JPWO2014156424A1 - UV-curable light-shielding composition - Google Patents

Abstract

An object of the present invention is to provide an ultraviolet curable light-shielding composition capable of forming a sufficiently cured light-shielding cured product that is ultraviolet curable and thick. The present invention is an ultraviolet curable light-shielding composition comprising an ultraviolet curable compound and a glass filler containing nickel oxide and cobalt oxide.

Description

  The present invention relates to a light-shielding composition that effectively shields visible light and is excellent in ultraviolet curability.

  Light-shielding materials are widely used in various applications such as semiconductor devices, display devices, electro-optical devices, light-emitting devices, packaging materials, optical lenses such as cameras. For example, Patent Document 1 discloses the use of ultraviolet transmission heat ray absorbing glass having a specific metal oxide composition and excellent heat resistance as a glass filter of an ultraviolet irradiation apparatus for resin curing.

  In addition, various resins can be subjected to various processing such as molding, curing, adhesion and the like according to the characteristics, and since the function can be imparted to the resin by blending various functional components, as the light-shielding material, A light-shielding resin composition in which a light-shielding function is imparted to a resin by blending a light-shielding substance with the resin is widely used. It should be noted that what kind of wavelength the light shielding property is required depends on the application.

  Among them, for light-shielding materials that require light-shielding properties against visible light, such as light-shielding materials related to display devices, light-shielding materials for optical lenses, black matrix for color filters, and black stripes for lens sheets, carbon has been conventionally used. Blacks, acetylene blacks, coal tars, black pigment precursors, and the like blended with various resins have been developed (for example, Patent Documents 2 and 3).

  However, since the light-shielding resin composition in which various black pigments are mixed with these ultraviolet curable resins absorbs even ultraviolet rays, it cannot be cured to the deep part of the resin composition even when irradiated with ultraviolet rays. However, it was not possible to obtain a cured product that was thick and light-shielding and sufficiently cured. Therefore, the practical use of the resin composition as described above has not spread.

  Regarding such problems, the applicant of the present application has a refractive index at which the difference in refractive index between the photocurable resin 100 parts by weight and the refractive index of the cured product of the photocurable resin is 0.1 or more, A photocurable light-shielding resin composition containing 1 to 20 parts by weight of a particle of a compound that is incompatible and dispersible with a photocurable resin and does not contain a black pigment, wherein the particle size of the compound particle is 0 Developed a photo-curable light-shielding resin composition having a light transmittance at 300 to 800 nm of 1 to 100%, and a cured product of the photo-curable light-shielding resin composition having a thickness of 0.5 to 100 μm. And obtained a patent (Patent Document 4). The compound is a specific metal oxide or a specific resin.

JP-A 63-282139 Japanese Patent Laid-Open No. 9-40887 JP 2012-214039 A Japanese Patent No. 5129924

  The present invention is an ultraviolet curable light-shielding composition capable of forming a light-cured cured product that is ultraviolet curable, thick, and sufficiently cured by a configuration different from the invention described in Patent Document 4. The purpose is to provide goods.

  For example, for light-shielding materials that are required for light shielding against visible light, such as those used in display devices such as displays and optical lenses, basically only visible light that can be sensed by the eyes needs to be blocked. The presence or absence of light-shielding is not a problem in most cases.

Therefore, the inventor absorbs and blocks visible light as described above, but based on the idea that the above problem can be solved by giving the material the property of transmitting ultraviolet light. By using a specific glass filler having such characteristics, it has been found that an ultraviolet curable light-shielding composition capable of forming a sufficiently cured light-shielding cured product can be obtained. To complete.
That is, the gist of the present invention is as follows.

(1) An ultraviolet curable light-shielding composition comprising an ultraviolet curable compound and a glass filler containing nickel oxide and cobalt oxide.
(2) The ultraviolet curable light-shielding composition according to (1), wherein the glass filler content in the ultraviolet curable light-shielding composition is 5 to 95% by weight.
(3) The ultraviolet curable light-shielding composition according to (1) or (2), further comprising a photopolymerization initiator.
(4) The ultraviolet curable light-shielding composition according to any one of (1) to (3), wherein the ultraviolet curable compound comprises a (meth) acrylate oligomer and a (meth) acrylate monomer.
(5) The difference between the refractive index of the glass filler and the refractive index of the cured product of the ultraviolet curable composition obtained by removing the solid component from the ultraviolet curable light-shielding composition is -0.03 to +0. The ultraviolet curable light-shielding composition according to (3) or (4), which is 03.
(6) An ultraviolet light initiator and a visible light initiator are included as the photopolymerization initiator, and the content of the visible light initiator in the ultraviolet curable light-shielding composition is 0.01 to 0.15% by weight. The ultraviolet curable light-shielding composition according to any one of (3) to (5) above.
(7) including a filler other than the glass filler, and the difference between the refractive index of the filler and the refractive index of the cured product of the ultraviolet curable composition obtained by removing the solid component from the ultraviolet curable light-shielding composition The absolute value is 0.06 or more, and the content of the filler in the ultraviolet curable light-shielding composition is 0.5 to 5% by weight, according to any one of the above (3) to (6). UV-curable light-shielding composition.
(8) The ultraviolet curable light-shielding composition according to any one of (1) to (7), wherein the glass filler has an average particle size of 0.5 to 150 μm.
(9) A cured product of the ultraviolet curable light-shielding composition according to any one of (1) to (8) above.
(10) An optical device member having the cured product according to (9).

  According to the present invention, an ultraviolet curable light-shielding material capable of forming a sufficiently cured light-shielding cured product having a thickness different from that of the invention described in Patent Document 4 and having a large film thickness. Compositions are provided.

Hereinafter, the present invention will be described in detail.
[Ultraviolet curable light shielding composition]
<Ultraviolet curable compound>
The ultraviolet curable light-shielding composition of the present invention (hereinafter also referred to as “the composition of the present invention”) contains an ultraviolet curable compound and can be cured by irradiation with ultraviolet light. In this specification, ultraviolet rays refer to light having a wavelength in the range of 250 nm to less than 400 nm.

  As the ultraviolet curable compound, a conventionally known compound that causes a curing reaction (polymerization reaction, crosslinking reaction, etc.) upon irradiation with ultraviolet rays can be used without particular limitation, and examples thereof include (meth) acrylate oligomers, ( Examples include meth) acrylate monomers, epoxy oligomers, epoxy monomers, oxetane oligomers, and oxetane monomers. In the present specification, “(meth) acrylate” means methacrylate or acrylate, “(meth) acryl” means methacryl or acryl, and “(meth) acryloyl” means methacryloyl or acryloyl. Means. Moreover, the said ultraviolet curable compound can be used individually by 1 type or in combination of 2 or more types.

((Meth) acrylate oligomer)
The (meth) acrylate oligomer has properties such as adhesion, and conventionally known UV curable compounds can be used as the compound. Examples thereof include urethane (meth) acrylate oligomer and epoxy (meth). Examples include acrylate oligomers, polyester (meth) acrylates, and polyether (meth) acrylate oligomers.

((Meth) acrylate monomer)
The (meth) acrylate monomer includes a compound having a (meth) acryloyl group but not containing a (meth) acryl group. The (meth) acrylate monomer is used to adjust the viscosity, adhesiveness, curability and the like of the composition of the present invention,
As a specific example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, isodecyl ( (Meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, Butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethoxy Ethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxybenzyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, octafluoropentyl ( (Meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, allyl (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,4-butanediol (Meth) acrylate, (meth) acryloylmorpholine, 1,6-hexanediol (meth) acrylate, polyethylene glycol di (meth) acrylate, die Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxypivalic acid ester, neopentyl glycol di (meth) acrylate, tri Methylolpropane di (meth) acrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin, 3-methylpentanediol (meth) acrylate, α, ω-diacrylbisdiethylene glycol phthalate, trimethylolpropane tri ( (Meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, penta Risuri Tall tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tri (meth) acrylate of tri- hydroxyethyl isocyanurate, dipentaerythritol hexa (meth) acrylate;
These EO and / or PO adducts;
α, ω-tetraallylbistrimethylolpropane tetrahydrophthalate, 2-hydroxyethyl (meth) acryloyl phosphate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acryloxyethyl phosphate, Examples include N-vinylpyrrolidone and oligomers having these photoreactive functional groups.

(Epoxy oligomer)
Examples of the epoxy oligomer include:
Diglycidyl ethers of bisphenols such as biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrachlorobisphenol A, tetrabromobisphenol A;
Polyglycidyl ethers of novolak resins such as phenol novolak, cresol novolak, brominated phenol novolak, ortho cresol novolak;
Ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol, ethyleneoside adduct of bisphenol A, propylene oxide addition of bisphenol A Diglycidyl ethers of alkylene glycols such as
Glycidyl esters such as glycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-Epoxy-6'-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, lactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4'-epoxy Hexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexyl) ether, bis (3,4 Epoxycyclohexylmethyl) ether, tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis (3,4-epoxycyclohexylmethyl) -4,5-epoxytetrahydrophthalate, bis (3,4-epoxycyclohexyl) diethyl Examples thereof include alicyclic epoxy compounds such as siloxane; and oligomers having these photoreactive functional groups.

(Epoxy monomer)
Examples of the epoxy monomer include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, pt-butylphenyl glycidyl ether, and dibromophenyl glycidyl ether.

(Oxetane oligomer)
Examples of the oxetane oligomer include silsesquioxane derivatives having an oxetanyl group.

(Oxetane monomer)
Examples of the oxetane monomer include (for example, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-{[3-ethyloxetane-3-yl] methoxy}. Methyl} oxetane, 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxyethyloxetane, 4,4′-bis ((3-ethyl- 3-oxetanyl) methoxymethyl) biphenyl and (3-ethyl-3-oxetanyl) methoxymethyl (meth) acrylate).

  As the ultraviolet curable compound which is a constituent component of the composition of the present invention described above, a (meth) acrylate oligomer and a (meth) acrylate monomer are preferable from the viewpoint of adhesion to an adherend.

(Content of UV curable compound)
The content of the ultraviolet curable compound in the ultraviolet curable light-shielding composition (in 100% by weight) of the present invention is such that the composition is sufficiently cured and the glass filler can sufficiently exhibit its function. From the viewpoint, it is usually 10 to 99.9% by weight, preferably 20 to 80% by weight, and more preferably 20 to 70% by weight.

<Glass filler>
The ultraviolet curable light shielding composition of the present invention contains a glass filler containing nickel oxide and cobalt oxide. This has the property of absorbing visible light and transmitting ultraviolet light. By including such a glass filler, when the composition of the present invention is irradiated with ultraviolet rays, it is unlikely to be absorbed by the components in the composition, and is effectively used for the curing reaction of the composition. . At the same time, since the glass filler has a function of absorbing visible light, the composition of the present invention can achieve both sufficient curing with a sufficient film thickness and high visible light shielding property in a cured product. . Such effects cannot be obtained if nickel oxide and cobalt oxide are not made into the form of glass filler, and both are simply added to the composition.

As the cobalt oxide contained in the glass filler, both CoO and Co ₂ O ₃ can be used, and Co ₃ O ₄ which is a mixture thereof can also be used.

  The composition ratio of cobalt oxide in the glass filler is preferably 1 to 20% by weight, and more preferably 3 to 15% by weight, from the viewpoint of the ability to absorb visible light and transmit ultraviolet light. Also for nickel oxide, from the same viewpoint, the constituent ratio in the glass filler is preferably 0.1 to 5% by weight, more preferably 0.3 to 3% by weight.

  From the viewpoint of curing to a deeper part, the glass filler and the ultraviolet curable compound preferably have the same refractive index. Adjust the refractive index appropriately by adjusting the constituents of nickel oxide and cobalt oxide and other glass fillers (eg silicon dioxide, aluminum oxide, boron oxide, sodium oxide, lithium oxide, barium oxide, calcium oxide, antimony oxide) Can be adjusted. According to other required characteristics, the glass filler can be imparted with the characteristics by appropriately adjusting the constituents of the glass filler.

  Furthermore, from the viewpoint of deep curability, the difference in refractive index between the glass filler and the base resin cured product (the refractive index of the glass filler−the refractive index of the base resin cured product) is −0.03 to +0.03. Is preferable, and it is more preferable that it is 0-0.02. The base resin cured product is an ultraviolet curable compound obtained by removing a solid component such as a glass filler from the base curing component, that is, the composition of the present invention, among the components constituting the composition of the present invention. It refers to a cured product obtained by curing an ultraviolet curable composition comprising a photopolymerization initiator described later. The solid component is a substance that exists in a solid state in the composition of the present invention, and is a solid as a simple substance, but in the composition of the present invention, for example, a substance that is dissolved in an ultraviolet curable compound is present. Not included.

  For example, when the components of the ultraviolet curable light shielding composition are 10 parts by weight of a methacrylate oligomer, 10 parts by weight of an acrylate monomer, 10 parts by weight of an epoxy oligomer, 30 parts by weight of a glass filler, and 2 parts by weight of a photopolymerization initiator, The base resin cured product is a cured product of an ultraviolet curable composition comprising 10 parts by weight of a methacrylate oligomer, 10 parts by weight of an acrylate monomer, 10 parts by weight of an epoxy oligomer, and 2 parts by weight of a photopolymerization initiator.

The refractive index is a refractive index with respect to light having a wavelength of 633 nm, and the measurement method is as follows. The composition of the base curing component is sandwiched between a PET film and a slide glass so that the thickness is 0.5 mm, and cured by 6000 mJ / cm ² light irradiation with a metal halide lamp (ECS-301 made by Eye Graphics). Then, the cured film is peeled off from the PET film to produce a refractive index test piece. The refractive index of the test piece with respect to light having a wavelength of 633 nm is measured using a prism coupler (MODEL2010 manufactured by Metricon).

  It is preferable that the average particle diameter of the glass filler used for this invention is 0.5-150 micrometers from a viewpoint of the favorable dispersibility in the composition of this invention of the said glass filler, and its hardened | cured material. In addition, in this specification, an average particle diameter is a median diameter (D50).

  The glass filler can be produced by a known method. For example, glass is produced from various raw materials by a general method such as a melt quench method, a gas phase synthesis method or a sol-gel method, and then subjected to a pulverization step. If necessary, the particle size can be adjusted with a sieve to obtain a powdery glass filler. Moreover, the average particle diameter of the glass filler obtained can be adjusted by adjusting the grade of the grinding | pulverization in these grinding | pulverization processes.

  In this invention, the glass filler demonstrated above can be used individually by 1 type or in combination of 2 or more types. Further, the glass filler content in the composition of the present invention (in 100% by weight) may vary depending on the film thickness of the target cured product, the amount of nickel oxide and cobalt oxide in the glass filler, etc., but is sufficiently visible. From the viewpoint of achieving both a light shielding effect and a sufficient curing reaction of the curing component, it is preferably 5 to 95% by weight, more preferably 10 to 80% by weight, and still more preferably 10 to 70% by weight.

<Photopolymerization initiator>
In order to effectively cure the ultraviolet curable light shielding composition of the present invention, a photopolymerization initiator is usually added to the composition of the present invention.

As the photopolymerization initiator, a compound conventionally used for the application can be used without particular limitation, and specific examples thereof include:
Benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone 2-chlorobenzophenone, p, p′-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin-n-butyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetate Carbonyl group photopolymerization initiators such as enone and 4-N, N′-dimethylacetophenones; sulfide photopolymerization initiators such as diphenyl disulfide and dibenzyl disulfide; quinone photopolymerization initiators such as benzoquinone and anthraquinone; azo Ultraviolet photoinitiators such as azo photopolymerization initiators such as bisisobutyronitrile and 2,2′-azobispropane, and
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholinophenyl)- And visible light initiators such as butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

  The amount of the photopolymerization initiator used is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts per 100 parts by weight of the ultraviolet curable compound from the viewpoint of effectively performing the curing reaction of the ultraviolet curable compound. Parts by weight.

  Further, from the viewpoint of deep curable, the ultraviolet curable curable light-shielding composition of the present invention includes both an ultraviolet light initiator and a visible light initiator, and the ultraviolet curable light-shielding composition of the visible light initiator. The content in the product is preferably 0.01 to 0.15% by weight.

<Other ingredients>
The photocurable light-shielding composition of the present invention may further comprise other known additives, for example, fillers other than the glass filler, antioxidants, light stabilizers, silane coupling agents, thermal polymerization, depending on the purpose. Inhibitors, leveling agents, surfactants, colorants, storage stabilizers, plasticizers, lubricants, solvents, anti-aging agents, wettability improvers, mold release agents and the like can be contained. In addition, the composition of the present invention contains an organic / inorganic coloring pigment within a range not impairing the effects of the present invention (with respect to 100 parts by weight of the ultraviolet curable compound) in order to reduce the visible light transmittance of the cured product. For example, several parts by weight or less, particularly 1 part by weight or less).

  In particular, the composition of the present invention contains 0.5 to 5% by weight of a specific filler other than the glass filler from the viewpoint of improving the light shielding property while minimizing the influence on the deep curability of the composition. preferable. The filler is a filler whose absolute value of the difference between the refractive index of the filler and the refractive index of the cured base resin (refractive index of filler−refractive index of the cured base resin) is 0.06 or more. The definition of the base resin cured product and the method of measuring the refractive index are as described above.

  As such a filler, various known fillers can be used as long as the refractive index difference from the cured base resin is satisfied (and contained in the range of 0.5 to 5% by weight). There is no particular restriction.

<Method for producing ultraviolet curable light-shielding composition>
The ultraviolet curable light-shielding composition of the present invention can be produced by mixing the above-described components by a conventional method. The order of adding each component is not particularly limited.

[Usage of UV-curable light shielding composition]
The ultraviolet curable light-shielding composition of the present invention is effectively cured by irradiation with ultraviolet rays. In particular, because it contains a specific glass filler that absorbs visible light and transmits ultraviolet light as a light-shielding substance, the irradiated ultraviolet light is effectively used for curing the composition. It is difficult for things to be absorbed by things.

Therefore, according to the composition of the present invention, it is possible to form a cured product having a wide range of film thickness, for example, a film thickness of 0.5 mm or more (usually 10 mm or less). The conditions for ultraviolet curing can vary depending on the composition of the composition, the desired film thickness, etc. For example, a urethane filler and a methacrylate monomer are used as the ultraviolet curable compound, and a glass filler containing nickel oxide and cobalt oxide is used. When used and the target film thickness is 2 mm, the ultraviolet irradiation amount is 3000 to 6000 mJ / cm ² .

  In addition, when the composition of the present invention contains a visible light initiator as a photopolymerization initiator, it causes a curing reaction more effectively by irradiating visible light in addition to ultraviolet light, and further deeper. It can be cured.

  In the cured product obtained from the composition of the present invention, the ultraviolet curable compound is cured by a polymerization reaction or a crosslinking reaction to form a strong structure, and the glass filler is uniformly dispersed in the cured product. This glass filler imparts a visible light shielding function to the cured product.

  Therefore, the cured product has excellent visible light shielding properties, and for example, the transmittance of light having a thickness of 0.5 mm and a wavelength of 500 nm is usually 1% or less, preferably 0 to 0.1%.

  In this way, a wide range of film thicknesses can be realized, and a cured product having excellent light-shielding properties for visible light is formed. It can be used for a light-shielding material, specifically, a light-shielding sealant for a display device.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited at all by these.

<Preparation of glass filler>
Various glass fillers having chemical compositions shown in Table 1 below were prepared according to known methods. The glass fillers UVG-1C, UVG-6C, UVG-9C, UVG-10C, and UVG-12C all have an average particle diameter (median diameter) of 6.7 μm.

<Evaluation of deep curing>
The deep curing of the ultraviolet curable light-shielding compositions prepared in the following examples and comparative examples was evaluated as follows.

The prepared composition was put in a 6 mmφ black tube, and irradiated with 300 mW / cm ² of ultraviolet rays for 12 seconds (ultraviolet ray irradiation amount: 3600 mJ / cm ² ) with a high-pressure mercury lamp (LC5 manufactured by Hamamatsu Photonics). The obtained cured product was taken out from the tube and the thickness was measured with a micrometer.

<Evaluation of transmittance>
The transmittance of the cured product of the ultraviolet curable light-shielding composition prepared in Examples and Comparative Examples was evaluated as follows.

The composition was sandwiched between glass slides to a thickness of 0.5 mm, and cured by irradiating light of 6000 mJ / cm ^{2 with} a metal halide lamp (ECS-301 manufactured by Eye Graphics) to prepare a transmittance test piece. The transmittance of the test piece with respect to light having a wavelength of 500 nm was measured using an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation).

<Evaluation of refractive index>
The refractive index of the base resin cured product was evaluated as follows. The composition of the base curing component is sandwiched between a PET film and a slide glass so that the thickness is 0.5 mm, and cured by 6000 mJ / cm ² light irradiation with a metal halide lamp (ECS-301 made by Eye Graphics). The cured film was peeled off from the PET film to prepare a refractive index test piece. The refractive index of the test piece with respect to light having a wavelength of 633 nm was measured using a prism coupler (MODEL2010 manufactured by Metricon).

[Comparative Examples 1-4 and Examples 1-3]
Various components were mixed in the composition shown in Table 2 below to prepare ultraviolet curable light shielding compositions of Comparative Examples 1 to 4 and Examples 1 to 3. About each of them, the deep part hardening and the transmittance | permeability were evaluated. The results are also shown in Table 2.

From Table 2, from the ultraviolet curable light-shielding compositions of Comparative Examples 1 and 2 in which a blue pigment and carbon black are blended as a light-shielding substance, a thick cured product cannot be obtained.
From the ultraviolet curable light-shielding compositions of Examples 1 to 3 in which a glass filler containing nickel oxide and cobalt oxide was blended, a thick cured product was obtained, and the cured product of Comparative Examples 1 and 2 was used. Have achieved the same level of light-shielding properties as the cured product,
Furthermore, it turns out that the hardened | cured material with a thick film thickness cannot be obtained in the ultraviolet curable light shielding composition of the comparative examples 3 and 4 which mix | blended both nickel oxide and cobalt oxide in the form of a glass filler instead.

[Examples 4 to 21]
Various components were mixed in the composition shown in Table 3 below to prepare UV curable light shielding compositions of Examples 4 to 21. About each of them, evaluation of deep part hardening, the transmittance | permeability, and the refractive index of hardened | cured base resin was performed. The results are shown in Table 3, and the data of Example 2 are also shown for reference.

  Comparing Examples 4 and 6 to 21 and Examples 2 and 5, when the refractive index difference between the glass filler and the base resin cured product is controlled to -0.03 to +0.03, the deep curability can be improved. I understand that I can do it.

  Comparing Examples 11, 12, 15-21 to Examples 10, 13, and 14, the composition of the present invention comprises an ultraviolet light initiator and a visible light initiator, and a visible light initiator in the composition. It turns out that deep-part sclerosis | hardenability can further be improved by making content into 0.01 to 0.15 weight%.

  When Examples 13 to 15 and Examples 19 to 21 are compared, it is a filler other than the glass filler used in the present invention, and the absolute value of the difference in refractive index from the base resin cured product is 0.06 or more. It can be seen that, when blended with a content of 0.5 to 5% by weight, the light-shielding property can be greatly enhanced without significantly affecting the deep curability.

Claims (10)

  An ultraviolet curable light-shielding composition comprising an ultraviolet curable compound and a glass filler containing nickel oxide and cobalt oxide.   The composition for ultraviolet curable light shielding according to claim 1, wherein the content of the glass filler in the ultraviolet curable light shielding composition is 5 to 95% by weight.   Furthermore, the ultraviolet curable light shielding composition of Claim 1 or 2 containing a photoinitiator.   The ultraviolet curable light-shielding composition according to any one of claims 1 to 3, wherein the ultraviolet curable compound comprises a (meth) acrylate oligomer and a (meth) acrylate monomer.   The difference between the refractive index of the glass filler and the refractive index of the cured product of the ultraviolet curable composition obtained by removing the solid component from the ultraviolet curable light-shielding composition is -0.03 to +0.03. The ultraviolet curable light-shielding composition according to claim 3 or 4.   An ultraviolet light initiator and a visible light initiator are included as the photopolymerization initiator, and the content of the visible light initiator in the ultraviolet curable light-shielding composition is 0.01 to 0.15% by weight. The ultraviolet curable light-shielding composition according to any one of 3 to 5. Including fillers other than the glass filler,
The absolute value of the difference between the refractive index of the filler and the refractive index of the cured product of the ultraviolet curable composition obtained by removing the solid component from the ultraviolet curable light-shielding composition is 0.06 or more,
The ultraviolet curable light-shielding composition according to any one of claims 3 to 6, wherein the content of the filler in the ultraviolet curable light-shielding composition is 0.5 to 5% by weight.   The ultraviolet curable light-shielding composition according to claim 1, wherein the glass filler has an average particle size of 0.5 to 150 μm.   Hardened | cured material of the composition for ultraviolet curable light-shielding of any one of Claims 1-8.   An optical device member having the cured product according to claim 9.