50 mass parts of (A) component.   Furthermore, the photocurable resin composition in any one of Claim 1 or 2 which contains 5-20 mass parts with respect to the total of 100 mass parts of said (A) and (B) (D) thiol compound. .   Furthermore, (E) 1-50 mass parts of filler which has an average particle diameter of 10 micrometers or less and which has light-shielding property with respect to a total of 100 mass parts of (A) component and (B) component are contained. The photocurable resin composition in any one.   Furthermore, the photocurable resin composition in any one of Claims 1-4 containing (F) leuco compound.   The photocurable light-shielding coating material containing the photocurable resin composition in any one of Claim 4 or 5.   The light leakage prevention material containing the photocurable resin composition in any one of Claim 4 or 5.   A liquid crystal display panel, wherein the photocurable light-shielding coating material according to claim 6 is applied to the outer periphery of the panel to shield it from light.   A liquid crystal display device using the liquid crystal display panel according to claim 8.   The photocurable resin composition according to any one of claims 1 to 5, the photocurable light-shielding coating material according to claim 6, and the light leakage preventing material according to claim 7, mainly having a wavelength around 365 nm based on an LED light source. A photocuring method characterized by irradiating an ultraviolet ray containing it.