KR20110087341A - Photo-curable resin composition exhibiting light-blocking properties and tackiness, and cured product thereof - Google Patents

Abstract

The present invention effectively cures by light, and thus provides a photocurable resin composition which can be cured even with a thick film thickness, has low light transmittance after curing, and has adhesiveness. The photocurable resin composition of this invention has a refractive index which the difference with the refractive index of (A) photocurable resin, (B) tackifier, (C) hardened | cured material of the said (A) component and (B) component becomes 0.01 or more, A compound which is incompatible and dispersible with respect to the said (A) component and (B) component, and (D) black pigment is included.

Description

Photocurable resin composition having light-shielding property and adhesiveness and cured product thereof {PHOTO-CURABLE RESIN COMPOSITION EXHIBITING LIGHT-BLOCKING PROPERTIES AND TACKINESS, AND CURED PRODUCT THEREOF}

This invention relates to the photocurable resin composition which has light-shielding property and adhesiveness after hardening. The photocurable resin composition of this invention is used suitably for fixation of optical material components, such as a liquid crystal panel, prevention of light leakage of a backlight, and prevention of entrance of external light as a sealing compound of optical instruments, especially a liquid crystal display.

Recently, in order to realize and maintain high sensitivity, display light such as liquid crystal displays, optical lenses, optical pickups, sensors, and the like, transmitted light from outside or leaked light from inside passing through the member or the fixed resin layer It is indispensable to reduce the loss by leakage light from the gap. The schematic diagram of the conventional liquid crystal display is shown in FIG. Particularly, in a portion where various properties such as adhesiveness, adhesiveness, strength, durability, and moisture resistance are required, such as a fixed resin layer, it is necessary to make these properties and light-shielding compatible with the same resin.

In order to achieve the above-mentioned demands, by using the refractive index difference between the cured product of the photocurable resin of the base resin and the compound added thereto, it is effectively cured by light, and thus curable even with a resin having a thick film thickness. The photocurable resin composition with low light transmittance of cured resin obtained is reported (patent document 1).

Moreover, in reality, the method of hardening a film after punching a non-hardened adhesive film in a frame shape and bonding to a glass substrate is generally used.

Japanese Patent Laid-Open No. 2007-119684

When using a photocurable resin composition as a sealing compound etc. of a liquid crystal display, after forming a photocurable resin composition on a board | substrate etc. in a frame form, photocurable resin is hardened and a to-be-adhered substance (liquid crystal panel) is photocurable resin The process of adhering with a composition is performed. Here, in order to use the photocurable resin composition of patent document 1 as a sealing compound etc. of a liquid crystal display, it is required to mix | blend a thermosetting resin with the photocurable resin composition, and to give adhesiveness to the photocurable resin composition after photocuring. do. Therefore, in addition to the photocuring process, a thermosetting process is required, and a long time is required for this thermosetting process. Moreover, the part of a liquid crystal display may contain what is deformed at about 70 degreeC, and in this case, there exists a problem that the part of a liquid crystal display deforms in the thermosetting process of a photocurable resin composition.

In addition, as a method of using the adhesive film processed into the frame shape, the punching width of the film is limited to about 0.5 mm, and there is a limit to the high density mounting, and since a film portion which is not used after punching occurs, the material There is a problem of low yield.

Moreover, in the method of using the film processed in the frame shape, since the handling of the film after processing takes time, and the bonding process of the film is difficult to mechanize, in reality, a person bonds the film by hand and a production line The problem is that automation is difficult.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, when the photocurable resin composition has adhesiveness after photocuring, it discovered that the said subject can be achieved when using it as a sealing compound etc. of a liquid crystal display, and completed this invention.

That is, the object of the present invention is to effectively cure by light, and therefore, it is possible to cure even with a thick film thickness, and after curing, it has a low light transmittance, has adhesiveness, and is also excellent in various properties such as strength, durability, and moisture resistance. It is to provide a chemical composition.

The first invention is

(A) Photocurable resin, (B) Tackifier, (C) The refractive index which becomes a difference with the refractive index of the hardened | cured material of the said (A) component and (B) component becomes 0.01 or more, The said (A) component and (B) It is related with the photocurable resin composition containing the compound and (D) black pigment which are incompatible and dispersible with respect to the component.

The second invention relates to a photocurable resin composition wherein the component (C) is selected from the group consisting of aluminum oxide powder and titanium oxide powder.

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

The fourth invention relates to a photocurable resin composition in which the component (B) is an acrylic, silicone, maleimide, rosin ester, terpene, rubber, or aromatic hydrogenated petroleum tackifier.

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

According to a sixth aspect of the present invention, the photocurable composition has 20 to 170 parts by weight of the component (B), 0.2 to 80 parts by weight of the component (C) and 0.1 to 35 parts by weight of the component (D). It relates to a resin composition.

7th this invention further relates to the photocurable resin composition containing a photoinitiator.

8th this invention relates to the hardened | cured material of said photocurable resin composition.

A ninth aspect of the present invention relates to an optical instrument member comprising the cured product described above.

A tenth aspect of the present invention relates to an optical instrument comprising the optical instrument member described above.

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

Since the photocurable resin composition of this invention hardens efficiently with light, thick film hardening is possible, and the hardened | cured material obtained is low in light transmittance from inside and outside, ie, it is high in light-shielding property, and is excellent in adhesiveness, and is excellent in strength, durability, and durability. It is also excellent in various properties such as wetness. In addition, since the photocurable resin composition can be printed or dispensed, the use rate of the photocurable resin composition is high, the formation of fine lines is easy, and the production line can be automated. Can be.

For this reason, the photocurable resin composition of this invention is suitable as a sealing compound of optical instruments, especially a liquid crystal display.

1 is a view showing a conventional optical device member.
2 is a view showing the concept of the optical device member of the present invention.
3 is a schematic view of a sample of Example 1. FIG.
4 is a diagram showing the relationship between the film thickness and the transmittance of the photocurable resin composition.
5 is a diagram illustrating a relationship between a film thickness and a reflectance of the photocurable resin composition.
It is a schematic diagram of the sample for peeling strength test.
7 is a schematic view of the peel strength test method.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

The photocurable resin composition of this invention has a refractive index which the difference with the refractive index of (A) photocurable resin, (B) tackifier, (C) hardened | cured material of the said (A) component and (B) component becomes 0.01 or more, It is characterized by including the compound which is incompatible and dispersible with respect to the said (A) component and (B) component, and (D) black pigment. In the present invention, by combining the component (C) and the component (D), light shielding is achieved by thick film curing, light shielding, and light absorption by the component (D) using the light reflectivity of the component (C).

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

The photocurable resin in this invention will not be specifically limited if it is resin hardened | cured by light, such as visible light and an ultraviolet-ray, For example, acrylic modified resin, such as (meth) acrylic resin, urethane acrylate resin, and polyester acrylate resin. ; Epoxy resins; An oxetane resin is mentioned. As photocurable resin, Preferably, an acrylic modified resin and an epoxy resin are mentioned.

Acrylic modified resins are defined as mono- and polyfunctional (meth) acrylate compounds having acryloyl or methacryloyl groups, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl Acrylate, t-butyl acrylate, isobutyl acrylate, ethylhexyl 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-ethoxy ethoxyethyl Acrylate, methoxydiethylene glycol acrylate, ethoxy diethylene glycol acrylate, methoxy dipropylene glycol acrylate, Octafluoropentyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol acrylate, 1,4-butanediol acrylate, acrylo Ilmorpholine, 1,6-hexanediol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypy Dispersing ester, neopentyl glycol diacrylate, trimethylolpropanediacrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α, ω-diacrylic Bisdiethylene glycol phthalate, trimethylol propane triacrylate, pentaerythrite acrylate, pentaerythrite hexaacrylate, dipentaerythritol monohydroxy Pentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tri (meth) acrylate of trihydroxyethyl isocyanurate, dipentaerythritol hexaacrylate, and EO and / or PO thereof Adduct, (alpha), (omega)-tetraallyl bistrimethylol propane tetrahydro phthalate, 2-hydroxyethyl acryloyl phosphate, a trimethylol propane trimethacrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth ) Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentyl glycol dimethacrylate, diacryloxyethyl Phosphates, N-vinylpyrrolidone and oligomers having these photoreactive functional groups can be exemplified. As an oligomer, the (meth) acrylate compound which has a polyether skeleton, a polycarbonate skeleton, or a polyester skeleton is mentioned. As a commercially available product, polycarbonate-based acrylate (product name: UN5500) made by Negami Kogyo Co., Ltd., polyester-based acrylate (product name: UN7700), poly by Nippon Kosei Kagaku Kogyo Co., Ltd. Ether acrylate (product name: UV3700B); and the like. Among the acrylic modified resins described above, polycarbonate-based acrylates are particularly preferred as the component (A).

An epoxy resin is defined as a compound which has a molecular structure which has one or more epoxy groups, For example, biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol Polyglycides of novolak resins such as diglycidyl ethers of bisphenols such as F, tetrachlorobisphenol A, tetrabromobisphenol A, phenol novolac, cresol novolak, brominated phenol novolak, orthocresol novolak Dyl ethers, ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, neopentylglycol, trimethylolpropane, 1,4-cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, bisphenol A Diglycidyl ethers of alkylene glycols such as propylene oxide adducts, glycidyl esters of hexahydrophthalic acid and diglycols of dimer acid Glycidyl esters such as diester, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3', 4'-epoxycyclohexane Carboxylate, 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, te La (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis (3,4-epoxycyclohexylmethyl) -4,5-epoxytetrahydrophthalate, bis (3,4-epoxycyclohexyl) diethyl Alicyclic epoxy compounds, such as a siloxane, and oligomer which has these photoreactive functional groups can be illustrated. Among the above epoxy resins, bisphenol A is particularly preferable as the component (A). Epoxy resin can be used together with acrylic modified resin.

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

(B) component in this invention forms base resin simultaneously with (A) component. (B) A component is a tackifier and provides adhesiveness to the photocurable resin composition after hardening. Examples of the component (B) include tackifiers such as acrylic, silicone, maleimide, rosin ester, terpene, rubber, aromatic petroleum, and the like. Acrylic, rosin, terpene, and the like in terms of heat resistance and compatibility Aromatic hydrogenated petroleum type is preferable. As a commercially available product, the foodstuff polyol type xylene resin (modified product) K140 represented by General formula (1) etc. are mentioned.

The photocurable resin composition of this invention can contain one or a combination of two or more of (B) component.

The refractive index of the hardened | cured material of (A) component and (B) component hardens the mixture of (A) component and (B) component, and is made with D line using an Abbe refractometer (made by Atago Co., Ltd.) with respect to the mixture. Measure

The component (C) in the present invention has a refractive index such that a difference between the refractive index of the cured product of the component (A) and the component (B) is 0.01 or more, and is incompatible with the component (A) and the component (B) and is dispersible. It is a compound which has, and is selected by the refractive index of the hardened | cured material of (A) component and (B) component, and incompatibility with respect to (A) component and (B) component and dispersibility. Component (C) has a refractive index of at least 0.01 greater than that of the cured product of the (A) component and the component (B) (high refractive index compound) and the refractive index of the cured product of the component (A) and the component (B). It is largely divided into a compound having a low refractive index compound. (C) component is an organic compound or an inorganic compound.

ZnO and TiO ₂ (titanium oxide) are used for the inorganic compound as the (C) component in which the cured product (also called a base resin) of the component (A) and the component (B) which can be used in the present invention and the refractive index differ by 0.01 or more. , 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, preferably Examples thereof include Al ₂ O ₃ , TiO ₂ and ZrO ₂ having a refractive index of 1.60 or more. As a commercially available product, the alumina filler (product name: AO-902H) made from Admatex Co., Ltd. is mentioned. Here, Al ₂ O ₃ and TiO ₂ are particularly preferable because they are excellent in light reflectivity. An inorganic compound can also coat the surface with various inorganic and organic compounds. In addition, the shape of an inorganic compound may be arbitrary shapes, such as spherical shape, needle shape, and plate shape, Although the particle size is not limited, It is more preferable that the particle size is small. The particle diameter is preferably 0.1 to 100 mu m, more preferably 0.1 to 10 mu m, especially 0.1 to 1 mu m.

The organic compound as the (C) component having a refractive index of 0.01 or more different from the base resin usable in the present invention may be either a liquid, a solid monomer, an oligomer, or a polymer compound, and may be a thermoplastic resin, a thermosetting resin, or a photocurable resin. Although either of them is not a problem, it should be incompatible and good in dispersibility with respect to the photocurable resin which is a base resin. For example, styrol resins, such as (meth) acrylic resin, urethane acrylate resin, polyester acrylate resin, epoxy resin, oxetane resin, polystyrene, polyethylene terephthalate, polyvinylcarbazole, and polycarbo of bisphenol A Nate, polyvinyl chloride, polytetrabromobisphenol A glycidyl ether, polybisphenol S glycidyl ether, polyvinylpyridine, thiourethane resin, thioepoxy resin, fluorine-containing (meth) acrylates, alkylene fluoride ether Crystalline polymers such as polyfunctional (meth) acrylates, silicone-containing (meth) acrylates, and polyunsaturated and bifunctional or more functional oligomers (average molecular weight: 4000 or less). . In addition, when an organic compound is solid, the shape may be arbitrary shapes, such as spherical shape, needle shape, and plate shape, Although the particle diameter is not limited, It is preferable that the particle size is small. The particle diameter thereof is preferably 0.1 to 100 m, more preferably 0.1 to 10 m, and particularly 0.1 to 1 m. When the organic compound is a liquid, the compound is dispersed in the photocurable resin. The particle diameter of the dispersed particles is preferably 0.1 to 100 µm, more preferably 0.1 to 10 µm, particularly 0.1 to 1 µm.

The refractive index is illustrated below about some of the compounds which can be used as (C) component in this invention.

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), polytetrafluoro Low ethylene (1.35), methyl methacrylate resin (1.49), vinyl chloride resin (1.54), silicone oil (1.4).

In this invention, the difference of the refractive index of (C) component and the refractive index of the hardened | cured material of (A) component and (B) component becomes like this. Preferably it is 0.05 or more, More preferably, it is 0.1 or more, Especially preferably, it is 0.15 or more.

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

"Incompatibility" with respect to 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), and the component (A) and ( "Dispersibility" with respect to B) component means that the mixture of (C) component, (A) component, and (B) component does 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. It is preferable that (D) component provides light-shielding property by addition of a small amount, in order to maintain workability of a photocurable resin composition. As (D), an inorganic or organic pigment is mentioned. Examples of the inorganic pigments include inorganic powders containing carbon powder, ivory black, mals black, pitch black, lamp black, copper, iron, chromium, manganese and cobalt, titanium black and the like. It is preferable that it is carbon powder, carbon black, acetylene black, Ketjen black, carbon nanotube, natural graphite powder, artificial graphite powder, etc. are more preferable, The viewpoint of providing light-shielding property to the photocurable resin composition after hardening by addition of a small amount In particular, carbon black, acetylene black and Ketjen black are particularly preferred. Examples of the organic pigments include aniline black and perylene black, with perylene black being preferred. Examples of commercially available products include black pigments (product name: NBD-0744) manufactured by Nikko Bikkusu Co., Ltd .. (If there is an exemplified range or a preferred range for the particle size of the black pigment, please write it.)

The photocurable resin composition of this invention can contain one or a combination of two or more of (D) component.

The photocurable resin composition of this invention is 20-170 weight part of (B) component, 0.2-80 weight part of (C) component, and 0.1-35 weight part of (D) component with respect to 100 weight part of (A) component. It may be wealth.

In the photocurable resin composition of this invention, 30-150 weight part is preferable with respect to 100 weight part of (A) component, and 50-120 weight part is more preferable.

In the photocurable resin composition of this invention, 1-50 weight part is preferable with respect to 100 weight part of (A) component, 5-40 weight part is more preferable, 8-30 weight part is especially preferable.

In the photocurable resin composition of this invention, 0.1-20 weight part is preferable with respect to 100 weight part of (A) component, 0.1-10 weight part is more preferable, 0.14-0.7 weight part is especially preferable.

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 dispensability. Here, the viscosity of a photocurable resin composition is measured on condition of room temperature with a cone plate type rotor using the RE-10U type | mold viscosity meter manufactured by AXING KK.

The photocurable resin composition of this invention can contain a photoinitiator further. As photopolymerization initiators, commercially available radical or cationic initiators are generally included, for example carbonyl machinery: benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2, 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzo Phenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-one , 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylholate, 2,2-diethoxyacetophenone, 4-N, N'-dimethylacetophenone ; Sulfide type: diphenyl disulfide, dibenzyl disulfide; Quinones: benzoquinone, anthraquinone; Azo system: Azobisisobutyronitrile and 2,2'- azobis propane can be illustrated. As a commercially available product, 1-hydroxycyclohexyl phenyl ketone (product name: IRGACURE 184) made from Chiba Japan Co., Ltd., a eutectic mixture of 50 parts of 1-hydroxycyclohexyl phenyl ketones and 50 parts of benzophenone (Product name: Irgacure 500) etc. are mentioned. A photoinitiator can be used in the quantity generally used, for example, in the quantity of 1-10 weight part with respect to 100 weight part of photocurable resins of (A) component. The irradiation light may be any one of visible light, ultraviolet light, radiation, and electron beam, but ultraviolet light is preferable in view of adhesiveness after curing.

Moreover, in order to improve 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.

Although the photocurable resin composition of this invention can contain a solvent for the purpose of the improvement of printability, etc., it is also preferable to use it as a solvent from the viewpoint of environmental consideration and the utilization rate of a photocurable resin composition.

According to the objective, the photocurable resin composition of this invention further contains other well-known additives, for example, antioxidant, a ultraviolet absorber, a light stabilizer, a silane coupling agent, a thermal polymerization inhibitor, a leveling agent, surfactant, a coloring agent, Storage stabilizers, plasticizers, lubricants, fillers, anti-aging agents, wettability improvers, mold release agents and the like can be added.

The photocurable resin composition of this invention can mix and manufacture each said component by a conventional method, and can manufacture it. The addition order of each component is not specifically limited. When a high refractive index or a low refractive index compound is a liquid phase, it is preferable to disperse | distribute the said compound to photocurable resin with a fine particle diameter.

The photocurable resin composition of this invention can be printed and dispensed by the method known to those skilled in the art, such as a screen printing machine and a dispenser, and can form a fine line easily. 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. In addition, the line width of the fine line is preferably 500 µm or more, and more preferably 600 µm or more in terms of light shielding, adhesiveness, and sealing properties.

The photocurable resin composition of this invention can be hardened | cured effectively by light, such as visible light and an ultraviolet-ray, and can harden | cure in the film thickness of a wide range, for example, the range of 0.5 micrometer or more. Although the conditions of photocuring can change with the composition, the film thickness, etc. of a resin composition, For example, a component (A): acrylic resin, a component (B): acrylic tackifier, a component (C): alumina, a component ( D): In the case of carbon black and film thickness: 100 micrometers, an ultraviolet-ray irradiation amount is 1000 mJ / cm <2> or more.

The present invention includes a cured product of the photocurable resin composition. Since this hardened | cured material has light-shielding property and adhesiveness, and is excellent in various characteristics, such as intensity | strength, durability, and moisture resistance, it satisfy | fills the characteristic of resin for fixation (sealing) and resin for light shielding simultaneously. The cured product of the present invention has a light transmittance at 300 to 800 nm in a film thickness ranging from 30 μm to 150 μm of 1% or less, for example 0.5% or less, preferably 0.1% or less, especially 0.05% or less, Furthermore, it can be 0.01% or less.

In the present invention, the term "having adhesiveness" refers to a state in which the adherend has both viscosities that enable leakage to the adherend and elasticity that is difficult to peel off from the adherend after being adhered to the photocurable resin composition after curing. it means.

The present invention also includes an optical instrument member comprising the cured product described above. As an optical device member, a liquid crystal panel, a sensor, an optical pick, an optical lens, LED is mentioned, for example. The present invention is particularly suitable for liquid crystal panels.

The invention further relates to an optical instrument comprising the optical instrument member described above. 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.

<Examples>

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to these Examples. In the following, "parts" are based on weight.

(Examples 1 to 6 and Comparative Example 1)

First, Examples 1-6 were performed in order to investigate the influence on the deep-curing property of the photocurable resin composition which the addition amount of a component (D) has.

(Production of Photocurable Resin Composition)

Polycarbonate-based urethane acrylate (product name: UN-5500, a weight average molecular weight: about 50,000) 84 parts, Kyosei Chemical Co., Ltd. 2-hydroxyl as a (A) component 14 parts of ethyl methacrylate (product name: HO) and 2 parts of lauryl acrylate (product name: LA) manufactured by Kyo Kaisha Chemical Co., Ltd., polyol type xylene resin manufactured by Food Company Ltd. as a component (B) (modified product) ) (K140) 84 parts, alumina filler (product name: AO-902H, average particle diameter: 0.7 탆, refractive index: 1.76) made by Admatex Co., Ltd. as a component (C) 14 parts, Nikko Vicus Co., Ltd. as (D) component Black pigment (product name: NBD-0744) manufactured by Shikigaisha Co., Ltd. 0.14 to 7.0 parts (see Table 1 below), as a photopolymerization initiator, a mixture of 50 parts of 1-hydroxycyclohexylphenyl ketone manufactured by Chiba Japan Co., Ltd. and 50 parts of benzophenone (Product name: Irgacure 500) 4.2 parts were mixed and the photocurable resin composition was produced. As Comparative Example 1, only the component (D) was 0 parts, and the photocurable resin composition mixed in the same manner as in Examples 1 to 6 was adjusted. In addition, the refractive index of the hardened | cured material of component (A) and (B) component was 1.52.

(Filling Tube of Photocurable Composition)

As shown in FIG. 3, the 5 mm diameter ultraviolet-ray black polyethylene tube was stuck on the aluminum plate. After filling the prepared photocurable resin composition to the tip of a black tube so that it might become a tube height of 1-2 mm on an aluminum plate, the black tube was sealed and the sample was produced.

(Light irradiation)

In the manufactured sample, a metal manufactured by iGraphics Co., Ltd. was used with a ride type UV lamp (model number: MO3-L31), and the measured value by the UV sensor (model number: UV-35) manufactured by Oak Co., Ltd. was 3,000. UV was irradiated to be mJ / cm 2. In addition, irradiation was performed so that only UV light parallel to a UV lamp (in the depth direction with respect to the resin) may enter.

(Measurement of the Cured Part of the Photocurable Composition)

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

(result)

The results are shown in Table 1.

As shown in Table 1, when the addition amount of a black pigment was 4.2 parts or less, it demonstrated that the photocurable composition of 110 micrometers or more in thickness can be hardened. In the point that the hardening thickness of 200-300 micrometers is obtained, the addition amount of a more preferable black pigment is 0.14-0.7 parts.

(Example 7)

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

(Production of Photocurable Resin Composition)

Polycarbonate-based urethane acrylate (product name: UN-5500, a weight average molecular weight: about 50,000) 84 parts, Kyosei Chemical Co., Ltd. 2-hydroxyl as a (A) component 14 parts of ethyl methacrylate (product name: HO) and 2.0 parts of lauryl acrylate (product name LA) manufactured by Kyo Kaisha Chemical Co., Ltd., polyol type xylene resin (modified product) manufactured by Food Co., Ltd. as a component (B). (K140) 84 parts, alumina filler (product name: AO-902H, average particle diameter: 0.7 micrometer, refractive index: 1.76) made by Admatex Co., Ltd. as a component (C) 21 parts, Nikko Bikkus corpse as (D) component 0.42 parts of black pigment (product name: NBD-0744) by Kaisha, and a mixture of 50 parts of 1-hydroxycyclohexylphenyl ketone manufactured by Chiba Japan Co., Ltd. and 50 parts of benzophenone (product name: Irgacure 500) as a photopolymerization initiator are 4.2 parts. Mix by light To prepare a resin composition. In addition, the refractive index of the hardened | cured material of component (A) and (B) component was 1.52.

(Application of Photocurable Composition)

Subsequently, the photocurable resin composition prepared by apply | coating at the width | variety: 1 mm, length: 50 mm, thickness 50 micrometers, or 100 micrometers was applied to the crown glass substrate of thickness: 1.0 mm using the dispenser, and the sample was produced.

(Light irradiation)

In the same manner as in Examples 1 to 6, the produced samples were irradiated with UV.

(Production of Samples of Cured Photocurable Resin Compositions of Thickness 200, 300, 500 µm)

Samples of the cured photocurable resin composition having a thickness of 200, 300, and 500 µm were prepared by repeating the application of the photocurable composition having a thickness of 100 µm and the light irradiation.

(Measurement of Light Transmittance)

Using a sample having a film thickness of 50, 100, 200, 300, 500 µm as described above using an ultraviolet visible spectrophotometer (model number: U-best V-570) manufactured by Nippon Bunko Co., Ltd. Light transmittances 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) Measured.

(result)

The obtained results are shown in Table 2 below regarding the relationship between the film thickness and the transmittance of the photocurable resin composition.

From the result of Table 2, when the thickness of the photocurable resin composition after hardening was 100 micrometers or less, it demonstrated that it permeate | transmits an ultraviolet-ray or a visible light, and transmits visible region / infrared region light even if it is 200 micrometers in thickness. This result is considered to be the same also about the photocurable resin composition before hardening. On the other hand, if the thickness is 100 µm or more, the ultraviolet rays do not transmit, and if the thickness is 200 µm or more, preferably 300 µm or more, the ultraviolet / visible region to the visible / infrared region does not transmit or hardly transmits. It is demonstrated.

(Example 8)

Next, Example 8 was performed in order to investigate the influence on the light-shielding property of the cured photocurable resin composition which addition of a component (D) has.

(Production of Photocurable Resin Composition)

Polycarbonate-based urethane acrylate (product name: UN-5500, a weight average molecular weight: about 50,000) 84 parts, Kyosei Chemical Co., Ltd. 2-hydroxyl as a (A) component 10 parts of ethyl methacrylate (product name: HO) and 2.0 parts of lauryl acrylate (product name: LA) manufactured by Kyo Kaisha Chemical Co., Ltd., polyol type xylene resin manufactured by Food Company Ltd. as a component (B) (modified product) ) (K140) 84 parts, alumina filler (product name: AO-902H, average particle diameter: 0.7 탆, refractive index: 1.76) made by Admatex Co., Ltd. as a component (C) 14 parts, Nikko Vicus Co., Ltd. as (D) component 0.28 parts of black pigment (product name: NBD-0744) by Shikigaisha Co., Ltd., a mixture of 50 parts of 1-hydroxycyclohexylphenyl ketone manufactured by Chiba Japan Co., Ltd. and 50 parts of benzophenone (product name: Irgacure 500) 4.2 as a photopolymerization initiator 4.2 Light by mixing wealth To prepare a resin composition. As Comparative Example 2, only (D) component was made 0 parts, 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 component (A) and (B) component was 1.52.

(Application of Photocurable Composition)

Next, using the dispenser, the prepared photocurable resin composition was apply | coated on the crown glass substrate of thickness: 1.0 mm at width: 1 mm, length: 50 mm, and thickness of 100 micrometers, and the sample was produced.

(Light irradiation)

In the same manner as in Examples 1 to 6, the produced samples were irradiated with UV.

(Preparation of Sample of Cured Photocurable Resin Composition of Thickness 500 µm)

The sample of the cured photocurable resin composition with a film thickness of 500 micrometers was produced by repeating application | coating and light irradiation of the said photocurable composition in thickness of 100 micrometers four times further.

(Measurement of light transmittance)

In the same manner as in Example 2, the transmittance was measured and the reflectance was further measured. In addition, the reflectance was measured by the 90 degreeC absolute reflection method using the Nippon Bunko Corp. ultraviolet visible spectrophotometer (model number: U-best V-570).

(result)

The result of the relationship between the film thickness of a photocurable resin composition and a transmittance | permeability is shown in FIG. 4, and the result of the relationship of the film thickness of a photocurable resin composition and a reflectance is shown in FIG.

As shown in FIG. 4, the difference exists in the transmittance | permeability of Example 8 which added the component (D), and the comparative example 2 which did not add the component (D). As shown in FIG. 5, the reflectance of Example 8 is lowered to about 1/2 at a wavelength of 300 nm, compared to the reflectance of Comparative Example 2, and is about 1/5 of the reflectance of Comparative Example 2 at a wavelength of 350 nm or more. It was demonstrated that it falls below.

(Examples 9 to 16)

Next, Examples 9-16 were performed in order to investigate the effect which addition of a component (A) has on the adhesive strength of the cured photocurable resin composition.

(Production of Photocurable Resin Composition)

Polycarbonate-based urethane acrylate (product name: UN-5500, a weight average molecular weight: about 50,000) by Negami Kogyo Co., Ltd. as a component (A) in the amounts as shown in following Table 3, Kyoeisha Chemical Co., Ltd. 2-hydroxyl ethyl methacrylate (product name: HO) and Kyosisha Chemical Co., Ltd. Benzyl methacrylate (product name: BZ), and (B) as a component polyol type xylene manufactured by Kabuki Kaisha Alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) as a resin (modified product) (K140) and (C) component, and Nikko Vicus Co., Ltd. as (D) component As a black pigment (product name: NBD-0744) manufactured by Shikigaisha Co., Ltd., as a photopolymerization initiator, a mixture of 50 parts of 1-hydroxycyclohexylphenyl ketone manufactured by Chiba Japan Co., Ltd. and 50 parts of benzophenone (product name: Irgacure 500) is mixed. The photocurable resin composition was prepared. In addition, the refractive index of the hardened | cured material of component (A) and (B) component was 1.53.

(Preparation of Adhesive Strength Test Sample)

Using the photocurable resin composition thus prepared, as shown in Fig. 6, a glass plate of length: 75 mm, width: 25 mm, and thickness: 2.5 mm was partitioned with two spacers of 100 μm thickness and 1.5 cm in width. The photocurable resin composition was apply | coated to the groove | channel (coating length: 75 mm, application width: 15 mm, application thickness: 100 micrometers). After removing two spacers, the photocurable resin composition apply | coated on the glass plate was hardened by UV irradiation. Thickness: The polycarbonate (PC) plate of 500 micrometers was affixed, and the sample of the peel strength test was produced. 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)

The jig was affixed to the produced sample, the peel test was performed at 300 mm / min, and the shear test was carried out at 5 mm / min using the Shimadzu Corporation company tensile tester. 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, the addition amount of component (A) is 100 parts by weight, and the component (B) is 55 to 85 parts by weight, a peel strength of 1.0 N / 25 mm or more, shear strength of 2.2 MPa or more is obtained. It was demonstrated that the peeling strength of 1.2 N / 25 mm or more and the shearing strength of 2.9 MPa or more were obtained at 100 parts by weight of the added amount of the component (A) and 60 to 85 parts by weight of the component (B).

(Examples 17 to 23)

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

(Production of Photocurable Resin Composition)

Polycarbonate-based urethane acrylate (product name: UN-5500, weight average molecular weight: about 50,000) by Negami Kogyo Co., Ltd. as a component (A) in the quantity as shown in following Table 4, Kyoeisha Chemical Co., Ltd. 2-hydroxyl ethyl methacrylate (product name: HO) and Kyosisha Chemical Co., Ltd. Benzyl methacrylate (product name: BZ), and (B) as a component polyol type xylene manufactured by Kabuki Kaisha Alumina filler (product name: AO-902H, average particle diameter: 0.7 μm, refractive index: 1.76) as a resin (modified product) (K140) and (C) component, and Nikko Vicus Co., Ltd. as (D) component A black pigment manufactured by Shikigaisha Co., Ltd. (product name: NBD-0744), a mixture of 50 parts of 1-hydroxycyclohexylphenyl ketone manufactured by Chiba Japan Co., Ltd. and 50 parts of benzophenone (product name: Irgacure 500) are mixed as a photopolymerization initiator. The photocurable resin composition was prepared. In addition, the refractive index of the hardened | cured material of component (A) and (B) component was 1.53.

(Preparation of Adhesive Strength Test Sample, Adhesive Strength Test)

Using the manufactured photocurable resin composition, the sample was produced like Example 9-16, and peel strength and shear strength were measured.

(result)

Table 4 shows the results of the peel test and shear test.

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

The photocurable resin composition of this invention is capable of thick film hardening, has low light transmittance after hardening, has adhesiveness, and is excellent in various characteristics, such as strength, durability, and moisture resistance. Productivity is greatly improved and it is suitable as resin for manufacturing, such as various optical apparatus members and molded resin which require light shielding property.

1 LCD panel
2 fixed (sealed) resin layer
3 boards
4 back light
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 plates
10 PC version
A transmitted light from outside
Leakage light from inside B (lossy light)
C ultraviolet

Claims (10)

(A) Photocurable resin, (B) Tackifier, (C) The refractive index which becomes a difference with the refractive index of the hardened | cured material of the said (A) component and (B) component becomes 0.01 or more, The said (A) component and (B) Photocurable resin composition containing the compound which is incompatible and dispersible with respect to a component, and (D) black pigment. The photocurable resin composition according to claim 1, wherein the component (C) is selected from the group consisting of aluminum oxide powder and titanium oxide powder. The photocurable resin composition of Claim 1 or 2 whose (D) component is carbon powder. The photocurable resin composition according to any one of claims 1 to 3, wherein the component (B) is an acrylic, silicone, maleimide, rosin ester, terpene, rubber or aromatic hydrogenated petroleum tackifier. The photocurable resin composition of any one of Claims 1-4 whose (A) component is acrylic modified resin or an epoxy resin. 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) according to any one of claims 1 to 5. The photocurable resin composition which is 0.1-35 weight part. The photocurable resin composition of any one of Claims 1-6 which further contains a photoinitiator. Hardened | cured material of the photocurable resin composition in any one of Claims 1-7. The optical device member containing the hardened | cured material of Claim 8. An optical instrument comprising the optical instrument member according to claim 9.

Images