JP5489447B2 - Photocurable resin composition having light-shielding property and adhesiveness and cured product thereof - Google Patents

Description

  The present invention relates to a photocurable resin composition having light shielding properties and adhesiveness after curing. The photocurable resin composition of the present invention is suitably used as a sealant for optical devices, particularly for liquid crystal displays, for fixing optical material components such as liquid crystal panels, for preventing light leakage from backlights, and for preventing external light from entering. It is done.

  In recent years, with the improvement in performance of electronic optical devices such as liquid crystal displays, optical lenses, optical pickups, and sensors, transmitted light from the outside that passes through members and fixed resin layers in order to achieve and maintain high sensitivity. It is indispensable to reduce the loss due to light leaked from the inside and light leaked from the gap. FIG. 1 shows a schematic diagram of a conventional liquid crystal display. In particular, in a portion where various properties such as adhesiveness, tackiness, strength, durability, and moisture resistance are required, such as a fixed resin layer, it is necessary to achieve both these properties and light shielding with the same resin.

  In order to achieve the above requirements, by utilizing the refractive index difference between the cured product of the photo-curable resin of the base resin and the compound added to it, it is effectively cured by light, and thus has a thick film thickness. A photocurable resin composition that can be cured even with a resin and has a low light transmittance of the resulting cured resin has been reported (Patent Document 1).

  At present, a method is generally used in which an uncured adhesive film is punched into a frame shape and bonded to a glass substrate, and then the film is cured.

JP 2007-119684 A

  When the photocurable resin composition is used as a sealing agent for a liquid crystal display, the photocurable resin composition is formed in a frame shape on a substrate or the like, and then the photocurable resin is cured to adhere. A step of adhering the (liquid crystal panel) with the photocurable resin composition is performed. Here, in order to use the photocurable resin composition described in Patent Document 1 as a sealant for a liquid crystal display, a photocurable resin composition is mixed with a thermosetting resin, and photocured after photocuring. The adhesive resin composition is required to be provided with adhesiveness. Therefore, in addition to the photocuring process, a thermosetting process is required, and this thermosetting process takes a long time. In addition, liquid crystal display components may include those that deform at about 70 ° C., and in this case, the liquid crystal display components are deformed in the thermosetting step of the photocurable resin composition. There is a problem.

  In addition, in the method using an adhesive film processed into a frame shape, the punching width of the film is limited to about 0.5 mm, and there is a limit to high-density mounting, and there is a film part that is not used after punching. Therefore, there is a problem that the material yield is low.

  In addition, in the method using a film processed into a frame shape, it takes time to handle the processed film. Further, since the film laminating process is difficult to mechanize, at present, human beings manually handle the film. There is a problem that it is difficult to automate the production line because they are pasted together.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be achieved when the photocurable resin composition has adhesiveness after photocuring and is used as a sealing agent for liquid crystal displays. The headline and the present invention were completed.

  That is, the object of the present invention is to cure effectively by light, so that even a thick film can be cured, and after curing, the light transmittance is low, the adhesiveness, and the strength, durability, moisture resistance, etc. It is providing the photocurable resin composition which is excellent also in these various characteristics.

The first aspect of the present invention is
(A) Photocurable resin, (B) Tackifier, (C) Refractive index having a difference between the refractive index of the cured product of component (A) and component (B) is 0.01 or more The present invention relates to a photocurable resin composition comprising a compound that is incompatible and dispersible with the component (A) and the component (B), and (D) a black pigment.

  2nd this invention relates to the photocurable resin composition in which (C) component is selected from the group which consists of an aluminum oxide powder and a titanium oxide powder.

  3rd this invention relates to the photocurable resin composition whose (D) component is carbon powder.

  The fourth aspect of the present invention is a photocurable resin composition, wherein the component (B) is an acrylic, silicone, maleimide, rosin ester, terpene, rubber, or aromatic hydrogenated petroleum tackifier. Related to things.

  5th this invention relates to the photocurable resin composition whose (A) component is an acrylic modified resin or an epoxy resin.

  In the sixth aspect of the present invention, the component (B) is 20 to 170 parts by weight, the component (C) is 0.2 to 80 parts by weight, and the component (D) is 0.1 parts per 100 parts by weight of the component (A). It is related with the photocurable resin composition which is -35 weight part.

  The seventh invention further relates to a photocurable resin composition containing a photopolymerization initiator.

  The eighth aspect of the present invention relates to a cured product of the above-described photocurable resin composition.

  The ninth aspect of the present invention relates to an optical device member including the above cured product.

  A tenth aspect of the present invention relates to an optical apparatus including the above-described optical apparatus member.

  The concept of the electro-optical device member of the present invention is shown in FIG.

  The photocurable resin composition of the present invention can be cured with a thick film because it is efficiently cured with light, and the resulting cured product has low light transmittance from the inside and outside, that is, has high light shielding properties and is adhesive. Excellent and various properties such as strength, durability and moisture resistance. In addition, since the photocurable resin composition can be printed, dispensed, etc., the usage rate of the photocurable resin composition is high, the fine line can be easily formed, and the production line can be automated. Therefore, productivity can be greatly improved.

  For these reasons, the photocurable resin composition of the present invention is suitable as a sealant for optical devices, particularly liquid crystal displays.

  The present invention is described in detail below.

  The photocurable resin composition of the present invention has a difference between (A) a photocurable resin, (B) a tackifier, (C) the refractive index of the cured product of the component (A) and the component (B). It contains a compound having a refractive index of 0.01 or more, incompatible with (A) component and (B) component and dispersibility, and (D) black pigment. In the present invention, by combining the (C) component and the (D) component, the light reflectivity of the (C) component is utilized to realize thick film curing and light shielding, and light shielding by the light absorption by the (D) component is realized. This is a feature.

  (A) component in this invention forms what is called a base resin with (B) component, and can also form a continuous phase also in the hardened | cured material which hardened | cured the photocurable resin composition.

  The photocurable resin in the present invention is not particularly limited as long as it is a resin that is cured by light such as visible light and ultraviolet light. For example, acrylic modified resins such as (meth) acrylic resin, urethane acrylate resin, and polyester acrylate resin; epoxy Resin; Oxetane resin is mentioned. As a photocurable resin, Preferably, an acrylic modified resin and an epoxy resin are mentioned.

  The acrylic-modified resin is defined as a monofunctional and polyfunctional (meth) acrylate compound having an acryloyl group or a methacryloyl group. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl Acrylate, isobutyl acrylate, ethyl hexyl acrylate, isodecyl acrylate, n-hexyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, butoxyethyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate Methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, octafluoropentyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol acrylate, 1 , 4-butanediol acrylate, acryloyl morpholine, 1,6-hexanediol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate ester Neopentyl glycol diacrylate Trimethylolpropane diacrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α, ω-diacrylbisdiethylene glycol phthalate, trimethylolpropane triacrylate, pentaerythritol acrylate Pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tri (meth) acrylate of trihydroxyethyl isocyanurate, dipentaerythritol hexaacrylate, and their EO and / or Or PO adduct, α, ω-tetraallylbistrimethylolpropane tetrahydrophthalate, 2-hydroxy ester Ruacryloyl phosphate, trimethylolpropane trimethacrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, Examples thereof include 6-hexanediol di (meth) acrylate, neopentylglycol dimethacrylate, diacryloxyethyl phosphate, N-vinylpyrrolidone and oligomers having these photoreactive functional groups. Examples of the oligomer include (meth) acrylate compounds having a polyether skeleton, a polycarbonate skeleton, or a polyester skeleton. Commercially available products include polycarbonate acrylate (product name: UN5500) manufactured by Negami Kogyo Co., Ltd., polyester acrylate (product name: UN7700), and polyether acrylate (product name: Nippon Synthetic Chemical Industry Co., Ltd.). UV3700B) and the like. Of the above acrylic-modified resins, polycarbonate acrylate is particularly preferable as the component (A).

  The epoxy resin is defined as a compound having a molecular structure having one or more epoxy groups, for example, biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F. Diglycidyl ethers of bisphenols such as tetrachlorobisphenol A and tetrabromobisphenol A, polyglycidyl ethers of novolac resins such as phenol novolak, cresol novolak, brominated phenol novolak, orthocresol novolak, ethylene glycol, polyethylene glycol, Polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1 Diglycidyl ethers of alkylene glycols such as 4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycidyl esters such as glycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl -3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate Lactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis (3,4-epoxycyclohexyl) Examples thereof include alicyclic epoxy compounds such as (xylmethyl) -4,5-epoxytetrahydrophthalate and bis (3,4-epoxycyclohexyl) diethylsiloxane, and oligomers having these photoreactive functional groups. Of the above epoxy resins, bisphenol A is particularly preferable as the component (A). Epoxy resins can be used in combination with acrylic-modified resins.

  (A) component in this invention is not specifically limited by the refractive index after hardening, The photocurable resin which gives the hardened | cured material which has arbitrary refractive indexes can be used. In the present invention, the component (A) is selected from the above resins as one or a mixture of two or more in consideration of the performance required at the site to be used.

  The component (B) in the present invention forms a base resin together with the component (A). Component (B) is a tackifier and imparts tackiness to the cured photocurable resin composition. Examples of the component (B) include tackifiers such as acrylic, silicone, maleimide, rosin ester, terpene, rubber and aromatic petroleum. From the viewpoint of heat resistance and compatibility, acrylic Type, rosin ester type, terpene type and aromatic hydrogenated petroleum type are preferred. Commercially available products include formula (1):

A polyol type xylene resin (modified product) (K140) manufactured by Fudo Co., Ltd.

  The photocurable resin composition of the present invention may contain one of the components (B) or a combination of two or more thereof.

  The refractive index of the cured product of the component (A) and the component (B) is obtained by curing a mixture of the component (A) and the component (B), and using the Abbe refractometer (manufactured by Atago Co., Ltd.) for the mixture by the D line. taking measurement.

  The component (C) in the present invention has a refractive index such that the difference between the refractive index of the cured product of the component (A) and the component (B) is 0.01 or more, and the component (A) and the component (B) It is a compound that is incompatible and dispersible with respect to the refractive index of the cured product of component (A) and component (B), and incompatibility and dispersibility with respect to component (A) and component (B). The The component (C) is composed of a compound (high refractive index compound) having a refractive index larger by 0.01 or more than the refractive index of the cured product of the components (A) and (B), and the components (A) and (B). It is roughly classified into compounds having a refractive index smaller than the refractive index of the cured product by 0.01 or more (low refractive index compounds). (C) A component is an organic compound or an inorganic compound.

Examples of the inorganic compound as the component (C) having a refractive index different by 0.01 or more from the cured product (also referred to as base resin) of the component (A) and the component (B) that can be used in the present invention include ZnO, TiO ₂ (oxidation). _{titanium), CeO 2, Sb 2 O} 5, SnO 2, ITO, Y 2 O 3, La 2 O 3, ZrO 2, Al 2 O 3 ( aluminum oxide), silica, opal glass, white carbon are encompassed, Preferably, Al ₂ O ₃ , TiO ₂ or ZrO ₂ having a refractive index of 1.60 or more is used. Examples of commercially available products include alumina filler (product name: AO-902H) manufactured by Admatechs Corporation. Here, Al ₂ O ₃ and TiO ₂ are particularly preferable because they are excellent in light reflectivity. The surface of the inorganic compound may be coated with various inorganic / organic compounds. Further, the shape of the inorganic compound may be any shape such as a spherical shape, a needle shape, a plate shape, and the particle size is not limited, but a smaller particle size is more preferable. The particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly 0.1 to 1 μm.

  The organic compound as the component (C) having a refractive index different by 0.01 or more from the base resin that can be used in the present invention may be a liquid or solid monomer, oligomer, or polymer compound, and may be a thermoplastic resin, There is no problem whether it is a thermosetting resin or a photocurable resin, but it must be incompatible with the photocurable resin that is the base resin and has good dispersibility. For example, (meth) acrylic resin, urethane acrylate resin, polyester acrylate resin, epoxy resin, oxetane resin, polystyrene resin such as polystyrene, polyethylene terephthalate, polyvinyl carbazole, polycarbonate of bisphenol A, polyvinyl chloride, polytetrabromobisphenol A glycidyl Ether, polybisphenol S glycidyl ether, polyvinyl pyridine, thiourethane resin, thioepoxy resin, fluorine-containing (meth) acrylates, fluorinated alkylene ether oligomers (average molecular weight: 4000 or less) monofunctional and bifunctional or more polyfunctional Crystalline polymers such as (meth) acrylates, silicon-containing (meth) acrylates, polyethylene and polytetrafluoroethylene are included.When the organic compound is solid, the shape thereof may be any shape such as a spherical shape, a needle shape, or a plate shape, and the particle size is not limited, but a smaller particle size is preferable. The particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly 0.1 to 1 μm. When the organic compound is in a liquid state, the compound is dispersed in a photocurable resin. The particle diameter of the dispersed particles is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly 0.1 to 1 μm.

The refractive index of some of the compounds that can be used as the component (C) in the present invention is exemplified below.
ZnO (refractive index 1.90), TiO ₂ (refractive index 2.3 to 2.7), CeO ₂ (refractive index 1.95), Sb ₂ O ₅ (refractive index 1.71), SnO ₂ , ITO ( Refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂ O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.05), Al ₂ O ₃ (refractive index 1. 6-1.8), melamine resin (1.6), nylon (1.53), polystyrene (1.6), polyethylene (1.53), polytetrafluoroethylene (1.35), methyl methacrylate resin (1.49), vinyl chloride resin (1.54), silicone oil (1.4).

  In the present invention, the difference between the refractive index of the component (C) and the refractive index of the cured product of the components (A) and (B) is preferably 0.05 or more, more preferably 0.1 or more, particularly preferably 0. .15 or more.

  The photocurable resin composition of the present invention may contain one or a combination of two or more of organic and inorganic high refractive index compounds and organic and inorganic low refractive index compounds as the component (C).

  "Incompatible" with the component (A) and the component (B) means that the component (C) is not uniformly mixed with the mixture of the component (A) and the component (B). "Dispersible" with respect to the component (B) and the component (B) means that the component (C) and the mixture of the component (A) and the component (B) do not separate into two layers immediately after stirring.

(D) component in this invention is a black pigment, and provides light-shielding property to a photocurable resin composition. In order to maintain the workability of the photocurable resin composition, the component (D) is preferably one that imparts light-shielding properties with a small amount of addition. (D) includes inorganic or organic pigments. Examples of the inorganic pigment include carbon powder, ivory black, mars black, peach black, lamp black, inorganic black containing titanium, copper, iron, chromium, manganese, cobalt, and the like. It is preferably a carbon powder, more preferably carbon black, acetylene black, ketjen black, carbon nanotube, natural graphite powder, artificial graphite powder, and the like. From the viewpoint of imparting, carbon black, acetylene black, and ketjen black are particularly preferable. Examples of the organic pigment include aniline black and perylene black, and perylene black is preferable. Examples of commercially available products include black pigments (product name: NBD-0744) manufactured by Nihongo Bix Corporation .

  The photocurable resin composition of the present invention may contain one of the components (D) or a combination of two or more thereof.

  In the photocurable resin composition of the present invention, the component (B) is 20 to 170 parts by weight, the component (C) is 0.2 to 80 parts by weight and the component (D) with respect to 100 parts by weight of the component (A). May be 0.1 to 35 parts by weight.

  In the photocurable resin composition of the present invention, the component (B) is preferably 30 to 150 parts by weight and more preferably 50 to 120 parts by weight with respect to 100 parts by weight of the component (A).

  In the photocurable resin composition of the present invention, the component (C) is preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight, and 8 to 30 parts by weight with respect to 100 parts by weight of the component (A). Is particularly preferred.

  In the photocurable resin composition of the present invention, the component (D) is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the component (A). .14 to 0.7 parts by weight is particularly preferred.

  The photocurable resin composition of the present invention preferably has a viscosity of 5,000 to 200,000 mPa · s, and more preferably 10,000 to 80,000 mPa · s, from the viewpoints of printability and dispenseability. Here, the viscosity of the photocurable resin composition is measured using a RE-10U viscometer manufactured by Toki Sangyo Co., Ltd. under a room temperature condition with a cone plate rotor.

  The photocurable resin composition of the present invention may further contain a photopolymerization initiator. Examples of the photopolymerization initiator include generally commercially available radical or cationic initiators. For example, carbonyl group systems: benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2 -Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, Benzoin isobutyl ether, benzoin-n-butyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N, N′-dimethylacetophenones; sulfide systems: diphenyl disulfide, dibenzyl disulfide; Examples include quinone series: benzoquinone, anthraquinone; azo series: azobisisobutyronitrile, 2,2′-azobispropane. Commercially available products include 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184) manufactured by Ciba Japan Co., Ltd., and a eutectic mixture of 50 parts of 1-hydroxycyclohexyl phenyl ketone and 50 parts of benzophenone (product name: IRGACURE 500). Etc. A photoinitiator can be used in the quantity generally used, for example, the quantity of 1-10 weight part with respect to 100 weight part of photocurable resin of (A) component. Irradiation light may be visible light, ultraviolet light, radiation, or electron beam, but ultraviolet light is preferable from the viewpoint of adhesiveness after curing.

  Moreover, in order to improve the adhesiveness after hardening, the photocurable resin composition of this invention can contain a bubble in the range which does not impair the effect of this invention.

  The photocurable resin composition of the present invention may contain a solvent for the purpose of improving printability, but is used without a solvent from the viewpoint of environmental considerations and the usage rate of the photocurable resin composition. It is also preferable.

  Depending on the purpose, the photocurable resin composition of the present invention may further include other known additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, and leveling. Agents, surfactants, colorants, storage stabilizers, plasticizers, lubricants, fillers, anti-aging agents, wettability improvers, mold release agents, and the like can be added.

  The photocurable resin composition of the present invention can be produced by mixing the above components by a conventional method. The order of adding each component is not particularly limited. When the high refractive index or low refractive index compound is liquid, it is preferable to disperse the compound in a photocurable resin with a fine particle size.

  The photocurable resin composition of the present invention can be printed and dispensed by methods known to those skilled in the art, such as a screen printing machine and a dispenser, and can easily form fine lines. The line width of the fine line is preferably 1000 μm or less, more preferably 700 μm or less, and particularly preferably 600 μm or less. Further, from the viewpoint of light shielding properties, adhesiveness, and sealing properties, the fine line width is preferably 500 μm or more, and more preferably 600 μm or more.

The photocurable resin composition of the present invention can be effectively cured by light such as visible light and ultraviolet light, and can be cured in a wide range of film thickness, for example, in a range of 0.5 μm or more. . The photocuring conditions may vary depending on the composition and film thickness of the resin composition. For example, component (A): acrylic resin, component (B): acrylic tackifier, component (C): alumina, component (D): Carbon black, when the film thickness is 100 μm, the ultraviolet irradiation amount is 1000 mJ / cm ² or more.

  The present invention includes a cured product of the photocurable resin composition. This cured product has light-shielding properties and adhesiveness, and has excellent properties such as strength, durability, and moisture resistance. Satisfied. The cured product of the present invention has a light transmittance at 300 to 800 nm of 1% or less, for example 0.5% or less, preferably 0.1% or less, particularly 0.05% in a film thickness in the range of 30 μm to 150 μm. Hereinafter, it can be further 0.01% or less.

  In the present invention, “having adhesiveness” means that the adherend adheres to the photocurable resin composition after curing, the viscosity that allows the adherend to wet, and the adherend after being attached. It means a state having both elasticity that it is difficult to peel off from the body.

  The present invention also includes an optical device member containing the above cured product. Examples of the optical device member include a liquid crystal panel, a sensor, an optical pick, an optical lens, and an LED. The present invention is particularly suitable for a liquid crystal panel.

  The present invention further relates to an optical apparatus including the above-described optical apparatus member. Examples of the optical device include various displays, digital cameras, various recording media players, and the like, and are particularly suitable for liquid crystal displays.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, “part” is based on weight.

(Examples 1-6 and Comparative Example 1)
First, Examples 1-6 were performed in order to investigate the influence of the addition amount of the component (D) on the deep curability of the photocurable resin composition.

(Preparation of photocurable resin composition)
As the component (A), 84 parts of polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Negami Kogyo Co., Ltd., 2-hydroxylethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd. ) 14 parts, and 2 parts of lauryl acrylate (product name: LA) manufactured by Kyoeisha Chemical Co., Ltd., as component (B), polyol type xylene resin (modified product) manufactured by Fudou Co., Ltd. (K140) 84 parts, as component (C) , 14 parts by weight, alumina filler (product name: AO-902H, average particle size: 0.7 μm, refractive index: 1.76) manufactured by Admatechs Co., Ltd. Name: NBD-0744) 0.14 to 7.0 parts (see Table 1), as a photopolymerization initiator, Ciba Japan Co., Ltd. 1- Mud alkoxy phenyl ketone 50 parts of benzophenone, 50 parts mixture (product name: IRGACURE 500) 4.2 parts were mixed and a photocurable resin composition was prepared. As Comparative Example 1, only the component (D) was changed to 0 part, and the others were mixed in the same manner as in Examples 1 to 6 to prepare a photocurable resin composition. In addition, the refractive index of the hardened | cured material of a component (A) and (B) component was 1.52.

(Filling tube with photocurable composition)
As shown in FIG. 3, a 5 mm-diameter ultraviolet transparent black polyethylene tube was attached on an aluminum plate. After filling the prepared photocurable resin composition to the tip of the black tube so that the height of the tube was 1 to 2 mm on the aluminum plate, the black tube was sealed to prepare a sample.

(Light irradiation)
Eye Graphics Co., Ltd. uses a ride type UV lamp (model number: MO3-L31), and the measured value with a UV sensor (model number: UV-35) manufactured by Oak Manufacturing Co., Ltd. is 3,000 mJ / cm. UV was irradiated so that it might be set to ² . Irradiation was performed so that only UV light parallel to the UV lamp (in the depth direction with respect to the resin) could enter.

(Measurement of the cured portion of the photocurable composition)
The cured part of the photocurable composition was taken out from the black tube after UV irradiation, and the thickness of the cured part was measured with a micrometer. The measurement was performed at n = 5.

(result)
The results are shown in Table 1.

  As shown in Table 1, it was demonstrated that a photocurable composition having a thickness of 110 μm or more can be cured if the amount of black pigment added is 4.2 parts or less. From the standpoint of obtaining a cured thickness of 200 to 300 μm, a more preferable addition amount of the black pigment is 0.14 to 0.7 part.

(Example 7)
Next, Example 7 was performed in order to investigate the relationship between the film thickness of the cured photocurable resin composition and the light shielding property.

(Preparation of photocurable resin composition)
As the component (A), 84 parts of polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Negami Kogyo Co., Ltd., 2-hydroxylethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd. ) 14 parts, Kyoeisha Chemical Co., Ltd. lauryl acrylate (product name LA) 2.0 parts, (B) component, Fudou Co., Ltd. polyol type xylene resin (modified product) (K140) 84 parts, (C) component As an alumina filler (product name: AO-902H, average particle size: 0.7 μm, refractive index: 1.76) 21 parts by Admatechs Co., Ltd. (Product name: NBD-0744) 0.42 parts, 1-hydroxycyclohexacene manufactured by Ciba Japan Co., Ltd. as a photopolymerization initiator Le phenyl ketone 50 parts of benzophenone, 50 parts mixture (product name: IRGACURE 500) 4.2 parts were mixed to prepare a photocurable resin composition. In addition, the refractive index of the hardened | cured material of a component (A) and (B) component was 1.52.

(Application of photocurable composition)
Next, the prepared photocurable resin composition was applied to a crown glass substrate having a thickness of 1.0 mm using a dispenser with a width of 1 mm, a length of 50 mm, and a thickness of 50 μm or 100 μm. Was made.

(Light irradiation)
As in Examples 1 to 6, the prepared samples were irradiated with UV.

(Preparation of samples of cured photocurable resin compositions having thicknesses of 200, 300, and 500 μm)
Samples of the cured photocurable resin composition having a film thickness of 200, 300, and 500 μm were prepared by repeating the application of the photocurable composition at a thickness of 100 μm and the light irradiation.

(Measurement of light transmittance)
Using the samples with the film thicknesses of 50, 100, 200, 300, and 500 μm produced as described above with an ultraviolet-visible spectrophotometer (model number: U-best V-570) manufactured by JASCO Corporation, Wavelengths of 300 nm (ultraviolet region), 400 nm (ultraviolet / visible region), 500 nm (visible region), 600 nm (visible region), 700 nm (visible region), 800 nm (visible region / infrared region) The transmittance was measured.

(result)
Table 2 shows the obtained results regarding the relationship between the film thickness and the transmittance of the photocurable resin composition.

From the results of Table 2, when the thickness of the cured photocurable resin composition is 100 μm or less, ultraviolet light or visible light is transmitted, and even when the thickness is 200 μm, visible light / infrared light is transmitted. It has been demonstrated to penetrate. This result is considered to be the same for the photocurable resin composition before curing. On the other hand, when the thickness is 100 μm or more, ultraviolet rays do not transmit, and when the thickness is 200 μm or more, preferably 300 μm or more, ultraviolet rays / visible light region to visible light region / infrared light region do not transmit or hardly transmit. Proven.

(Preparation of photocurable resin composition)
As the component (A), 84 parts of polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Negami Kogyo Co., Ltd., 2-hydroxylethyl methacrylate (product name: HO) manufactured by Kyoeisha Chemical Co., Ltd. ) 10 parts, Kyoeisha Chemical Co., Ltd. lauryl acrylate (product name: LA) 2.0 parts, (B) as component (Budo) polyol type xylene resin (modified product) (K140) 84 parts, (C) As component, alumina filler manufactured by Admatechs Co., Ltd. (product name: AO-902H, average particle size: 0.7 μm, refractive index: 1.76), 14 parts, (D) component, black pigment manufactured by Nihongo Bix Co., Ltd. (Product name: NBD-0744) 0.28 parts, 1-hydroxycyclohexane manufactured by Ciba Japan Co., Ltd. as a photopolymerization initiator Mixture of 50 parts sill phenyl ketone and benzophenone 50 parts (product name: IRGACURE 500) 4.2 parts were mixed to prepare a photocurable resin composition. As Comparative Example 2, only the component (D) was changed to 0 part, and the others were mixed in the same manner as in Example 8 to prepare a photocurable resin composition. In addition, the refractive index of the hardened | cured material of a component (A) and (B) component was 1.52.

(Application of photocurable composition)
Next, using a dispenser, the prepared photocurable resin composition with a width of 1 mm, a length of 50 mm, and a thickness of 100 μm is applied onto a 1.0 mm thick crown glass substrate to produce a sample. did.

(Light irradiation)
As in Examples 1 to 6, the prepared samples were irradiated with UV.

(Preparation of a sample of a cured photocurable resin composition having a thickness of 500 μm)
A sample of a cured photocurable resin composition having a thickness of 500 μm was produced by repeating the application of the photocurable composition at a thickness of 100 μm and light irradiation four more times.

(Measurement of light transmittance)
In the same manner as in Example 2, the transmittance and the reflectance were further measured. The reflectance was measured by an absolute reflection method using a UV-visible spectrophotometer (model number: U-best V-570) manufactured by JASCO Corporation.

FIG. 4 shows the result of the relationship between the wavelength and the transmittance in the photocurable resin composition, and FIG. 5 shows the result of the relationship between the wavelength and the reflectance in the photocurable resin composition.

  As shown in FIG. 4, there is a difference in transmittance between Example 8 in which component (D) was added and Comparative Example 2 in which component (D) was not added. As shown in FIG. 5, the reflectance of Example 8 is reduced to about ½ at a wavelength of 300 nm as compared with the reflectance of Comparative Example 2, and about the reflectance of Comparative Example 2 at a wavelength of 350 nm or more. It has been demonstrated that it drops to 1/5 or less.

(Examples 9 to 16)
Next, Examples 9 to 16 were performed in order to examine the influence of the addition of the component (A) on the adhesive strength of the cured photocurable resin composition.

(Preparation of photocurable resin composition)
In the amount shown in Table 3, as the component (A), as a component, polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Negami Kogyo Co., Ltd., 2-hydroxyl manufactured by Kyoeisha Chemical Co., Ltd. Ethyl methacrylate (product name: HO), benzyl methacrylate (product name: BZ) manufactured by Kyoeisha Chemical Co., Ltd., (B) component, polyol type xylene resin (modified product) (K140), (C) component manufactured by Fudou Co., Ltd. As an alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) manufactured by Admatechs Co., Ltd. : NBD-0744), as a photopolymerization initiator, 1-hydroxycyclohexyl phenyl keto manufactured by Ciba Japan Co., Ltd. 50 parts of benzophenone, 50 parts mixture (product name: IRGACURE 500) were mixed to prepare a photocurable resin composition. In addition, the refractive index of the hardened | cured material of a component (A) and (B) component was 1.53.

(Preparation of adhesive strength test sample)
Using the prepared photocurable resin composition, as shown in FIG. 6, it was defined by two spacers having a thickness of 100 μm on a glass plate having a length of 75 mm, a width of 25 mm, and a thickness of 2.5 mm. The photocurable resin composition was applied to a groove having a width of 1.5 cm (application length: 75 mm, application width: 15 mm, application thickness: 100 μm). After removing the two spacers, the photocurable resin composition applied on the glass plate was cured by UV irradiation. Thickness: A polycarbonate (PC) plate having a thickness of 500 μm was bonded to prepare a sample for a peel strength test. Although hardening of the photocurable resin composition was performed similarly to Examples 1-6, UV light was irradiated from the glass side.

(Adhesive strength test)
A jig was attached to the prepared sample, and a peel test was performed at 300 mm / min and a shear test was performed at 5 mm / min using a tensile tester manufactured by Shimadzu Corporation. The results are shown in Table 3.

(result)
Table 3 shows the results of the peel test and the shear test.

  As can be seen from Table 3, when the amount of component (A) added is 100 parts by weight and component (B) is 55 to 85 parts by weight, a peel strength of 1.0 N / 25 mm or more and a shear strength of 2.2 MPa or more are obtained. It is demonstrated that when the amount of component (A) added is 100 parts and component (B) is 60 to 85 parts by weight, a peel strength of 1.2 N / 25 mm or more and a shear strength of 2.9 MPa or more can be obtained. It was done.

(Examples 17 to 23)
Next, Examples 17 to 23 were performed in order to examine the influence of the addition of the component (B) on the adhesive strength of the cured photocurable resin composition.

(Preparation of photocurable resin composition)
In the amount shown in Table 4, as the component (A), as a component, polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Negami Kogyo Co., Ltd., 2-hydroxyl manufactured by Kyoeisha Chemical Co., Ltd. Ethyl methacrylate (product name: HO), benzyl methacrylate (product name: BZ) manufactured by Kyoeisha Chemical Co., Ltd., (B) component, polyol type xylene resin (modified product) (K140), (C) component manufactured by Fudou Co., Ltd. As an alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) manufactured by Admatechs Co., Ltd. : NBD-0744), as a photopolymerization initiator, 1-hydroxycyclohexyl phenyl keto manufactured by Ciba Japan Co., Ltd. 50 parts of benzophenone, 50 parts mixture (product name: IRGACURE 500) were mixed to prepare a photocurable resin composition. In addition, the refractive index of the hardened | cured material of a component (A) and (B) component was 1.53.

(Preparation of adhesive strength test sample, adhesive strength test)
Using the prepared photocurable resin composition, a sample was prepared in the same manner as in Examples 9 to 16, and peel strength and shear strength were measured.

(result)
Table 4 shows the results of the peel test and the shear test.

    As can be seen from Table 4, the amount of component (A) added is 100 parts by weight, the amount of component (B) added is 70 to 116 parts, the peel strength is 1.0 N / 25 mm or more, and the shear is 3.7 MPa or more. It was proved that the strength was obtained, and the peel strength of 1.6 N / 25 mm or more and the shear strength of 4.3 MPa or more were obtained when the added amount of the component (B) was 70 to 101 parts.

  The photocurable resin composition of the present invention is capable of thick film curing, has low light transmittance after curing, has adhesiveness, and is excellent in various properties such as strength, durability, and moisture resistance. Yes. Productivity is greatly improved, and it is suitable as a resin for manufacturing various optical equipment members and molding resins that require light shielding properties.

It is a figure which shows the conventional optical equipment member. It is a figure which shows the concept of the optical equipment member of this invention. 2 is a schematic diagram of a sample of Example 1. FIG. It is a figure which shows the relationship between the wavelength in a photocurable resin composition, and the transmittance | permeability. It is a figure which shows the relationship between the wavelength in a photocurable resin composition, and a reflectance. It is a schematic diagram of the sample for a peel strength test. It is a schematic diagram of a peel strength test method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 LCD panel 2 Fixed (sealing) resin layer 3 Board | substrate 4 Backlight 5 Photocurable resin composition after hardening which has light-shielding property and adhesiveness 6 Photocurable resin composition before hardening 7 Black tube 8 Aluminum plate 9 Glass plate 10 PC plate A Transmitted light from outside B Leaked light from inside (lost light)
C UV

Claims (7)

(A) a photo-curable resin which is an acrylic-modified resin or an epoxy resin , (B) an acrylic, rosin ester, terpene or aromatic petroleum tackifier, (C) the component (A) and (B And (D) a compound having a refractive index such that the difference from the refractive index of the cured product of the component is 0.1 or more, incompatible with the component (A) and the component (B), and dispersible. A photocurable resin composition containing a black pigment that is carbon powder , wherein (B) component is 20 to 170 parts by weight, and (C) component is 0.2 to 80 with respect to 100 parts by weight of component (A). The photocurable resin composition whose weight part and (D) component are 0.1-35 weight part .   The component (B) has the formula (1):

The photocurable resin composition according to claim 1, which is a polyol-modified xylene resin represented by: The photocurable resin composition according to claim 1 or 2 , wherein the component (C) is selected from the group consisting of aluminum oxide powder and titanium oxide powder. Furthermore, the photocurable resin composition of any one of Claims 1-3 containing a photoinitiator. Hardened | cured material of the photocurable resin composition of any one of Claims 1-4 . An optical device member comprising the cured product according to claim 5 . An optical apparatus comprising the optical apparatus member according to claim 6 .

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