TWI447159B - A photohardenable resin composition having shading and adhesion, and a hardened product thereof - Google Patents

Description

Photocurable resin composition having light blocking property and adhesive property and cured product thereof

The present invention relates to a photocurable resin composition having light blocking properties and adhesion after curing. The photocurable resin composition of the present invention can be suitably used for fixing an optical material such as a liquid crystal panel or preventing light leakage of a backlight or preventing external light from entering the sealing agent of an optical device, particularly a liquid crystal display.

In recent years, with the high performance of displays such as liquid crystal displays or optical optical devices such as optical lenses, optical pickups, and sensors, in order to achieve and maintain high sensitivity, transmitted light from the outside of the passing member or the fixed resin layer or The loss of light from the internal light leakage and light leakage from the gap is indispensable. In Fig. 1, a schematic diagram of a conventional liquid crystal display is shown. In particular, in the case where the resin layer is fixed, various properties such as adhesion, adhesion, strength, durability, and moisture resistance can be sought, and it is necessary to make such characteristics and light-shielding in the same resin.

In order to achieve the above-mentioned requirements, a photocurable resin composition which is effective by utilizing a difference in refractive index between a cured product of a photocurable resin of a base resin and a compound added thereto has been reported. Since the resin is hardened, the resin having a thick film thickness can be cured, and the obtained cured resin has a low light transmittance (Patent Document 1).

Further, at present, a method in which an unhardened adhesive film is impact-processed into a frame shape and bonded to a glass substrate to cure the film is generally used.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2007-119684

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 form an adherend (liquid crystal panel). The photocurable resin composition is then subjected to a step. Here, in order to use the photocurable resin composition described in Patent Document 1 as a sealing agent for a liquid crystal display, it is possible to find a photocurable resin which is prepared by photocuring a photocurable resin composition and a photocurable resin. The composition imparts adhesion. Therefore, in addition to the step of photohardening, a step of thermosetting is required, and this step of thermal hardening takes a long time. Further, the parts of the liquid crystal display may be deformed at about 70 ° C. In this case, in the thermal curing step of the photocurable resin composition, the problem of deformation of the parts of the liquid crystal display still exists.

Moreover, by using a method of processing a frame-shaped adhesive film, the impact width of the film is limited to about 0.5 mm, limited in high-density encapsulation, and the film portion which is not used after the impact is generated, so that the material is available. The problem of low yield.

Further, in the method of processing a film formed into a frame shape, the handleability of the film after processing is troublesome, and further, the bonding step of the film is difficult to mechanize, and therefore, the film is bonded by hand by hand. Problems such as the difficulty of automating the production line still exist.

As a result of intensive studies, the inventors of the present invention have found that when the photocurable resin composition is formed into a photocurable adhesive and is used as a sealant for a liquid crystal display, the above problems can be attained. invention.

That is, an object of the present invention is to provide a photocurable resin composition which is effectively cured by light, so that it can be cured even with a thick film thickness, and has low light transmittance, adhesion, and strength after hardening. Various properties such as durability and moisture resistance are also excellent.

According to a first aspect of the invention, there is provided a photocurable resin composition comprising: (A) a photocurable resin; (B) an adhesion imparting agent; (C) having the component (A) and (B); The difference in refractive index of the cured product is a refractive index of 0.01 or more, a compound which is incompatible with the component (A) and the component (B), and a dispersible compound, and (D) a black pigment.

According to a second aspect of the invention, there is provided a photocurable resin composition, wherein the component (C) is selected from the group consisting of alumina powder and titanium oxide powder.

The third aspect of the invention relates to a photocurable resin composition in which the component (D) is a carbon powder.

According to a fourth aspect of the invention, there is provided a photocurable resin composition, wherein the component (B) is an acrylic resin, a polyoxyxene system, a maleimide system, a rosin ester system, a terpene system, a rubber system, or an aromatic hydrogenation. Petroleum system adhesion imparting agent.

The fifth aspect of the invention relates to a photocurable resin composition, wherein the component (A) is an acrylic modified resin or an epoxy resin.

The present invention relates to a photocurable resin composition, wherein the component (B) is 20 to 170 parts by weight, the component (C) is 0.2 to 80 parts by weight, and (D), based on 100 parts by weight of the component (A). The composition is 0.1 to 35 parts by weight.

The invention of the seventh aspect relates to a photocurable resin composition further comprising a photopolymerization initiator.

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

The ninth aspect of the invention relates to an optical machine component comprising the above-mentioned cured product.

The invention of claim 10 relates to an optical device comprising the above-described optical machine member.

The concept of the electro-optical machine component of the present invention is shown in FIG.

Since the photocurable resin composition of the present invention can be efficiently cured by light, it can be cured by a thick film, and the obtained cured product has low light transmittance from inside and outside, that is, high light blocking property, excellent adhesion, and strength. It is also excellent in various properties such as durability and moisture resistance. Further, since the photocurable resin composition can be printed or dispensed, the use ratio of the photocurable resin composition is high, and fine lines are easily formed. Further, the production line can be automated, so that productivity can be sufficiently improved.

Therefore, the photocurable resin composition of the present invention can be suitably used as a sealant for an optical device, particularly a liquid crystal display.

[Formation for implementing the invention]

The invention is described in detail below.

The photocurable resin composition of the present invention contains (A) a photocurable resin, (B) an adhesiveness imparting agent, and (C) a cured product having the component (A) and the component (B). The difference in refractive index is 0.01 or more, the compound (A) and the component (B) are incompatible and dispersible, and (D) a black pigment. In the present invention, the component (C) and the component (D) are characterized in that the light reflectance of the component (C) is used to achieve thick film hardening and light shielding, and the light absorption by the component (D) is used to achieve light-shielding.

In the present invention, the component (A) forms a so-called base resin together with the component (B), and a continuous phase can be formed even in a cured product obtained by curing the photocurable resin composition.

The photocurable resin of the present invention is not particularly limited as long as it is a resin which is cured by light such as visible light or ultraviolet light, and examples thereof include (meth)acrylic resin, urethane acrylate resin, and poly Acrylic modified resin such as ester acrylate resin; epoxy resin; oxetane resin. The photocurable resin is preferably, for example, an acrylic modified resin or an epoxy resin.

The acrylic modified resin is defined as a monofunctional and polyfunctional (meth) acrylate compound having an acrylonitrile group or a methacryl oxime group, and examples thereof include methacrylate, ethyl acrylate, and n-propyl group. Acrylate, n-butyl acrylate, tert-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, methoxy diethylene glycol acrylate, ethoxy diethylene glycol acrylate, methoxy two Propylene glycol acrylate, octafluoropentyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butyl Glycol acrylate, 1,4-butanediol acrylate, propylene sulfhydryl Porphyrin, 1,6-hexanediol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, Hydroxytrimethylacetate, neopentyl glycol diacrylate, trimethylolpropane diacrylic acid, 1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin, 3-methyl Pentyl glycol acrylate, α,ω-diacrylic bis diethylene glycol phthalate, trimethylolpropane triacrylate, pentaerythritol acrylate, pentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentoxide, five Pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris(meth) acrylate of trishydroxyethyl tripolyisocyanate, dipentaerythritol hexaacrylate, and EO and/or PO adducts thereof, α, ω-four Allyl ditrimethylolpropane tetrahydrofurfurate, 2-hydroxyethyl propylene decyl phosphate, trimethylolpropane trimethacrylate, ethylene glycol di(meth) acrylate, tetraethyl Diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(methyl)propyl Acid ester, 1,6-hexanediol di(meth)acrylate, neopentyl glycol dimethacrylate, dipropylene oxyethyl phosphate, N-vinylpyrrolidone and photoreactivity thereof An oligomer of a functional group. The oligomer may, for example, be a (meth) acrylate compound having a polyether skeleton, a polycarbonate skeleton or a polyester skeleton. The commercially available product is, for example, a polycarbonate acrylate (product name: UN5500) manufactured by Kokusai Industrial Co., Ltd., a polyester acrylate (product name: UN7700), and a polyether made by Nippon Synthetic Chemical Industry Co., Ltd. It is an acrylate (product name: UV3700B). Among the above acrylic modified resins, the component (A) is preferably a polycarbonate acrylate.

The epoxy resin is defined as a compound having a molecular structure containing one or more epoxy groups, and examples thereof include bisphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and tetramethyl group. Bisphenol A, tetramethyl bisphenol F, tetrachlorobisphenol A, tetrabromobisphenol A, etc. bisphenolic diglycidyl ethers, phenol novolacs, cresol novolacs, brominated phenol novolacs, Polyglycidyl ethers of novolac resin such as o-cresol novolac, ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trishydroxyl Alkylene glycol diglycidyl ethers such as propane, 1,4-cyclohexanedimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct a glycidyl ester such as a glycidyl hexahydrophthalic acid or a diglycidyl ester of a dibasic acid, or a 3,4-epoxycyclohexylmethyl-3',4'-epoxy ring. Hexane carboxylate, 3,4-epoxycyclohexylethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl-3 ',4'-Epoxy-6'-methylcyclohexanecarboxylate, vinylcyclohexene Oxide, 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy Cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate, bis(3,4-epoxycyclohexylmethyl)adipate, lactone modification 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), methylene double (3,4-epoxycyclohexanecarboxylate), dicyclohexadiene diepoxide, bis(3,4-epoxycyclohexyl)ether, bis(3,4-epoxy ring) Hexylmethyl)ether, tetrakis(3,4-epoxycyclohexylmethyl)butanetetracarboxylate, bis(3,4-epoxycyclohexylmethyl)-4,5-epoxytetra An alicyclic epoxy compound such as hydroquinone ester or bis(3,4-epoxycyclohexyl)diethyloxane or an oligomer having such a photoreactive functional group. Among the above epoxy resins, the component (A) is particularly preferred as bisphenol A. The epoxy resin can be used together with an acrylic modified resin.

The component (A) in the present invention is not particularly limited as long as it depends on the refractive index after curing, and a photocurable resin which imparts a cured product having an arbitrary refractive index can be used. In the present invention, the component (A) can be selected from the above-mentioned resins, and one or a mixture of two or more kinds can be selected in consideration of the properties obtained in the site to be used.

The component (B) in the present invention forms a base resin together with the component (A). The component (B) is an adhesiveness imparting agent, and imparts adhesiveness to the cured photocurable resin composition. The component (B) may, for example, be an adhesiveness imparting agent such as an acrylic, a polyoxygen, a maleimide, a rosin ester, a terpene, a rubber or an aromatic petroleum, and has heat resistance and compatibility. The viewpoint is preferably an acrylic, rosin ester, terpene or aromatic hydrogenated petroleum system. The commercially available product can be, for example, given by formula (1):

The polyol type xylene resin (modified product) (K140) manufactured by Fudow Co., Ltd. is shown.

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

The refractive index of the hardened material of the component (A) and the component (B) was hardened by the mixture of the component (A) and the component (B), and the Abbe refractive index (manufactured by Atago Co., Ltd.) was used for the mixture, and the measurement was carried out by the D line.

In the present invention, the component (C) has a refractive index of 0.01 or more from the refractive index of the cured product of the component (A) and the component (B), and the component (A) and the component (B) are non-component. The compound which is compatible and has dispersibility can be selected depending on the refractive index of the cured product of the component (A) and the component (B), and the incompatibility and dispersibility of the component (A) and the component (B). The component (C) can be roughly classified into a compound having a refractive index higher than that of the cured material of the component (A) and the component (B) by 0.01 or more (high refractive index compound) and having a refractive index (A) component. And a compound having a refractive index of the cured component (B) which is smaller than 0.01 (low refractive index compound). The component (C) is an organic compound and an inorganic compound.

The inorganic compound of the (C) component which is a cured product (also referred to as a base resin) of the component (A) and the component (B) which can be used in the present invention and which has a refractive index of 0.01 or more, for example, contains ZnO, TiO ₂ ( Titanium oxide), CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ITO, Y ₂ O ₃ , La ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ (alumina), cerium oxide, olivine, glass, white carbon Preferably, for example, Al ₂ O ₃ , TiO ₂ or ZrO _{2 having a} refractive index of 1.60 or more is used. The commercially available product may, for example, be an alumina filler (product name: AO-902H) manufactured by the company Admatechs. Here, Al ₂ O ₃ and TiO ₂ are particularly excellent in light reflectivity. The inorganic compound may be coated on the surface by various inorganic or organic compounds. Further, the shape of the inorganic compound may be any shape such as a spherical shape, a needle shape, or a plate shape, and the particle diameter thereof is not limited, but the smaller the particle diameter, the better. The particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly preferably 0.1 to 1 μm.

The base resin which can be used in the present invention and the organic compound of the component (C) having a refractive index of 0.01 or more can be either a liquid or a solid monomer, an oligomer, or a polymer compound. Further, any of the thermoplastic resin, the thermosetting resin, and the photocurable resin is not problematic, but it is incompatible with the photocurable resin of the base resin and has good dispersibility. For example, a styrene resin containing a (meth)acrylic resin, a urethane resin, a polyester acrylate resin, an epoxy resin, an oxetane resin, or a polystyrene, or a polyterephthalic acid may be mentioned. Ethylene glycol, polyvinyl carbazole, polycarbonate of bisphenol A, polyvinyl chloride, polytetrabromobisphenol A glycidyl ether, polybisphenol S glycidyl ether, polyvinyl pyridine, thiamine Monofunctional and difunctional polyfunctional groups of urethane resin, sulfur epoxy resin, fluorine-containing (meth) acrylate, fluorinated alkyl ether, oligomer (average molecular weight: 4000 or less) (Meth) acrylates, crystalline polymers containing bismuth (meth) acrylates, polyethylene or polytetrafluoroethylene. Further, when the organic compound is in a solid form, the shape thereof may be any shape such as a spherical shape, a needle shape, or a plate shape, and the particle diameter thereof is not limited, but the smaller the particle diameter, the better. The particle diameter thereof is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly preferably 0.1 to 1 μm. When the organic compound is in a liquid form, the compound is dispersed in the photocurable resin. The particle diameter of the dispersed particles is preferably from 0.1 to 100 μm, more preferably from 0.1 to 10 μm, particularly preferably from 0.1 to 1 μm.

In the present invention, the refractive index of some compounds which can be used as the component (C) 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 to 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), polyoxyxylene 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 component (A) and the component (B) is preferably 0.05 or more, more preferably 0.1 or more, and particularly preferably 0.15 or more.

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

The term "incompatible" with respect to the components (A) and (B) means that the component (C) is not uniformly mixed with the mixture of the components (A) and (B), and the component (A) and (B) are mixed. The "dispersibility" of the component means that the mixture of the component (C) and the component (A) and the component (B) is stirred and is not separated into two layers.

In the present invention, the component (D) is a black pigment, and the light-curable resin composition is provided with a light-shielding property. The component (D) is a process for maintaining the workability of the photocurable resin composition, and it is preferred to impart a light-shielding property with a small amount of addition. The component (D) may, for example, be an inorganic or organic pigment. Examples of the inorganic pigment include inorganic black, titanium black, and the like which contain carbon powder, ivory black, Mars black, asphalt black, lamp black, copper, iron, chromium, manganese, cobalt, and the like. It is preferably carbon powder, more preferably carbon black, acetylene black, Ketjen black, carbon nanotube, natural graphite powder, artificial graphite powder, etc., which is composed of a small amount of added light-hardening resin after hardening. The viewpoint of imparting light shielding properties to the material is particularly preferably carbon black, acetylene black or ketjen black. The organic pigment may, for example, be aniline black or ruthenium black, and is preferably ruthenium. The commercially available product may, for example, be a black pigment (product name: NBD-0744) manufactured by Rihong BICS Co., Ltd., or the like. (The photocurable resin composition of the present invention may contain one or a combination of two or more of the components (D) in the range of the range of the black pigment and the preferred range.

The photocurable resin composition of the present invention may be 20 to 170 parts by weight based on 100 parts by weight of the component (A), 0.2 to 80 parts by weight of the component (C) and 0.1 to (D). ~35 parts by weight.

The photocurable resin composition of the present invention is preferably used in an amount of 30 to 150 parts by weight, more preferably 50 to 120 parts by weight, per 100 parts by weight of the component (A).

The photocurable resin composition of the present invention is preferably used in an amount of from 1 to 50 parts by weight, more preferably from 5 to 40 parts by weight, even more preferably from 8 to 30 parts by weight, per 100 parts by weight of the component (A).

The photocurable resin composition of the present invention is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.14 to 0.7 part by weight, per 100 parts by weight of the component (A).

The photocurable resin composition of the present invention preferably has a viscosity of 5,000 to 200,000 mPa·s, more preferably 10,000 to 80,000 mPa·s, from the viewpoint of printability and dispensing properties. Here, the viscosity of the photocurable resin composition was measured using a RE-10U viscometer manufactured by Toki Sangyo Co., Ltd., and a Cone Plate type rotor, at room temperature.

The photocurable resin composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator may comprise a commercially available radical or cationic initiator, such as a carbonyl system: benzophenone, diethylidene, benzyl, benzoin, ω-bromoacetamidine. Benzene, chloroacetone, acetophenone, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoethyl benzene, p-di Methylaminopropione, 2-chlorobenzophenone, p,p'-bisdiethylaminobenzophenone, michelone, 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, methyl benzhydrazide, 2,2-diethoxyethyl benzene, 4-N,N'-dimethyl Acetylbenzene; thioether system: diphenyl disulfide, diphenylmethyl disulfide; lanthanide: benzoquinone, onion: azo; azobisisobutyronitrile, 2,2'-even Nitrogen dipropane. The commercially available product may, for example, be a mixture of 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184) manufactured by Ciba Japan Co., Ltd., 50 parts of 1-hydroxycyclohexyl phenyl ketone and 50 parts of benzophenone. (product name: IRGACURE 500) and so on. The amount of the photopolymerization initiator to be used is, for example, 1 to 10 parts by weight based on 100 parts by weight of the photocurable resin of the component (A). The irradiation light system may be any of visible light, ultraviolet light, radiation, and electron beam, but is preferably ultraviolet light from the viewpoint of adhesion after curing.

Further, the photocurable resin composition of the present invention has an adhesive property after the adhesion is cured, and may contain bubbles insofar as the effects of the present invention are not impaired.

The photocurable resin composition of the present invention may contain a solvent for the purpose of improving the printability, etc., but it is also preferably used without a solvent from the viewpoint of environmental considerations and the use ratio of the photocurable resin composition.

The photocurable resin composition of the present invention may further contain other known additives depending on the purpose, such as an antioxidant, an ultraviolet absorber, a photostabilizer, a decane coupling agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, A coloring agent, a storage stabilizer, a plasticizer, a slip agent, a filler, an anti-aging agent, a wettability improver, a release agent, and the like.

The photocurable resin composition of the present invention can be produced by mixing the above components by a usual method. The order of addition of each component is not particularly limited. When the high refractive index or low refractive index compound is in a liquid form, the compound is preferably dispersed in a fine particle diameter in the photocurable resin.

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

The photocurable resin composition of the present invention can be effectively cured by light such as visible light or ultraviolet light, and can be cured in a film thickness in a wide range of film thicknesses of, for example, 0.5 μm or more. The photohardening conditions may vary depending on the composition of the resin composition, the film thickness, and the like, but for example, the component (A): an acrylic resin, the component (B): an acrylic adhesion imparting agent, and the component (C): alumina, a component ( D): When carbon black is used and the film thickness is 100 μm, the amount of ultraviolet irradiation is 1000 mJ/cm ² or more.

The present invention is a cured product containing a photocurable resin composition. Since the cured product is excellent in various properties such as light resistance and adhesion, and has excellent properties such as strength, durability, and moisture resistance, it satisfies the properties of the resin for sealing (sealing) and the resin for light shielding. In the film thickness of the cured product of the present invention, the light transmittance in the range of from 300 μm to 150 μm may be 1% or less, for example, 0.5% or less, preferably 0.1% or less, and particularly preferably 0.05% or less. It should be 0.01% or less.

In the present invention, the term "adhesive" means that when the adherend is in contact with the cured photocurable resin composition, it is hard to be wetted by the adherend, and after sticking, it is difficult to be The state of both elasticity of the body peeling.

The present invention also encompasses an optical machine component having the above cured product. The optical machine component may be, for example, a liquid crystal panel, a sensor, an optical pickup, an optical lens, or an LED. The invention is particularly applicable to liquid crystal panels.

The invention further relates to an optical machine comprising the above described optical machine components. The optical device can be, for example, various displays, digital cameras, various recording media players, etc., and is particularly suitable for liquid crystal displays.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the examples. In the following, "parts" are weight basis.

(Examples 1 to 6 and Comparative Example 1)

First, the influence of the amount of the component (D) added on the deep curing property of the photocurable resin composition was examined, and Examples 1 to 6 were carried out.

(Modulation of photocurable resin composition)

A polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Kokusai Industrial Co., Ltd. as a component (A), 84 parts, manufactured by Kyoeisha Chemical Co., Ltd. 14 parts of hydroxyethyl methacrylate (product name: HO), 2 parts of lauryl acrylate (product name: LA) of Kyoeisha Chemical Co., Ltd., and polyol type 2 of Fudow Co., Ltd. as component (B) 84 parts of toluene resin (modified product) (K140), 14 parts of alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) made by Admatechs Co., Ltd. as component (C) (D) Ingredients: Nipponki Vics Co., Ltd. made black pigment (product name: NBD-0744) 0.14 to 7.0 parts (refer to Table 1), and 1-hydroxycyclohexylphenyl group produced by Ciba Japan Co., Ltd. as a photopolymerization initiator 50 parts of the ketone and 4.2 parts of a compound (product name: IRGACURE 500) of 50 parts of benzophenone were mixed to prepare a photocurable resin composition. In Comparative Example 1, only the (D) component was 0 parts, and the photocurable resin composition which was mixed in the same manner as in Examples 1 to 6 was prepared. Further, the cured product of the components (A) and (B) had a refractive index of 1.52.

(filling of the photocurable resin composition in the tube body)

As shown in Fig. 3, a black polyethylene tube of 5 mm diameter was permeated on an aluminum plate. After the tube body was formed to have a height of 1 to 2 mm on the aluminum plate, the prepared photocurable resin composition was filled to the front end of the black tube body, and the black tube body was sealed to prepare a sample.

(light irradiation)

The measured value of the UV sensor (model: UV-35) manufactured by the company OAK was used as the sample produced by the Eyegraphics Co., Ltd. using the Light type UV lamp (model: MO3-L31). UV irradiation was performed at 3,000 mJ/cm ² . Further, the irradiation system is performed only on the UV light in which the UV lamps are parallel (in the depth direction with respect to the resin).

(Measurement of hardened portion of photocurable resin composition)

The hardened portion of the photocurable resin composition was taken out from the black tube after the UV irradiation, and the thickness of the hardened portion was measured by a micrometer. The measurement was n=5.

(result)

The results are shown in Table 1.

As shown in Table 1, when the amount of the black pigment added was 4.2 or less, it was confirmed that the photocurable resin composition having a thickness of 110 μm or more can be cured. From the point where the hardening thickness of 200 to 300 μm is obtained, the addition amount of the black pigment is preferably 0.14 to 0.7 parts.

(Example 7)

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

(Modulation of photocurable resin composition)

A polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Kokusai Industrial Co., Ltd. as a component (A), 84 parts, manufactured by Kyoeisha Chemical Co., Ltd. 14 parts of hydroxyethyl methacrylate (product name: HO), and 2.0 parts of lauryl acrylate (product name: LA) of Kyoeisha Chemical Co., Ltd., and polyol type 2 of Fudow Co., Ltd. as component (B) 84 parts of a toluene resin (modified product) (K140), and 21 parts of an alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) manufactured by Admatechs Co., Ltd. as a component (C). (D) Ingredients: 0.42 parts of black pigment (product name: NBD-0744) made by Vios Co., Ltd., and 50 parts of 1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Japan Co., Ltd. as a photopolymerization initiator A mixture of 50 parts of a ketone (product name: IRGACURE 500) was mixed and prepared to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.52.

(Coating of photocurable composition)

Next, a prepared photocurable resin composition was applied onto a ruthenium glass substrate having a thickness of 1.0 mm on a ruthenium-plated glass substrate having a thickness of 1.0 mm, a length of 50 mm, a thickness of 50 μm or a thickness of 100 μm to prepare a sample.

(light irradiation)

The prepared sample was irradiated with UV in the same manner as in Examples 1 to 6.

(Production of a sample of a photocurable resin composition having a thickness of 200, 300, and 500 μm)

The sample of the photocurable resin composition having a thickness of 200, 300, and 500 μm was produced by coating the photocurable resin composition having a thickness of 100 μm and irradiating the light.

(Measurement of light transmittance)

A sample having a film thickness of 50, 100, 200, 300, or 500 μm prepared as described above was used, and an ultraviolet-visible spectrophotometer (Model: U-best V-570) manufactured by JASCO Corporation was used, and the measurement wavelength was 300 nm ( Transmittance of light in the ultraviolet region), 400 nm (ultraviolet/visible region), 500 nm (visible region), 600 nm (visible region), 700 nm (visible region), and 800 nm (visible region/infrared region).

(result)

The relationship between the film thickness of the photocurable resin composition and the transmittance was shown in Table 2.

From the results of Table 2, it was confirmed that the thickness of the photocurable resin composition after curing was 100 μm or less, and it was transmitted through ultraviolet light or visible light, and transmitted through the visible light region/infrared region light even when the thickness was 200 μm. As a result, it is considered that the photocurable resin composition before curing is also the same. In addition, when the thickness is 100 μm or more, ultraviolet rays are not transmitted, and when the thickness is 200 μm or more, preferably 300 μm or more, it is confirmed that the ultraviolet/visible light region to the visible light region/infrared region is not transmitted or hardly transmitted.

(Example 8)

Next, the effect of the addition of the component (D) on the light-shielding property of the cured photocurable resin composition was investigated, and Example 8 was carried out.

(Modulation of photocurable resin composition)

A polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Kokusai Industrial Co., Ltd. as a component (A), 84 parts, manufactured by Kyoeisha Chemical Co., Ltd. 10 parts of hydroxyethyl methacrylate (product name: HO), 2.0 parts of lauryl acrylate (product name: LA) of Kyoeisha Chemical Co., Ltd., and polyol type 2 of Fudow Co., Ltd. as component (B) 84 parts of toluene resin (modified product) (K140), 14 parts of alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) made by Admatechs Co., Ltd. as component (C) (D) Ingredients: 0.28 parts of black pigment (product name: NBD-0744) made by Vios Co., Ltd., and 50 parts of 1-hydroxycyclohexyl phenyl ketone manufactured by Ciba Japan Co., Ltd. as a photopolymerization initiator A mixture of 50 parts of a ketone (product name: IRGACURE 500) was mixed and prepared to prepare a photocurable resin composition. In Comparative Example 2, only the (D) component was 0 parts, and the photocurable resin composition which was mixed in the same manner as in Example 8 was prepared. Further, the cured product of the components (A) and (B) had a refractive index of 1.52.

(Coating of photocurable composition)

Next, using a dispenser, a photocurable resin composition prepared by coating was applied to a ruthenium glass substrate having a thickness of 1.0 mm to a width of 1 mm, a length of 50 mm, and a thickness of 100 μm to prepare a sample.

(light irradiation)

The prepared sample was irradiated with UV in the same manner as in Examples 1 to 6.

(Production of a sample of a photocurable resin composition having a thickness of 500 μm)

A sample of the photocurable resin composition having a thickness of 500 μm was produced by further coating and coating the photocurable resin composition having a thickness of 100 μm four times.

(Measurement of light transmittance)

In the same manner as in Example 2, the transmittance was measured, and the reflectance was further measured. Further, the reflectance was measured by a 90 ° C absolute reflection method using an ultraviolet-visible spectrophotometer (Model: U-best V-570) manufactured by JASCO Corporation.

(result)

The result of the relationship between the film thickness of the photocurable resin composition and the transmittance is shown in Fig. 4, and the result of the relationship between the film thickness of the photocurable resin composition and the reflectance is shown in Fig. 5 .

As shown in FIG. 4, the transmittance of Example 8 in which the component (D) was added and Comparative Example 2 in which the component (D) was not added was inferior. As shown in FIG. 5, it was confirmed that the reflectance of Example 8 was lowered to about 1/2 in the wavelength of 300 nm as compared with the reflectance of Comparative Example 2, and the wavelength was lowered to the reflection of Comparative Example 2 at a wavelength of 350 nm or more. The rate is about 1/5 or less.

(Examples 9 to 16)

Next, in order to investigate the influence of the addition of the component (A) on the adhesion strength of the cured photocurable resin composition, Examples 9 to 16 were carried out.

(Modulation of photocurable resin composition)

In the amount shown in Table 3, polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) made by Industrial Co., Ltd., which is the component (A), was used. 2-hydroxyethyl methacrylate (product name: HO) manufactured by Chemicals Co., Ltd., and benzyl methacrylate (product name: BZ) of Kyoeisha Chemical Co., Ltd., and Fudow Co., Ltd. as component (B) A polyol-type xylene resin (modified product) (K140), an alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) made by Admatechs Co., Ltd. as (C) component, As a component (D), a black pigment (product name: NBD-0744) made by Viking Co., Ltd., and a 1-hydroxycyclohexyl phenyl ketone prepared by Ciba Japan Co., Ltd. as a photopolymerization initiator, and benzophenone A mixture of 50 parts (product name: IRGACURE 500) was mixed to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.53.

(Production of adhesion strength test specimen)

Using the prepared photocurable resin composition, as shown in Fig. 6, a width of 1.5 cm on a glass plate having a length of 75 mm, a width of 25 mm, and a thickness of 2.5 mm separated by two spacers having a thickness of 100 μm. The groove-coating photocurable resin composition (coating length: 75 mm, coating width: 15 mm, coating thickness: 100 μm). After removing the two spacers, the photocurable resin composition applied to the glass plate was cured by UV irradiation. A polycarbonate (PC) plate having a thickness of 500 μm was attached to prepare a sample for the peel strength test. The curing of the photocurable resin composition was carried out in the same manner as in Examples 1 to 6, but the UV light was irradiated from the glass side.

(adhesion strength test)

For the test specimens to be produced, a tensile tester manufactured by Shimadzu Corporation was used, and the peel test was conducted at 300 mm/min, and the shear test was carried out at 5 mm/min. The results are shown in Table 3.

(result)

The results of the peel test and the shear test are shown in Table 3.

As is clear from Table 3, it was confirmed that the amount of the component (A) added was 100 parts by weight, and the component (B) was 55 to 85 parts by weight, and a peel strength of 1.0 N/25 mm or more and a shear strength of 2.2 MPa or more were obtained. When the amount of the component (A) is 100 parts by weight and the 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.

(Examples 17 to 23)

Next, in order to investigate the influence of the addition of the component (B) on the adhesion strength of the cured photocurable resin composition, Examples 17 to 23 were carried out.

(Modulation of photocurable resin composition)

In the amount shown in Table 4, a polycarbonate urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) manufactured by Industrial Co., Ltd., which is a component (A), was used. 2-hydroxyethyl methacrylate (product name: HO) manufactured by Chemicals Co., Ltd., and benzyl methacrylate (product name: BZ) of Kyoeisha Chemical Co., Ltd., and Fudow Co., Ltd. as component (B) A polyol-type xylene resin (modified product) (K140), an alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) made by Admatechs Co., Ltd. as (C) component, As a component (D), a black pigment (product name: NBD-0744) made by Viking Co., Ltd., and a 1-hydroxycyclohexyl phenyl ketone prepared by Ciba Japan Co., Ltd. as a photopolymerization initiator, and benzophenone A mixture of 50 parts (product name: IRGACURE 500) was mixed to prepare a photocurable resin composition. Further, the cured product of the components (A) and (B) had a refractive index of 1.53.

(Preparation of adhesion strength test specimen, adhesion strength test)

Using the prepared photocurable resin composition, samples were prepared in the same manner as in Examples 9 to 16, and peel strength and shear strength were measured.

(result)

The results of the peel test and the shear test are shown in Table 4.

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

(industrial use possibility)

The photocurable resin composition of the present invention can be cured by a thick film, has low light transmittance after curing, has adhesiveness, and is excellent in various properties such as strength, durability, and moisture resistance. The production property is sufficiently improved, and it is applied as a resin for manufacturing various optical device members or molding resins which are required to be light-shielding.

1. . . LCD panel

2. . . Fixed (sealed) resin layer

3. . . Substrate

4. . . Backlight

5. . . Photocurable resin composition after curing with light blocking property and adhesiveness

6. . . Photocurable resin composition before hardening

7. . . Black tube

8. . . Aluminum plate

9. . . glass plate

10. . . PC board

A. . . Transmitting light from the outside

B. . . Light leakage from inside (loss of light)

C. . . Ultraviolet light

Figure 1 is a diagram showing a conventional optical machine component.

Fig. 2 is a conceptual view showing an optical machine component of the present invention.

Figure 3 is a schematic view of a sample of Example 1.

Fig. 4 is a graph showing the relationship between the film thickness of the photocurable resin composition and the transmittance.

Fig. 5 is a graph showing the relationship between the film thickness of the photocurable resin composition and the reflectance.

Fig. 6 is a schematic view showing a sample for peel strength test.

Figure 7 is a schematic view of the peel strength test method.

Claims (10)

A photocurable resin composition comprising: (A) a photocurable resin, (B) an adhesiveness imparting agent, and (C) a refractive index of a cured product of the component (A) and the component (B) a refractive index of 0.01 or more, a compound which is incompatible with the component (A) and the component (B) and having dispersibility, and (D) a black pigment, based on 100 parts by weight of the component (A) ( The component B) is 20 to 170 parts by weight, and the component (D) is 0.1 to 35 parts by weight. The photocurable resin composition according to claim 1, wherein the component (C) is selected from the group consisting of alumina powder and titanium oxide powder. The photocurable resin composition according to claim 1 or 2, wherein the component (D) is a carbon powder. The photocurable resin composition according to claim 1 or 2, wherein the component (B) is an acrylic, a polyoxygen, a maleimine, a rosin ester, a terpene, a rubber, or An aromatic hydrogenated petroleum-based adhesion imparting agent. The photocurable resin composition according to claim 1 or 2, wherein the component (A) is an acrylic modified resin or an epoxy resin. The photocurable resin composition according to claim 1 or 2, wherein the component (C) is 0.2 to 80 parts by weight based on 100 parts by weight of the component (A). A photocurable resin composition according to claim 1 or 2, which further comprises a photopolymerization initiator. A cured product which is a cured product of the photocurable resin composition according to any one of claims 1 to 7. An optical machine component comprising the cured product of claim 8 of the patent application. An optical machine comprising the optical machine component of claim 9 of the patent application.