JP2015118349A - Resin composition for antireflection layer, antireflection layer, and optical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an antireflection layer, which can be cured in a short time and has excellent heat resistance and durability, and an antireflection layer having good characteristics with high yield by using the composition, and an optical device using the antireflection layer.SOLUTION: The resin composition for an antireflection layer comprises an alicyclic epoxy and a reaction initiator. The reaction initiator comprises a photoacid generator. The composition for an antireflection layer is in a varnish state at room temperature and has a property of suppressing shrinkage during curing, and thereby, the composition can be used for a member for an optical device that requires high dimensional accuracy.

Description

  The present invention relates to a resin composition for an antireflection layer, and more particularly to a transparent resin composition for an antireflection layer excellent in processability and heat resistance, an antireflection layer, and an optical device using the same.

  In general, the antireflection member prevents a decrease in contrast and reflection of an image due to reflection of external light in an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), or a liquid crystal display (LCD). Therefore, it is placed on the outermost surface of the display so as to reduce the reflectivity using the principle of optical interference.

For example, as described in Patent Document 1, such an antireflection member is formed by applying the coating composition only once on at least one side of the supporting substrate (hereinafter, the coating composition on the supporting substrate is 1). This is achieved by forming an antireflection layer composed of two layers having different refractive indices, the surface on which the coating is applied only once. In Patent Document 2, a multilayer film in which the amount of transmitted light is changed by alternately laminating a light absorption film and a dielectric film on one surface of a transparent substrate is changed from two or more kinds of films having different refractive indexes. And a method of laminating a multilayer antireflection layer comprising two or more kinds of films having different refractive indexes on two surfaces.
There are various other methods for producing an antireflection member, but there is a problem that it takes time to produce them.

Japanese Unexamined Patent Publication No. 2012-008158 JP 2010-175941 A

The present invention relates to a resin composition for an antireflection layer that can be cured in a short time and is excellent in heat resistance and durability, an antireflection layer having good characteristics at a high yield by using the same, and an optical device using the same The purpose is to provide.

The present invention is as follows.
(1) A resin composition for an antireflection layer comprising an alicyclic epoxy resin precursor represented by Chemical Formula 1 and / or Chemical Formula 2 and a polymerization initiator.

[In the above formula (1), -X- is _{-O -, - S -, -} SO -, - SO 2 -, - CH 2 -, - CH (CH 3) -, or -C _{(CH 3) 2} -Represents. ]

(2) The resin composition for an antireflection layer according to (1), wherein the polymerization initiator is a photoacid generator.
(3) The resin composition for an antireflection layer according to (1) or (2), wherein the ratio of the alicyclic epoxy resin in the resin composition is 50% to 100%.
(4) The resin composition for an antireflection layer according to any one of claims 1 to 3, wherein the content of the isomer of the compound according to (1) is 40% or less.
(5) The resin composition for an antireflection layer as described in any one of (1) to (4), which contains an antioxidant.
(6) An antireflection layer using the resin composition for an antireflection layer according to any one of (1) to (5).
(7) The antireflection layer according to (6), wherein the reflectance of incident light is 3% or less in the antireflection layer.
(8) The antireflection layer according to (6) or (7), wherein the antireflection layer has a refractive index of 1.4 to 1.6.
(9) The antireflection layer according to (8), wherein the product of the refractive index and the thickness is from 50 nm to 200 nm.
(10) The antireflection layer according to (9), wherein the layer has a thickness of 150 nm or less.
(11) The antireflection layer, which has an uneven structure on at least one surface thereof, and the height of the uneven structure is 0.02 μm or more and 0.95 μm or less. 2. The antireflection layer according to item 1.
(12) The antireflection layer according to (11), wherein the pitch of the uneven structure is 300 nm or less.
(13) An optical device having the antireflection layer according to any one of (6) to (12).
(14) A display device comprising the antireflection layer according to any one of (6) to (12).
(15) A liquid crystal display device comprising the antireflection layer according to any one of (6) to (12).
(16) An organic electroluminescence display device having the antireflection layer according to any one of (6) to (12).
(17) A lens having the antireflection layer according to any one of (6) to (12).
(18) An imaging device having the antireflection layer according to any one of (6) to (12).

According to the present invention, a resin composition for an antireflection layer that can be cured in a short time and is excellent in heat resistance and durability, an antireflection layer having good characteristics at a high yield by using this, and the same are used. An optical device can be provided.

The figure which shows the display apparatus which has an antireflection film The figure which shows the lens which has an antireflection film. The figure which shows the image pick-up element which has an antireflection film.

The present invention relates to a resin composition for an antireflection layer, wherein the resin composition for an antireflection layer contains an alicyclic epoxy resin precursor and a polymerization initiator.
Hereinafter, each material constituting the resin composition for an antireflection layer will be described in detail.

(A) Alicyclic epoxy resin The resin used in the present invention is preferably one that becomes liquid at room temperature or upon heating, particularly from the property of suppressing shrinkage during curing. Are preferably used, and those having the following chemical formulas can be most suitably used.

[In the above formula (1), -X- is _{-O -, - S -, -} SO -, - SO 2 -, - CH 2 -, - CH (CH 3) -, or -C _{(CH 3) 2} -Represents. ]

The ratio of (1) and (2) in the resin composition is preferably 50% to 100%, more preferably 60 to 100%. By containing (1) and (2) within this range, shrinkage during curing can be effectively reduced.
Further, the isomer ratio of (1) and (2) is preferably 40% or less, and more preferably 30% or less. When the isomer contrast of (1) and (2) is within this range, the reaction by the reaction initiator is effectively performed.

(Other resins)
In the present invention, a resin other than the alicyclic epoxy resin may be contained, and in particular, a heat and / or photocrosslinking resin can be suitably used.
Specifically, epoxy resins, oxetane resins, isocyanate resins, acrylate resins, olefin resins, cycloolefin resins, diallyl phthalate resins, polycarbonate resins, diallyl carbonate resins, urethane resins, melamine resins Examples include resins, polyimide resins, aromatic polyamide resins, polystyrene resins, polyphenylene resins, polysulfone resins, polyphenylene oxide resins, silsesquioxane compounds, and the like.

Among the above, especially an epoxy resin can be added to the extent that the compatibility and reactivity with the alicyclic epoxy resin are good and the characteristics of the alicyclic epoxy resin are not impaired. Examples of epoxy resins other than alicyclic epoxy resins include glycidyl type epoxy resins, and specific examples include novolak type epoxy resins such as phenol novolak type epoxy and cresol novolak type epoxy, bisphenol A type epoxy, and bisphenol F type. Bisphenol type epoxy resin such as epoxy, N, N-diglycidylaniline, N, N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aromatic glycidylamine type epoxy resin such as aminophenol type glycidylamine, hydroquinone type epoxy, Biphenyl type epoxy, stilbene type epoxy, triphenolmethane type epoxy, triphenolpropane type epoxy, alkyl-modified triphenolmethane type epoxy, triazine core Aralkyl type epoxy such as epoxy, dicyclopentadiene modified phenol type epoxy, naphthol type epoxy, naphthalene type epoxy, phenol aralkyl type epoxy having phenylene and / or biphenylene skeleton, naphthol aralkyl type epoxy having phenylene and / or biphenylene skeleton, etc. Epoxy resins, glycidyl type epoxy resins having a fluorene skeleton, n-butyl glycidyl ether, versatic acid glycidyl ester, styrene oxide, ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, butylphenyl glycidyl ether, and other monofunctional epoxy resins, Or what carried out hydrogenation of the benzene ring among the above is mentioned.

(B) Reaction initiator Examples of the reaction initiator used in the present invention include acid generators, base generators, acid anhydrides, crosslinking agents such as aliphatic amines, radical reaction initiators, and the like. It is preferable that it is a photo-acid generator at the point that is favorable.

  Examples of the photoacid generator include onium salts such as a Lewis acid diazonium salt, a Lewis acid iodonium salt, and a Lewis acid sulfonium salt. Specific examples of the photocationic initiator include phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorus hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-4-methylphenyl of arsenic hexafluoride Examples thereof include sulfonium salts, tri-4-methylphenylsulfonium salts of antimony tetrafluoride, and mixtures thereof.

In addition, examples of the thermal cationic reaction initiator include aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, boron trifluoride amine complexes, and mixtures thereof.
Moreover, you may mix the said photocationic reaction initiator and a thermal cationic reaction initiator.

Although content of such a cationic reaction initiator is not specifically limited, It is preferable that it is about 0.1-5 mass parts with respect to 100 mass parts of resin materials, and 0.5-3 weight part is especially preferable. . When the content is less than the lower limit, the reactivity of the resin material may be reduced, and when the content exceeds the upper limit, the resin composition may be brittle.
In the case of photocuring, in order to accelerate the curing reaction of the resin material, a sensitizer, an acid proliferating agent, and the like can be used together as necessary.

Examples of the anionic catalyst include amine-based reaction initiators. The molecular weight and structure are not particularly limited as long as the molecule contains two or more primary amines or secondary amines capable of forming a covalent bond with the epoxy group in the epoxy resin. Examples of such amine reaction initiators include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine aliphatic polyamine, isophoronediamine, 1, Alicyclic polyamines such as 3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-) Piperazine type polyamines such as methylpropyl) piperazine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), Polytetramethylene oxide - aromatic polyamines such as di -P- aminobenzoate and the like. These reaction initiators may be used alone or in combination of two or more kinds of reaction initiators. In addition, use of an imidazole compound alone or in combination with an amine-based reaction initiator may also be mentioned. Examples of the imidazole compound include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4. , 5-dihydroxy methyl imidazole, 2-C ₁₁ H ₂₃ - adds a generic imidazole or triazine and isocyanuric acid such as imidazole, to impart storage stability of 2,4-diamino-6- {2-methylimidazole - (1)}-Ethyl-S-triazine, or its isocyanate adduct, and the like, and these can be used alone or in combination.

Examples of acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, dodecynyl succinic anhydride, dichlorosuccinic anhydride, methyl nadic anhydride, Mellitic acid, methylhexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer, Examples thereof include tetrabromophthalic anhydride, polyazeline acid anhydride, chlorendic acid anhydride, benzophenone tetracarboxylic anhydride and the like, and these may be used alone or in combination. In addition, use of an imidazole compound in combination with an acid anhydride-based reaction initiator can also be mentioned. Examples of the imidazole compound include those described above.

(Other additives)
In addition, the resin composition may contain an antioxidant, a nanofiller, and the like.

(Antioxidant)
As the antioxidant, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like are used, and a hindered phenol-based antioxidant is particularly preferably used.
Examples of the hindered phenol antioxidant include BHT, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol = tetrakis [3- (3 ′, 5′-di-tert- Butyl-4′-hydroxyphenyl) propionate] and the like.

The content of the antioxidant in the resin varnish is preferably 0.01% by mass to 5% by mass, and more preferably about 0.1% by mass to 3% by mass. By setting the content of the antioxidant within the above range, a resin composition having low optical anisotropy is obtained, and a surface resin composition having a small degree of deterioration of optical anisotropy in a reliability test is obtained. can get.

Moreover, it is preferable that the weight average molecular weight of antioxidant is 200-2000, It is more preferable that it is 500-1500, It is further more preferable that it is 1000-1400. If the weight average molecular weight of the antioxidant is within the above range, volatilization of the antioxidant is suppressed and compatibility with a resin material (for example, an alicyclic epoxy resin) is secured. Such an antioxidant can realize a resin composition for an antireflection layer with little optical anisotropy even after a reliability test such as wet heat treatment.

Examples of phenolic antioxidants other than hindered phenolic antioxidants include, for example, semi-hindered phenolic antioxidants in which one of the substituents located so as to sandwich the hydroxyl group is substituted with a methyl group or the like. And a hindered phenolic antioxidant in which both of two substituents sandwiching a hydroxyl group are substituted with a methyl group or the like. These are added to the resin varnish in an amount less than that of the hindered phenol antioxidant.
Examples of phosphorus antioxidants include tridecyl phosphite and diphenyl decyl phosphite.

In addition, the synergistic effect is exhibited by using together a hindered phenolic antioxidant and phosphorus antioxidant. Thereby, the oxidation prevention of the resin material and the suppression of the deterioration of the optical anisotropy of the resin composition become more remarkable. This is because the hindered phenolic antioxidant and the phosphorus antioxidant differ in the antioxidant mechanism of the resin material, so that they work independently and have a synergistic effect. it is conceivable that.

The addition amount of antioxidants (particularly phosphorus antioxidants) other than such hindered phenolic antioxidants is preferably about 30 to 300 parts by mass with respect to 100 parts by mass of hindered phenolic antioxidants. And more preferably about 50 to 200 parts by mass. Thereby, a hindered phenolic antioxidant and other antioxidants can exhibit each effect without burying (cancelling), and can bring about a synergistic effect.

(Nano filler)
The resin composition may include a fiber or a particulate filler. The material of the inorganic filler contained in the resin composition according to the present disclosure is not particularly limited as long as it is an inorganic substance. In one or a plurality of embodiments, a metal oxide such as silica, alumina, titanium oxide, or a mineral such as mica. , Glass, or a mixture thereof. Examples of the glass include E glass, C glass, A glass, S glass, D glass, NE glass, T glass, low induction glass, and high induction glass.
When the inorganic filler is a fiber, the average fiber diameter of the fiber is 1-1000 nm from the viewpoint of reducing the thermal expansion coefficient of the cured resin and improving the transparency of the cured resin. Here, the fibers may be composed of single fibers that are sufficiently spaced so that the liquid precursors of the matrix resin enter between each other without being aligned. In this case, the average fiber diameter is the average diameter of single fibers. Further, the fiber may be one in which a plurality of single fibers are gathered in a bundle to constitute one yarn, and in this case, the average fiber diameter is the diameter of one yarn. Defined as an average value.
When the inorganic filler is a particle, the average particle diameter of the particle is 1-1000 nm from the viewpoint of reducing the thermal expansion coefficient of the cured resin and improving the transparency of the cured resin. Here, the average particle diameter of the particles refers to an average projected circle equivalent diameter, and is specifically measured by the method of the example. The shape of the particles is not particularly limited, but in one or a plurality of embodiments, from the viewpoint of reducing the coefficient of thermal expansion of the cured resin and improving the transparency of the cured resin, spherical or true spherical, rod-shaped, A flat plate shape or a combined shape thereof may be mentioned. In one or a plurality of embodiments, the proportion of the inorganic filler in the solid content in the polyamide solution according to the present disclosure is 1% by weight to 50% by weight, 2% by weight to 40% by weight, or 3% by weight to 30% by weight. It is.

(Description of cured product formed by curing the antireflection resin composition)
The resin composition of the present invention may be provided as a varnish that is an uncured resin.
First, the varnish will be described.
The resin varnish contains the aforementioned uncured resin material, other components, an organic solvent, and the like, and also contains the aforementioned reaction initiator, antioxidant, and the like as necessary.
In addition, the resin varnish may contain an oligomer or a monomer of a thermoplastic resin or a thermosetting resin as necessary as long as the characteristics are not impaired.
If necessary, the resin varnish may be defoamed.

(Curing varnish)
The varnish can be put into a mold as it is, cured and molded. It is also possible to cure and mold while pressing the mold.

Light curing (UV curing)
In order to cure the resin composition of the present invention, the necessary amount of accumulated light is preferably, for example, 50 to 5000 mJ / cm ² , more preferably 75 to 4000 mJ / cm ² , and 100 to Even more preferably, it is 3000 mJ / cm ² . Further, “curing” means that many functional groups that can participate in the curing reaction are reacted in the resin composition. Specifically, the epoxy ring opening rate of the resin composition is 50% or more. It means that.
The epoxy ring-opening rate is an index corresponding to the ring-opening ratio of the epoxy group in the resin cured product. As a method for measuring the epoxy ring-opening rate, first, an absorbance spectrum of a cured resin sample is obtained by Fourier transform infrared spectroscopy (FT-IR).

Then, the obtained absorbance spectrum, the area of the peak derived from the epoxy group located in the vicinity of a wave number of 914 cm ^-1, normalized to the area of the peak derived from the methylene groups located in the vicinity of a wave number of 2900 cm ^-1, which sample ""Epoxy relative strength". Here, the ratio of the peak area derived from the epoxy group to the peak area derived from the methylene group is defined as the epoxy relative strength X of the sample, and the epoxy ring opening rate of the sample to be obtained is defined as Y (%).
On the other hand, when measuring the epoxy relative strength of the sample, the epoxy relative strength of the resin composition before curing is measured in advance. Since it is presumed that the epoxy group is not ring-opened in the resin composition before curing, this can be used as a standard sample, and the epoxy relative strength of the resin composition corresponds to an epoxy ring-opening rate of 0%. Can be considered. The epoxy relative strength of the resin composition before curing is set to 100.
Moreover, after hardening by the said light irradiation, reaction can be advanced more by performing the process by a heat | fever as a secondary process.

The treatment temperature during the secondary treatment is preferably about 150 to 300 ° C, and more preferably about 200 to 280 ° C. The treatment time is preferably about 0.1 to 5 hours, more preferably about 0.2 to 3 hours. Thereby, reaction can be advanced efficiently.
When the reaction initiator is a thermal initiator, the primary heating conditions are 60 ° C. to 300 ° C., preferably 70 ° C. to 280 ° C., and the treatment time is 5 minutes to 3 hours, preferably 10 minutes to 2 hours.

(Antireflection layer)
The resin composition can form an antireflection layer.
The reflectance of incident light is preferably 3% or less, more preferably 2% or 1%. When the reflectance becomes these numerical values, an optical device with high performance can be manufactured.

The refractive index of the antireflection layer is preferably 1.4 to 1.6, more preferably 1.45 to 1.6. When the refractive index is within this range, the antireflection effect of the produced antireflection layer can be enhanced.

Moreover, the antireflection layer having a product of the refractive index and the thickness of 50 nm or more and 200 nm or less can be obtained by applying and curing the resin composition, and an antireflection effect can be obtained efficiently.

In addition, the thickness of the antireflection layer is preferably 150 nm or less, and more preferably 130 nm. When the thickness is in this range, the antireflection effect of the produced antireflection layer can be enhanced.

Specifically, die coating, spin coating, slit coating or the like can be used as the coating method. In particular, application by spin coating is preferable in terms of thinning with a uniform film thickness.

Examples of the curing method include UV light, heat, and a combination thereof.

Furthermore, by having irregularities on the surface, an antireflection effect can be obtained regardless of the thickness and refractive index.
Surfaces with unevenness heights of 1 μm or less and uneven structures with pitches of 300 nm or less can be processed without using molds such as reverse sputtering treatment and oxygen plasma treatment to spray fine particles of nm size on the surface, It can be obtained by an imprint method using a mold. In this case, a good antireflection effect can be obtained by an optical effect different from that of the antireflection layer in which the product of the refractive index and the thickness is 100 nm to 200 nm. Specifically, as described in JP-A-2001-264520, a fine concavo-convex film in which a fine concavo-convex pattern having a pitch equal to or less than the wavelength of light is formed on the surface of a film or the like has almost no resin at the bottom of the concavo-convex. Therefore, the closer to the surface side of the unevenness, the lower the proportion of resin, and the higher the proportion of air, the lower the refractive index. It is known that the vicinity of the outer surface approaches the refractive index (1.0) of air as much as possible, and has the same effect as if a number of layers in which the refractive index of light changes continuously is stacked. Therefore, the antireflection effect can be obtained without controlling the thickness.

(Optical device having antireflection layer)
Since the resin composition for an antireflection film of the present invention can be cured in a short time as described above, it is possible to efficiently produce an antireflection layer, and as a result, an optical that requires high dimensional accuracy. It can be used as a device member.
The optical device in the present invention represents a device group related to light absorption, transmission, and light emission, and specifically, a display device such as a liquid crystal display device or an organic electroluminescence display device, a lens, an image sensor, or the like. .
Hereinafter, although a specific example is given and demonstrated, this invention is not limited to these specific examples.

The resin composition can be cured in a short time as described above, and can also obtain high light transmittance by selecting a resin, such as a liquid crystal display device or an organic electroluminescence display device ( 1). An antireflection layer can be obtained by forming a layer with a predetermined thickness using a resin composition having a predetermined refractive index for these display devices, or by forming irregularities. The refractive index of the resin composition for producing a layer having an antireflection effect, the layer thickness conditions, and the unevenness conditions are as described above.

In addition to the above-described property of suppressing shrinkage during curing, the resin composition can also acquire high light transmittance by selecting a resin, and can be used as an antireflection layer for an optical lens. (Fig. 2). An antireflection layer can be formed by forming a layer with a predetermined thickness using a resin composition having a predetermined refractive index for the lens, or by forming irregularities. The refractive index of the resin composition for producing a layer having an antireflection effect, the layer thickness conditions, and the unevenness conditions are as described above.

Moreover, the said resin composition can be used for the reflection preventing layer for image sensors (FIG. 3). The image sensor is a CCD image sensor or a CMOS image sensor. In general, an image sensor performs photoelectric conversion with an array of a large number of light receiving elements formed on a substrate, and generates light by light energy when the light receiving elements are irradiated with light. The main operation is to transfer this electric charge to the outside by a CCD element or a CMOS element. The resin composition of the present invention is preferably used as an antireflection layer on the surface of the lens portion of the device. An antireflection layer can be obtained by forming a layer with a predetermined thickness using a resin composition having a predetermined refractive index on the surface of the lens portion, or by forming irregularities. The refractive index of the resin composition for producing a layer having an antireflection effect, the layer thickness conditions, and the unevenness conditions are as described above.

  Next, specific examples of the present invention will be described.

Example 1
(A) 100 parts by mass of bicyclohexyl-3,3′-dioxide (EBP, manufactured by Daicel) shown in the following compound (2) as an alicyclic epoxy resin precursor, and (B) an antimony sulfonium salt type as a reaction initiator 1 part by mass of a photoacid generator (SP-170, manufactured by ADEKA) was added, mixed until uniform, and then filtered through a filter having a hole diameter of 1 μm to prepare an optical resin composition.

On a transparent polyester film having a thickness of 125 μm (manufactured by Toyobo Co., Ltd.), an unwinding device, a die coater, a high-pressure mercury lamp, a shaping roll having an irregular shape with a period of 100 nm and a height of 200 nm, a heating furnace, and a winding device Using an industrial machine, apply this anti-reflective layer resin composition to a thickness of 0.09 μm, and integrate ultraviolet rays with a metal halide lamp with an illuminance of 150 mW / cm ² from the back while pressing the coated surface against the shaping roll. The film was irradiated with a light amount of about 900 mJ / cm 2 (irradiation time: 6 seconds) and heated at 80 ° C. for 10 minutes in a heating furnace under a nitrogen atmosphere to produce a film with an antireflection layer. This antireflection layer-attached film was bonded to a liquid crystal panel composed of a liquid crystal cell, an optical compensation plate, a polarizing plate, etc. with an adhesive, and a backlight unit was combined to produce a liquid crystal display. The reflectance at a wavelength of 550 nm on the surface of this liquid crystal display was measured and found to be 0.5%.

(Example 2)
(A) As an alicyclic epoxy resin precursor, 100 parts by mass of an alicyclic epoxy resin precursor (E-DOA, manufactured by Daicel) shown in the following compound (3), and (B) an antimony sulfonium salt type as a reaction initiator 1 part by mass of a photoacid generator (SP-170, manufactured by ADEKA) was added and mixed until uniform, followed by filtration with a filter having a hole diameter of 10 μm to prepare a resin composition for an antireflection layer.

The resin composition for the antireflection layer is applied to the surface of the lens having a diameter of 60 mm shown in FIG. A 150 mW / cm ² metal halide lamp was irradiated with ultraviolet rays with an integrated light quantity of about 900 mJ / cm 2 (irradiation time: 6 seconds), and heated in a heating furnace at 120 ° C. for 10 minutes to produce a lens with an antireflection layer. The reflectance at a wavelength of 550 nm on the lens surface with the antireflection layer was measured and found to be 0.1%.

(Example 3)
In Example 1, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)] (Irganox 1010, Ciba) which is a hindered phenol-based antioxidant as an antioxidant.・ Specialty Chemicals) 1
A resin composition was prepared with the same components as in Example 1 except that a mass part was added and mixed until uniform, followed by filtration with a filter having a hole diameter of 1 μm to prepare an optical resin composition. A lens with an antireflection layer was produced in the same manner as in Example 2. The reflectance at a wavelength of 550 nm on the lens surface with the antireflection layer was measured and found to be 0.1%. In addition, there was no change after standing in a heating furnace at 90 ° C./100 hours.

(Comparative example)
100 parts by mass of bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical) as an epoxy resin, 90 parts by weight of an acid anhydride (MH-70.0 (manufactured by Shin Nippon Rika Co., Ltd.)) as a reaction initiator, imidazole compound 2 M Z -A (manufactured by Shikoku Kasei Co., Ltd.) 1 part by weight was mixed until uniform, and then filtered through a filter having a hole diameter of 10 μm to produce a resin composition for an antireflection layer. The composition was applied with a spin coater to a thickness of 0.09 μm, and heated in a heating furnace at 200 ° C. for 60 minutes to produce a lens with an antireflection layer, which has a reflectance of 550 nm on the surface of the lens with the antireflection layer. Was 0.6%, but it took time to harden, so it was not applicable to mass production.

DESCRIPTION OF SYMBOLS 1 Film with antireflection layer 2 Transparent adhesive 3 Liquid crystal panel 4 Backlight system 5 Antireflection layer 6 Lens 7 Antireflection layer 8 Infrared cut filter 9 CCD element

Claims (18)

A resin composition for an antireflection layer comprising an alicyclic epoxy resin precursor represented by Chemical Formula 1 and / or Chemical Formula 2 and a polymerization initiator.

[In the above formula (1), -X- is _{-O -, - S -, -} SO -, - SO 2 -, - CH 2 -, - CH (CH 3) -, or -C _{(CH 3) 2} -Represents. ]
The resin composition for an antireflection layer according to claim 1, wherein the polymerization initiator is a photoacid generator. The resin composition for an antireflection layer according to claim 1 or 2, wherein a ratio of the alicyclic epoxy resin in the resin composition is 50% to 100%. The resin composition for an antireflection layer according to any one of claims 1 to 3, wherein the isomer content of the alicyclic epoxy resin precursor according to claim 1 is 40% or less. The resin composition for an antireflection layer according to any one of claims 1 to 4, further comprising an antioxidant. An antireflection layer using the resin composition for an antireflection layer according to any one of claims 1 to 5. The antireflection layer according to claim 6, wherein in the antireflection layer, the reflectance of incident light is 3% or less. The antireflection layer according to claim 6 or 7, wherein the antireflection layer has a refractive index of 1.4 to 1.6. The antireflection layer according to claim 8, wherein a product of the refractive index and the thickness is 50 nm or more and 200 nm or less. The antireflection layer according to claim 9, wherein the antireflection layer has a thickness of 150 nm or less. 11. The antireflection layer according to claim 6, wherein the antireflection layer has a concavo-convex structure on at least one surface thereof, and a height of the concavo-convex structure is 0.02 μm or more and 0.95 μm or less. The antireflection layer as described. The antireflection layer according to claim 11, wherein the uneven structure has a pitch of 300 nm or less. An optical device comprising the antireflection layer according to claim 6. A display device comprising the antireflection layer according to claim 6. A liquid crystal display device comprising the antireflection layer according to claim 6. The organic electroluminescent display apparatus which has an antireflection layer of any one of Claims 6 thru | or 12. A lens having the antireflection layer according to any one of claims 6 to 12. An imaging device comprising the antireflection layer according to claim 6.