CN109844571A - Antireflection material - Google Patents

Antireflection material Download PDF

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Publication number
CN109844571A
CN109844571A CN201780063063.3A CN201780063063A CN109844571A CN 109844571 A CN109844571 A CN 109844571A CN 201780063063 A CN201780063063 A CN 201780063063A CN 109844571 A CN109844571 A CN 109844571A
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mentioned
resin combination
rubber particles
weight
antireflection material
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高林尚史
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/54—Encapsulations having a particular shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Led Device Packages (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The purpose of the present invention is to provide with sufficient anti-reflection function and can prevent the total light flux of light source from reducing and antireflection material and the optical semiconductor device that is sealed to form by the antireflection material of photosemiconductor with high heat resistance impact.The purpose of the present invention is to provide anti-: a kind of antireflection material, it includes the solidfied materials for the resin combination for being dispersed with porous aggregate (A), it includes the solidfied materials for the resin combination for being dispersed with porous aggregate (A), wherein, the porous aggregate (A) forms the bumps for inhibiting reflection on the surface of the solidfied material, the resin combination contains: rubber particles are dispersed with the epoxide (B) of rubber particles obtained from being dispersed in alicyclic epoxy resin, acid anhydride type curing agent (C) and curing accelerator (D), the rubber particles have core-shell structure, it is made of the polymer with (methyl) acrylate as necessary monomer component, and have hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin on surface, the average grain diameter of the rubber particles is 10nm~50 0nm, maximum particle diameter is 50nm~1000nm, for the specific refractivity of the solidfied material of the refractive index of the rubber particles and the resin combination within ± 0.02, porous aggregate (A) is 4~40 weight % relative to the content of antireflection material total amount (100 weight %).And optical semiconductor sealed by above-mentioned antireflection material obtained by optical semiconductor device.

Description

Antireflection material
Technical field
The present invention relates to antireflection materials.In addition, the present invention relates to optical semiconductors sealed by the antireflection material and The optical semiconductor device obtained.In addition, the present invention relates to the resin combination for being suitable for manufacturing the antireflection material and using The manufacturing method of the antireflection material of the resin combination.This application claims the Japan that on October 11st, 2016 proposes in Japan is special It is willing to the priority of 2016-200398, and its contents are hereby incorporated herein by reference.
Background technique
In recent years, various within doors or in room outer display board, traffic signals, giant display unit etc., gradually adopt by Light emitting device (optical semiconductor device) of the optical semiconductor (LED element) as light source.As such optical semiconductor device, It has popularized usually on substrate (optical semiconductor board for mounting electronic) equipped with optical semiconductor, and photosemiconductor member The optical semiconductor device that part is sealed to form by transparent sealing material.On the sealing material in such optical semiconductor device, Reduction visual due to caused by the total reflection of the incident light from external illumination light, sunlight etc. in order to prevent, Anti-reflex treated is implemented on surface.
In the past, the method for assigning anti-reflection function as the surface to resin layer, there is known: by bead, silica Deng inorganic filler be dispersed in resin, to make the method for scatter incident light (for example, see patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-234767
Summary of the invention
Technical problem solved by the invention
However, in the resin of optical semiconductor sealing using patent document 1 method in the case where, it is found that be difficult to give Sufficient anti-reflection function, and ensure the total light flux of light source.I.e., it was found that following equilibrium relations: when an adequate amount of nothing of addition When machine filler is to obtain sufficient anti-reflection function, the significant reduction of the total light flux of light source, and when the cooperation for reducing inorganic filler When amount is to prevent the total light flux of light source from reducing, sufficient antireflection ability cannot be obtained.
In addition, in recent years, the high-output power of optical semiconductor device continues to develop, in this optical semiconductor device In sealing material, when being applied thermal shock as cold cycling (being repeated periodically heating and cooling), crack can be generated (rupture) causes non-luminous problem.Therefore, even if the sealing material in optical semiconductor device, which needs to have, is applied thermal shock It is not easy to produce the characteristic (sometimes referred to as " thermal shock resistance ") in crack.
Therefore, it is an object of the present invention to provide a kind of antireflection material, which can have sufficiently Anti-reflection function while prevent light source total light flux reduction, and have high heat resistance impact.
Further, it is another object of the present invention to provide the above-mentioned antireflection material for sealing photosemiconductor.
Further, it is another object of the present invention to provide a kind of optical semiconductor device, wherein optical semiconductor is above-mentioned Antireflection material is sealed.
Further, it is another object of the present invention to provide be suitable for manufacture above-mentioned antireflection material resin combination and The manufacturing method of the above-mentioned antireflection material of the resin combination is used.
Technical means to solve problem
The inventors of the present invention's discovery: when the combined amount of inorganic filler is reduced, the original of sufficient antireflection ability cannot be obtained Therefore first is that, inorganic filler is due to settling without being diffused on entire resin layer, as a result, will not be formed on the whole surface Uniform concave-convex, therefore, incident light cannot be scattered effectively, on the other hand, when increase combined amount is so that even if inorganic fill out Material can also be when obtaining antireflection ability even if generation sedimentation on the surface of entire resin layer, inorganic filler itself absorbs light, The significant reduction of total light flux.
To solve the above-mentioned problems, the inventors of the present invention have made intensive studies, as a result, it has been found that, when being mixed into porous aggregate conduct When constituting the filler in the resin layer of antireflection material, sufficient anti-reflection function can be assigned a small amount of addition.In addition, When using wherein the alicyclic epoxy resin of the rubber particles with specific structure is dispersed with as resin layer, thermal shock resistance Also excellent.It provides as a result, with sufficient anti-reflection function and excellent thermal shock resistance and the not significant light source that reduces The antireflection material of total light flux, and it was found that above-mentioned material is highly suitable as to the photosemiconductor member in optical semiconductor device The material that part is sealed, so as to complete the present invention.
That is, the present invention provides a kind of antireflection material, it includes the solidifications for the resin combination for being dispersed with porous aggregate (A) Object, wherein above-mentioned porous aggregate (A) forms the bumps for inhibiting reflection, above-mentioned resin combination on the surface of above-mentioned solidfied material Contain: rubber particles are dispersed with epoxide (B), the acid anhydrides of rubber particles obtained from being dispersed in alicyclic epoxy resin Class curing agent (C) and curing accelerator (D), above-mentioned rubber particles have core-shell structure, by having (methyl) acrylate to make It is constituted for the polymer of necessary monomer component, and there is hydroxyl and/or carboxyl to be used as on surface can be with ester ring type asphalt mixtures modified by epoxy resin The functional group of rouge reaction, the average grain diameter of above-mentioned rubber particles are 10nm~500nm, and maximum particle diameter is 50nm~1000nm, on The specific refractivity of the refractive index of rubber particles and the solidfied material of above-mentioned resin combination is stated within ± 0.02, porous aggregate It (A) is 4~40 weight % relative to the content of antireflection material total amount (100 weight %).
In above-mentioned antireflection material, above-mentioned porous aggregate (A) is evenly dispersed and spreads in entire above-mentioned solidfied material, and The bumps for inhibiting reflection are formed on the surface of the solidfied material.
In above-mentioned antireflection material, above-mentioned resin combination can be also 10m comprising specific surface area2/ g is below non-porous to be filled out Expect (F), relative to antireflection material total amount (100 weight %), above-mentioned porous aggregate (A) and above-mentioned nonporous packing (F's) always contains Amount is preferably 20~60 weight %
In above-mentioned antireflection material, above-mentioned porous aggregate (A) can be inorganic porous filler.
In above-mentioned antireflection material, above-mentioned resin combination may include transparent hardening resin composition.
In above-mentioned antireflection material, above-mentioned resin combination may include transparent hardening resin composition.
Above-mentioned antireflection material can be used for sealing photosemiconductor.
In addition, the present invention provides a kind of optical semiconductor device, wherein optical semiconductor is close by above-mentioned antireflection material institute Envelope.
In addition, the present invention provides a kind of resin combination, it is used to manufacture above-mentioned antireflection material and is dispersed with porous Filler (A), above-mentioned resin combination contain: rubber particles are dispersed with rubber granule obtained from being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and the curing accelerator (D) of son, above-mentioned rubber particles have core-shell structure, It is made of the polymer with (methyl) acrylate as necessary monomer component, and there is hydroxyl and/or carboxyl on surface As the functional group that can be reacted with alicyclic epoxy resin, the average grain diameter of above-mentioned rubber particles is 10nm~500nm, maximum Partial size is 50nm~1000nm, and the refractive index of above-mentioned rubber particles and the specific refractivity of the solidfied material of above-mentioned resin combination exist Within ± 0.02, porous aggregate (A) is 4~40 weight % relative to the content of resin combination total amount (100 weight %).
Above-mentioned resin combination can be liquid.
In above-mentioned resin combination, total amount (100 weights of the component volatilized in solidification relative to above-mentioned resin combination Measure %) amount can be 10 weight % or less.
In addition, the present invention provides a kind of manufacturing method of antireflection material, it is formed on the surface of above-mentioned antireflection material Inhibit the bumps of reflection, the above method includes: to solidify above-mentioned resin combination.
Invention effect
Antireflection material of the invention is due to above structure, even if in the feelings for the combined amount for reducing porous aggregate (A) Under condition, it is also possible to obtain sufficient anti-reflection function, and the significant reduction of the total light flux of light source can be prevented, and also have There is excellent thermal shock resistance.Therefore, light in optical semiconductor device is partly led by being used as antireflection material of the invention The material that volume elements part is sealed, available high quality (such as while inhibiting gloss, have sufficient brightness and height Durability) optical semiconductor device.
In addition, resin combination of the invention is above-mentioned anti-due to above-mentioned technical characteristic, being highly suitable for manufacturing Reflecting material.
Detailed description of the invention
Fig. 1 is an embodiment schematic diagram for indicating the optical semiconductor device comprising antireflection material of the invention.It is left Scheming (a) is perspective view, and right figure (b) is sectional view.
Specific embodiment
<antireflection material and resin combination>
Antireflection material of the invention includes the solidfied material for being dispersed with the resin combination of porous aggregate (A), wherein above-mentioned Porous aggregate (A) forms the bumps for inhibiting reflection on the surface of above-mentioned solidfied material, and above-mentioned resin combination contains: rubber particles Be dispersed with obtained from being dispersed in alicyclic epoxy resin the epoxides (B) of rubber particles, acid anhydride type curing agent (C), And curing accelerator (D), above-mentioned rubber particles have core-shell structure, by having (methyl) acrylate as necessary monomer group The polymer divided is constituted, and has hydroxyl and/or carboxyl as the function that can be reacted with alicyclic epoxy resin on surface Group, the average grain diameter of above-mentioned rubber particles are 10nm~500nm, and maximum particle diameter is 50nm~1000nm, above-mentioned rubber particles The specific refractivity of the solidfied material of refractive index and above-mentioned resin combination is within ± 0.02, and porous aggregate (A) is relative to anti-reflective The content for penetrating total amount of material (100 weight %) is 4~40 weight %.
In addition, being dispersed with porous inorganic filling materials in resin combination of the invention, above-mentioned resin combination contains: rubber Particle is dispersed with epoxide (B), the acid anhydride type curing agent of rubber particles obtained from being dispersed in alicyclic epoxy resin (C) and curing accelerator (D), above-mentioned rubber particles have core-shell structure, by having (methyl) acrylate as necessary monomer The polymer of component is constituted, and has hydroxyl and/or carboxyl as the official that can be reacted with alicyclic epoxy resin on surface It can roll into a ball, the average grain diameter of above-mentioned rubber particles is 10nm~500nm, and maximum particle diameter is 50nm~1000nm, above-mentioned rubber particles Refractive index and above-mentioned resin combination solidfied material specific refractivity within ± 0.02, porous aggregate (A) is relative to tree The content of oil/fat composition total amount (100 weight %) is 4~40 weight %, and above-mentioned resin combination is for manufacturing above-mentioned antireflection material Material.
Due to the porous structure of porous aggregate (A), compared with non-porous filler, relative to the apparent of resin combination Volume increases, and therefore, can spread a small amount of addition and evenly dispersed and spread over resin combination or its entire solidification In object, and uniform and subtle bumps can be formed on the surface of solidfied material.In addition, resin combination penetrates into porous knot In structure, the difference of the apparent specific gravity of porous aggregate (A) and resin combination is reduced, therefore dispersity becomes stable, and porous Interaction between the surface filler (A) is inhibited and is not easy to agglomerate, and porous aggregate (A), which can be present uniformly throughout, is dispersed in tree In oil/fat composition or its entire solidfied material, to form uniform and subtle bumps on solidfied material surface, can effectively it scatter Incident light.
It should be noted that in the present specification, the additive amount (usage amount) of porous aggregate (A) is to refer on a small quantity with weight Haggle over less, rather than is haggled over capacity (volume) few.
When using porous aggregate (A), compared with non-porous filler, even if usage amount is reduced, it can also effectively inhibit anti- It penetrates, therefore the significant reduction of the total light flux as caused by the light absorption of porous aggregate (A) itself can be inhibited, and can be true Protect sufficient anti-reflection function.
In addition, above-mentioned resin combination contains: rubber particles are dispersed with obtained from being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and the curing accelerator (D) of rubber particles, particle has as above-mentioned rubber There is core-shell structure, is made of the polymer with (methyl) acrylate as necessary monomer component, and there is hydroxyl on surface As the functional group that can be reacted with alicyclic epoxy resin, the average grain diameter of above-mentioned rubber particles is 10nm for base and/or carboxyl ~500nm, maximum particle diameter are 50nm~1000nm, the refractive index of above-mentioned rubber particles and the solidfied material of above-mentioned resin combination Specific refractivity is within ± 0.02.Due to using above-mentioned rubber particles, rubber components will not be dissolved out from rubber particles, be made solid The glass transition temperature for changing solidfied material obtained from resin combination solidifies will not be greatly reduced, and will not damage transparent Property.Also, solidfied material obtained from solidifying the resin combination containing the above-mentioned epoxide (B) for being dispersed with rubber particles With excellent heat resistance and the transparency, and show the excellent fracture-resistant (thermal shock resistance) for thermal impact.
Each constituent element is described in more detail below.
[porous aggregate (A)]
Porous aggregate (A) in antireflection material or resin combination of the invention is evenly dispersed and spreads over resin combination In object or its entire solidfied material, since dispersity is stablized, the porous aggregate (A) for being present in solidfied material surface, which has to be formed, to be used for Scatter the concave-convex effect of incident light.
The porous aggregate (A) of antireflection material for use in the present invention or resin combination is that the apparent specific gravity of filler is small In the true specific gravity of filler, and inside it with the inorganic or organic filler of porous structure.Hereinafter, they are distinguished sometimes Referred to as " inorganic porous filler (A1) ", " Porous-Organic filler (A2) ".
As inorganic porous filler (A1), well-known or conventional filler can be used, be not particularly limited, such as can lift Out: unorganic glass [such as pyrex, sodium borosilicate glass, water soda glass, aluminum silicate glass, quartz etc.], titanium dioxide Silicon, aluminium oxide, zircon, calcium silicates, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminium hydroxide, oxidation Iron, zirconium oxide, magnesia, titanium oxide, aluminium oxide, calcium sulfate, barium sulfate, forsterite, talcum, spinelle, glues zinc oxide It is to have that soil, kaolin, dolomite, hydroxyapatite, nepheline, which dodge the powder such as feldspar, christobalite, wollastonite, diatomite, talcum, The substance of porous structure or their formed body (such as spherical bead etc.) etc..In addition, can be lifted as inorganic porous filler (A1) Out: the known or conventional surface treatment in above-mentioned inorganic porous filler is [for example, even based on metal oxide, silane coupling agent, titanium Join agent, the surface treatment that organic acid, polyalcohol, the surface treating agents such as siloxanes carry out] used in substance etc..Pass through progress Compatibility and dispersibility between the component of resin combination can be improved in such surface treatment.Wherein, as inorganic more Hole filler (A1) from can be evenly dispersed and spread in resin combination or its entire solidfied material, and can effectively exist It is formed from the perspective of bumps on solidfied material surface, preferably porous, inorganic glass or porous silica (porous silica Filler).
Porous silica is not particularly limited, and fused silica, crystalline silica, high-purity can be used for example Known to synthetic silica, colloidal silicon dioxide etc. or conventional porous silica.It should be noted that as porous two Silica can be used through known or conventional surface treatment [for example, based on metal oxide, silane coupling agent, titanium coupling The hydrophobic surface treatments agent such as agent, organic acid, polyalcohol, organo-silicon compound carry out surface treatment] used in substance. In the present specification, " hydrophobicity is sometimes referred to as by the porous silica that hydrophobic surface treatments agent is surface-treated Porous silica ".
From improving and the compatibility of resin combination component and dispersed and improve the heat resistance of solidfied material (for example, resistance to It is heated aqueous) from the viewpoint of, preferably hydrophobic porous silica, as hydrophobic surface treatments agent, preferably organosilicon compound Object is (for example, trim,ethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, prestox ring tetrasilane, poly dimethyl silicon Oxygen alkane, cetyl silane, methacryl silanes, silicone oil etc.), more preferable dimethyl silicone polymer etc..
As Porous-Organic filler (A2), known or conventional filler can be used, be not particularly limited, such as can be used By styrene resin, acrylic resin, organic silicon resin, acrylicstyrene resinoid, vinyl chloride resin, partially Vinylidene chloride resin, amide resinoid, polyurethane based resin, phenolic resinoid, styrene-conjugated diene resinoid, propylene Polymer such as acid-conjugated diene resinoid, olefine kind resin, cellulosic resin (crosslinked including these polymer) etc. have Porous-Organics fillers such as high-molecular porous sintered body, polymeric foam body, gel porous body that machine object is constituted etc..
It is filled out in addition it is possible to use the inorganic-organic being made of the mixing material that above-mentioned inorganic matter and organic matter are formed is porous Material.
Above-mentioned porous aggregate (A) can be made of homogenous material, can also be made of two or more materials.Wherein, make For porous aggregate (A), from can be evenly dispersed and spread in resin combination or its entire solidfied material, and can solidify Object is effectively formed from the perspective of bumps on surface, preferably inorganic porous filler (A1), from availability and ease of manufacturing From the perspective of, more preferable porous silica (porous silica filler), and from the heat resistance of solidfied material (for example, resistance to It is heated aqueous) from the perspective of, further preferred hydrophobic porous silica (hydrophobic porous silica filler).
The shape of porous aggregate (A) is not particularly limited, and can enumerate, such as: powder, spherical, broken shape, threadiness, needle Shape, flakey.Wherein, it can be evenly dispersed from porous aggregate (A) and spreads in resin combination or its entire solidfied material, and And can be from the perspective of being effectively formed bumps on solidfied material surface, the porous aggregate (A) of preferably spherical or broken shape.
The medium particle diameter of porous aggregate (A) is not particularly limited, and can be evenly dispersed from porous aggregate (A) and spreads over tree In oil/fat composition or its entire solidfied material, and it is easy to be effectively formed uniform and subtle concaveconvex shape on solidfied material surface From the perspective of, medium particle diameter is preferably 0.1~100 μm, and more preferably 1~50 μm.It should be noted that above-mentioned medium particle diameter Referring to particle volume diameter that accumulated value in the size distribution measured by laser diffraction/scattering method is 50%, (mean volume is straight Diameter).
The porous structure of porous aggregate (A) can be carried out by various parameters such as specific surface area, pore volume, oil absorptions Limitation can select the porous aggregate of the type with the parameter suitable for antireflection material of the invention with being not particularly limited (A)。
The specific surface area of porous aggregate (A) is not particularly limited, evenly dispersed from porous aggregate (A) and spread over resin group It closes in object or its entire solidfied material, be easy to be formed uniform and subtle concaveconvex shape on the surface of solidfied material and effectively prevent From the perspective of only reflecting, specific surface area is preferably 10~2000m2/ g or more, more preferably 100~1000m2/g.If comparing table Area is 10m2/ g or more, then have following tendencies: porous aggregate (A) is evenly dispersed and spreads over resin combination or it is entire In solidfied material, and the anti-reflection function on solidfied material surface is improved.It on the other hand, is 2000m by specific surface area2/ g with Under, there are following tendencies: the viscosity of the resin combination containing porous aggregate (A) rises and thixotropy is inhibited, and really Mobility when preparation antireflection material is protected.It should be noted that above-mentioned specific surface area refers to, according to JIS K6430 annex E, the N2 adsorption specific surface area acquired based on the BET formula obtained according to Nitrogen adsorption isotherm at -196 DEG C.In addition, for by dredging In the case where the porous aggregate (A) that aqueous surface-treating agent is surface-treated, above-mentioned " specific surface area " refers in carry out table The specific surface area of porous aggregate (A) before surface treatment.
The pore volume of porous aggregate (A) is not particularly limited, evenly dispersed from porous aggregate (A) and spread over resin group It closes in object or its entire solidfied material, be easy to be formed uniform and subtle concaveconvex shape on the surface of solidfied material and effectively prevent From the perspective of only reflecting, pore volume is preferably 0.1~10mL/g, more preferably 0.2~5mL/g.If pore volume is 0.1mL/g or more, then there are following tendencies for porous aggregate (A): evenly dispersed and spread over resin combination or it entire solidifies In object, and it is easy to form concaveconvex shape on the surface of solidfied material.It on the other hand, is 5mL/g hereinafter, more by pore volume The tendency that the mechanical strength of hole filler (A) is improved.It should be noted that the pore volume of porous aggregate (A) can pass through mercury Plunging (porosimetry) measures broad pore distribution and acquires.
The oil absorption of porous aggregate (A) is not particularly limited, evenly dispersed from porous aggregate (A) and spread over resin combination In object or its entire solidfied material, it is easy to be formed uniform and subtle concaveconvex shape on the surface of solidfied material and effectively prevent From the perspective of reflection, oil absorption is preferably 10~2000mL/100g, more preferably 100~1000mL/100g.If oil suction Amount is 10mL/100g or more, then there is following tendency: porous aggregate (A) is dispersed in resin combination or its entire solidification In object, and it is easy to form concaveconvex shape on solidfied material surface.On the other hand, by oil absorption be 2000mL/100g hereinafter, The tendency that the mechanical strength of porous aggregate (A) is improved.It should be noted that porous aggregate (A) is 100g filler to oil mass The oil mass of absorption can be measured according to JIS K5101.
In antireflection material of the invention, porous aggregate (A) may be used alone, can also be used in combination two kinds with On.In addition, can be manufactured by well-known or conventional manufacturing method, such as can make for porous aggregate (A) With: trade name " SYLYSIA250N ", " SYLYSIA256 ", " SYLYSIA256N ", " SYLYSIA310 ", " SYLYSIA320 ", " SYLYSIA350 ", " SYLYSIA358 ", " SYLYSIA430 ", " SYLYSIA431 ", " SYLYSIA440 ", “SYLYSIA450”、“SYLYSIA470”、“SYLYSIA435”、“SYLYSIA445”、“SYLYSIA436”、 “SYLYSIA446”、“SYLYSIA456”、“SYLYSIA530”、“SYLYSIA540”、“SYLYSIA550”、 The SYLYSIA series such as " SYLYSIA730 ", " SYLYSIA740 ", " SYLYSIA770 "；Trade name " SYLOSPHERE C- 1504 ", the SYLOSPHERE such as " SYLOSPHERE C-1510 " series (more than, by Chemical plants of formula meetings of Fuji Silysia Society's manufacture)；Trade name " SUNSPHERE H-31 ", " SUNSPHERE H-32 ", " SUNSPHERE H-33 ", " SUNSPHERE H-51”、“SUNSPHERE H-52”、“SUNSPHERE H-53”、“SUNSPHERE H-121”、“SUNSPHERE H-122”、 The SUNSPHERE such as " SUNSPHERE H-201 " H series (being manufactured above by AGC SITEC Co., Ltd.) etc. is without hydrophobicity table The porous inorganic filling materials of surface treatment；Trade name " SYLOPHOBIC 702 ", " SYLOPHOBIC 4004 ", " SYLOPHOBIC 505”、“SYLOPHOBIC 100”、“SYLOPHOBIC 200”、“SYLOPHOBIC 704”、“SYLOPHOBIC 507”、 " SYLOPHOBIC 603 ", etc. SYLOPHOBIC serial (the above are the manufactures of Fuji's Silysia Chemical Co., Ltd.), trade name The Aerosil such as " Aerosil RX200 ", " Aerosil RX300 " series (the above are the manufactures of Evonik Degussa company)；Quotient (the above are AGC for the SUNSPHERE such as the name of an article " SUNSPHERE H-121-ET ", " SUNSPHERE H-51-ET " ET series The manufacture of Sitech Co., Ltd.) etc. the commercially available products such as hydrophobic porous silica.
Porous aggregate (A) in antireflection material or resin combination of the invention is relative to antireflection material or resin group The content (combined amount) for closing the total amount (100 weight %) of object is 4~40 weight %, preferably 4~35 weight %, more preferably 4 ~30 weight %.It is 4 weight % or more by the content of porous aggregate (A), porous aggregate (A) is evenly dispersed and spreads over resin In composition or the entire solidfied material of composition antireflection material, it is easy to form uniform concave-convex on entire solidfied material surface Shape.It on the other hand, is 40 weight % by the content of porous aggregate (A) hereinafter, using antireflection material of the invention or tree Oil/fat composition for example as the sealing material of optical semiconductor device in the case where, having can substantially ensure and prevent total light flux The tendency being substantially reduced.
Relative to the resin combination (100 parts by weight) for constituting antireflection material, antireflection material of the invention or resin The content (combined amount) of porous aggregate (A) in composition is usually 5~80 parts by weight, preferably 5~70 parts by weight, more preferably For 5~60 parts by weight.When the content of porous aggregate (A) is 5 parts by weight or more, porous aggregate (A) is evenly dispersed and spreads over Resin combination is constituted in the entire solidfied material of its antireflection material, is easy to be formed on entire solidfied material surface uniform recessed Convex form.On the other hand, when the content of porous aggregate (A) is 80 parts by weight or less, antireflection material of the invention is being used Or resin combination for example as the sealing material of optical semiconductor device in the case where, having can substantially ensure and prevent total light logical The tendency of amount being substantially reduced.
[resin combination]
The resin combination of composition solidfied material in antireflection material of the invention contains: rubber particles are dispersed in ester ring type The epoxide (B) that rubber particles are dispersed with obtained from epoxy resin (hereinafter, is sometimes referred to as in the present specification " epoxide (B) for being dispersed with rubber particles "), acid anhydride type curing agent (C) and curing accelerator (D), the rubber particles It with core-shell structure, is made of the polymer with (methyl) acrylate as necessary monomer component, and has on surface As the functional group that can be reacted with alicyclic epoxy resin, the average grain diameter of above-mentioned rubber particles is for hydroxyl and/or carboxyl 10nm~500nm, maximum particle diameter are 50nm~1000nm, the solidification of the refractive index of above-mentioned rubber particles and above-mentioned resin combination The specific refractivity of object is within ± 0.02.Above-mentioned resin combination is suitable as the optical semiconductor in optical semiconductor device Sealing material, that is, be suitable for optical semiconductor sealing resin combination, such as provide following solidfied materials: is solid by heating Change, have high transparency, durability (even if for example, being not easy to reduce the characteristic of the transparency because of heating or light, applying high temperature Also rupture or the characteristic removed from adherend etc. are not susceptible to when heat or thermal shock) it is excellent, especially thermal shock resistance is excellent Solidfied material.
[epoxide (B) for being dispersed with rubber particles]
The epoxide (B) for being dispersed with rubber particles in the present invention is that following rubber particles is made to be dispersed in ester ring Compound obtained by oxygen resin: above-mentioned rubber particles have core-shell structure, by having (methyl) acrylate as necessary single The polymer of body component is constituted, and on surface with hydroxyl and/or carboxyl as can be reacted with alicyclic epoxy resin Functional group, the average grain diameter of above-mentioned particle are 10nm~500nm, and maximum particle diameter is 50nm~1000nm, the folding of the rubber particles The specific refractivity of the solidfied material of rate and above-mentioned resin combination is penetrated within ± 0.02.
(rubber particles)
Rubber particles in the present invention have multilayered structure (core-shell structure), which includes having caoutchouc elasticity Core part and at least one layer of shell for covering above-mentioned core part.In addition, above-mentioned rubber particles are by having (methyl) acrylate Polymer as necessary monomer component is constituted, and there is hydroxyl and/or carboxyl to be used as on surface can be with ester ring type epoxy The functional group of resin reaction.When hydroxyl and/or carboxyl are not present on the surface of rubber particles, solidfied material is because of warm such as cold cyclings It impacts and gonorrhoea occurs, so that the transparency reduces, it is not preferable.
As the monomer component for the polymer for constituting the core part with caoutchouc elasticity, necessary component are as follows: (methyl) propylene (methyl) acrylate such as sour methyl esters, (methyl) ethyl acrylate, (methyl) butyl acrylate.As except (methyl) acrylate The monomer component that can contain in addition, such as can enumerate: the siloxanes such as dimethyl siloxane, phenyl methyl siloxane；Styrene, The aromatic vinyls ester such as α-methylstyrene；The nitriles such as acrylonitrile, methacrylonitrile；Butadiene, isoprene equiconjugate diene；It is poly- Urethane, ethylene, propylene, isobutene etc..
In the present invention, as the monomer component with the core part of caoutchouc elasticity is constituted, preferably combination includes (methyl) Acrylate and the combination for being selected from one or more of siloxanes, aromatic vinyl ester, nitrile, conjugated diene, such as can It enumerates: the bipolymers such as (methyl) acrylate/aromatic vinyl ester, (methyl) acrylate/conjugated diene；(methyl) third Terpolymers such as olefin(e) acid ester/aromatic vinyl ester/conjugated diene etc..
In core part with caoutchouc elasticity, other than above-mentioned monomer component, following reactivity crosslinkings can also be contained Monomer: corresponding to divinylbenzene, (methyl) allyl acrylate, ethylene glycol two (methyl) acrylate, Malaysia diene acid Have two in 1 mole of monomer of propyl ester, triallyl cyanurate, diallyl phthalate, butanediol diacrylate etc. The reactive cross-linking monomer of a above reactive functional groups.
As the monomer component for constituting the core part with caoutchouc elasticity of the invention, wherein from can be easily adjusted From the perspective of the refractive index of rubber particles, preferably (methyl) acrylate/aromatic vinyl ester bipolymer is (special It is butyl acrylate/styrene).
Core part with caoutchouc elasticity can be prepared by conventional method, can be enumerated, such as: it is poly- by emulsifying The legal method that above-mentioned monomer is polymerize.As emulsion polymerization method, it can be added at one time the above-mentioned monomer of whole amount, After a part of above-mentioned monomer can be made to be polymerize, remaining monomer is continuously or discontinuously added and is polymerize, can also make With the polymerization for having used seed particles.
Shell is preferably formed by the polymer different from the polymer for constituting above-mentioned core part.In addition, shell has hydroxyl And/or carboxyl is as the functional group that can be reacted with alicyclic epoxy resin.Thus, it is possible to improve and alicyclic epoxy resin The cementability of interface, it is available with excellent by solidifying the resin combination comprising the rubber particles with the shell Different fracture-resistant and not gonorrhoea, transparent solidfied material.Furthermore, it is possible to prevent the glass transition temperature of solidfied material from dropping It is low.
As the monomer component for constituting shell, necessary component has: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate etc. (methyl) acrylate, for example, (methyl) acrylate when structure nucleation portion is acrylic acid fourth When ester, it is preferable to use (methyl) acrylate in addition to butyl acrylate (for example, (methyl) methyl acrylate, (first for shell Base) ethyl acrylate, butyl methacrylate etc.).As the monomer component in addition to (methyl) acrylate contained, example It can such as enumerate: styrene, α-methylstyrene aromatic vinyl ester；Acrylonitrile, methacrylonitrile etc..In the present invention, make For the monomer component for constituting shell, (methyl) acrylate is preferably comprised, and containing a kind of or combination containing two or more upper Monomer is stated, in particular, preferably at least containing aromatic series second from the viewpoint of it can easily adjust the refractive index of rubber particles Enester.
In addition, as the monomer with hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin Component preferably comprises monomer corresponding with following compounds etc.: (methyl) acrylic acid hydroxyl alkane such as (methyl) acrylic acid 2- hydroxyl ethyl ester Base ester；The alpha, beta-unsaturated acids such as (methyl) acrylic acid；The alpha, beta-unsaturated acids acid anhydride such as maleic anhydride.
In the present invention, as the monomer component for constituting shell, (methyl) acrylate is preferably comprised, and containing selected from upper One of monomer or combination are stated containing two or more, such as can be enumerated: (methyl) acrylate/aromatic vinyl ester/(first Base) terpolymers such as acrylic acid hydroxy alkyl ester, (methyl) acrylate/aromatic ethenyl/alpha, beta-unsaturated acid；(methyl) Bipolymers (preferably (the first such as acrylate/(methyl) acrylic acid hydroxy alkyl ester, (methyl) acrylate/alpha, beta-unsaturated acid Base) bipolymers such as acrylate/(methyl) acrylic acid hydroxy alkyl ester, (methyl) acrylate/alpha, beta-unsaturated acid) etc..
In addition, shell can contain following reactive cross-linking monomers: correspond in addition to above-mentioned monomer as core part Divinylbenzene, (methyl) allyl acrylate, ethylene glycol two (methyl) acrylate, diallyl maleate, cyanurate There are more than two reactions in 1 mole of monomer of triallyl, diallyl phthalate, butanediol diacrylate etc. The reactive cross-linking monomer of property functional group.
It as the method with shell cladding core part, such as can enumerate: the copolymer for constituting shell is coated on by upper The method coated is stated in the core part of the surface with caoutchouc elasticity of method acquisition；The tool that will be obtained by the above method There is the core part of caoutchouc elasticity as trunk component, each component for constituting shell is graft-polymerized as branch component Method etc..
The average grain diameter of rubber particles is about 10~500nm or so in the present invention, preferably about 20~400nm or so.This Outside, the maximum particle diameter of rubber particles is about 50~1000nm or so, preferably about 100~800nm or so.If average grain diameter is super The maximum particle diameter for crossing 500nm or so or rubber particles is more than 1000nm, then with following tendencies: the transparency drop of solidfied material It is low, and the luminosity of photosemiconductor reduces.On the other hand, when average grain diameter is less than 10nm, or when the maximum grain of rubber particles When diameter is less than 50nm, resistance to rupture has the tendency that reduction.
Refractive index as rubber particles in the present invention is, for example, 1.40~1.60, and preferably 1.42~1.58 or so.This Outside, the refractive index of rubber particles with solidify the resin combination containing the rubber particles obtained by solidfied material specific refractivity It is preferred that in ± 0.02, more preferably within ± 0.018.When specific refractivity is more than ± 0.02, there is following tendency: solidfied material The transparency reduce, occur gonorrhoea sometimes, the luminosity of photosemiconductor reduces, and the function of photosemiconductor may be lost sometimes.
The refractive index of rubber particles can for example be acquired by following manner: in a mold by the injection molding of 1g rubber particles, and The compression molding at 210 DEG C, 4MPa obtains the plate with a thickness of 1mm, cuts out 20mm long × 6mm wide from obtained plate Test film, in the state of using single bromonaphthalene to make prism and above-mentioned test film closely sealed each other as intermediate fluid, using multi-wavelength Ah Shellfish refractometer (trade name " DR-M2 ", manufactured by Atago Co., Ltd.), 20 DEG C of measurement, the refractive index under sodium D-line.
The refractive index of the solidfied material of above-mentioned resin combination can for example be acquired by following manner: from passing through following light half That records in the item of conductor device is heating and curing in solidfied material obtained from method, cuts out the examination of 20mm long × 6mm wide × 1mm thickness Piece is tested, in the state of using single bromonaphthalene to make prism and above-mentioned test film closely sealed each other as intermediate fluid, uses multi-wavelength Abbe Refractometer (trade name " DR-M2 ", manufactured by Atago Co., Ltd.), 20 DEG C of measurement, the refractive index under sodium D-line.
(alicyclic epoxy resin)
Alicyclic epoxy resin in the present invention is that have more than one alicyclic ring (aliphatic hydrocarbon ring) and one in molecule The compound of above epoxy group.It as cycloaliphatic epoxy, such as can enumerate: have at least one (excellent in (i) molecule Choosing is more than two) chemical combination of ester ring oxygroup (epoxy group being made of two adjacent carbon atoms and oxygen atom for constituting alicyclic ring) Object；(ii) there is the compound for the epoxy group being bonded directly on alicyclic ring by singly-bound；(iii) there is alicyclic ring and glycidyl Compound etc..As the alicyclic epoxy resin in the present invention, machinability when preparation and when injection molding, It is preferred that the substance of liquid is presented under room temperature (25 DEG C).
As in above-mentioned (i) molecule at least one ester ring oxygroup compound contained by ester ring oxygroup, It is not particularly limited, wherein from the viewpoint of curability, preferably (two for constituting cyclohexane ring are adjacent for cyclohexene oxide base The epoxy group that carbon atom and oxygen atom are constituted).In particular, as the change in (i) molecule at least one ester ring oxygroup Object is closed, from the viewpoint of the transparency and heat resistance of solidfied material, there are more than two cyclohexene oxide bases preferably in molecule Compound, more preferably following formula (1) compound represented.
[chemical formula 1]
In formula (1), X indicates singly-bound or linking group (bivalent group with more than one atom).As above-mentioned company Connect group, can enumerate, such as: bivalent hydrocarbon radical, all or part of carbon-to-carbon double bond by alkenylene, carbonyl made of epoxidation, Ehter bond, ester bond, carbonate group, amide groups, they it is multiple be connected made of group etc..It should be noted that the substituent groups such as alkyl It can be bonded with more than one in the carbon atom of the alicyclic ring (ester ring oxygroup) in constitutional formula (1).
It is the compound of singly-bound as the X in formula (1), (3,4,3 ', 4 '-diepoxy) bicyclohexane can be enumerated.
As above-mentioned bivalent hydrocarbon radical, straight or branched alkylidene, the divalent ester ring type that carbon atom number is 1~18 can be enumerated Alkyl etc..The straight or branched alkylidene for being 1~18 as carbon atom number, such as can enumerate: methylene, methylmethylene, Dimethylmethylene, ethylidene, propylidene, trimethylene etc..It as above-mentioned divalent alicyclic type hydrocarbon, such as can enumerate: 1,2- Cyclopentylene, 1,3- cyclopentylene, cyclopentylidene base, 1,2- cyclohexylidene, 1,3- cyclohexylidene, 1,4- cyclohexylidene, cyclohexylidene The divalent such as base cycloalkylidene (including ring alkylidene radical) etc..
As above-mentioned all or part of carbon-to-carbon double bond, by alkenylene made of epoxidation, (sometimes referred to as " epoxidation is sub- Alkenyl ") in alkenylene can enumerate, such as: ethenylidene, allylidene, 1- butenylidene, 2- butenylidene, Aden's diene Straight or branched alkenylene (the packet that the carbon atom numbers such as base, inferior pentenyl, sub- hexenyl, heptene base, sub- octenyl are 2~8 Include sub- polyene-based) etc..In particular, preferably whole carbon-to-carbon double bonds are by Asia made of epoxidation as above-mentioned epoxidation alkenylene The alkenylene that alkenyl, more preferably whole carbon-to-carbon double bond are 2~4 by epoxidation and carbon atom number.
As above-mentioned linking group X, particularly preferably containing the linking group of oxygen atom, specifically, can enumerate :-CO- ,- O-CO-O- ,-COO- ,-O- ,-CONH-, epoxidation alkenylene；The group that these multiple groups are formed by connecting；One or two with On the group that is formed by connecting of these groups and one or more bivalent hydrocarbon radical.It can enumerate as bivalent hydrocarbon radical and show above Those of example.
By the representative example for the compound that above formula (1) indicates, can enumerate: 2,2- bis- (3,4- 7-oxa-bicyclo[4.1.0-1- bases) Bis- (3,4- 7-oxa-bicyclo[4.1.0-1- base) ethane of propane, bis- (3,4- epoxycyclohexyl-methyl) ethers, 1,2-, 1,2- epoxy-1,2- are double (3,4- 7-oxa-bicyclo[4.1.0-1- base) ethane, the compound etc. indicated by following formula (1-1)~(1-10).It should be noted that following formula L, m in (1-5), (1-7) respectively indicate 1~30 integer.R in following formula (1-5) is the alkylidene of carbon atom number 1~8, can It enumerates: methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub- sec-butyl, pentylidene, hexylidene, Asia The alkylidene of the straight or brancheds such as heptyl, octamethylene.Wherein, preferred carbon such as methylene, ethylidene, propylidene, isopropylidene The straight or branched alkylidene that atomicity is 1~3.N in following formula (1-9), (1-10)1~n6Respectively indicate 1~30 it is whole Number.
[chemical formula 2]
[chemical formula 3]
There is the compound for the epoxy group being bonded directly on alicyclic ring by singly-bound as above-mentioned (ii), such as can enumerate: The compound etc. indicated by following formula (2).
[chemical formula 4]
In formula (2), R ' be by structural formula from the alcohol of p valence remove p hydroxyl (- OH) obtained by group (p valence Organic group), p and q respectively indicate natural number.Alcohol [R ' (OH) as p valencep] can enumerate: including 2,2- bis- (methylols)- Polyalcohols such as n-butyl alcohol (alcohol etc. that carbon atom number is 1~15) etc..P is preferably that 1~6, q is preferably 1~30.When p is 2 or more When, the q in each () in the group of (in the bracket in outside) can be identical or different.As the chemical combination indicated by above formula (2) Object, it is specific enumerable: 1,2- epoxy -4- (2- Oxyranyle) hexamethylene adduct [example of 2,2- bis- (methylol)-n-butyl alcohols Such as, trade name " EHPE3150 " (manufacture of Daicel Co., Ltd.) etc.] etc..
There is the compound of alicyclic ring and glycidyl as above-mentioned (iii), such as can enumerate: 2,2- bis- [4- (2,3- rings Oxygen propoxyl group) cyclohexyl] propane, 2,2- bis- [3,5- dimethyl -4- (2,3- glycidoxy) cyclohexyl] propane, bisphenol A-type Epoxy resin hydrogenated products (bisphenol-A epoxy resin) etc.；Bis- [2- (2,3- glycidoxy) cyclohexyl] methane, [2- (2,3- glycidoxy)] cyclohexyl] [4- (2,3- glycidoxy) cyclohexyl] methane, bis- [4- (2,3- glycidoxy) Cyclohexyl] methane, bis- [3,5- dimethyl -4- (2,3- glycidoxy) cyclohexyl] methane, bisphenol f type epoxy resin hydrogenation production Object (A Hydrogenated Bisphenol A F type epoxy resin) etc.；A Hydrogenated Bisphenol A type epoxy resin；Hydrogenation phenolic resin varnish type epoxy resin (such as hydrogenate Phenol novolak type epoxy resin, the hydrogenation cresol novolak type ring for hydrogenating cresol novolak type epoxy resin, bisphenol-A Oxygen resin etc.)；Hydrogenate naphthalene type epoxy resin；By the hydrogenated epoxy resin etc. for the epoxy resin that triphenol methane obtains.
As above-mentioned cycloaliphatic epoxy, others can for example enumerate 1,2,8,9- bicyclic oxygen limonenes etc..
These alicyclic epoxy resins may be used alone, can also be used in combination it is two or more, under can be used for example State commercially available product: trade name " CELLOXIDE 2021P ", " CELLOXIDE 2081P " (being manufactured by Daicel Co., Ltd.).
The epoxide (B) for being dispersed with rubber particles in the present invention is obtained by following manner: by above-mentioned rubber granule Son is dispersed in above-mentioned alicyclic epoxy resin.The combined amount of rubber particles can according to need carry out appropriate adjustment, for example, phase The total amount of epoxide (B) for being dispersed with rubber particles is 0.5~30 weight % or so, preferably 1~20 weight % Left and right.When the dosage of rubber particles is less than 0.5 weight %, resistance to rupture has the tendency that reduction, on the other hand, works as rubber particles Dosage when being more than 30 weight %, heat resistance and the transparency have the tendency that reduction.
As the viscosity for the epoxide (B) for being dispersed with rubber particles, at 25 DEG C be preferably 400mPas~ 50000mPas, more preferably 500mPas~10000mPas.When the epoxide (B) for being dispersed with rubber particles (25 DEG C) of viscosity when being less than 400mPas, the transparency has the tendency that reduction, and when the epoxide that be dispersed with rubber particles (B) when (25 DEG C) of viscosity are higher than 50000mPas, the preparation and resin group of the epoxide (B) of rubber particles are dispersed with There is reduced tendency in the productivity for closing both preparations of object.
The viscosity for being dispersed with the epoxide (B) of rubber particles can be adjusted by using reactive diluent. As reactive diluent, can be properly used the viscosity under room temperature (25 DEG C) is that 200mPas aliphatic poly below shrinks Glycerin ether.It as above-mentioned aliphatic polyglycidyl ether, such as can enumerate: cyclohexanedimethanodiglycidyl diglycidyl ether, hexamethylene Hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, trimethylolpropane tris contracting Water glycerin ether, polypropylene glycol diglycidyl ether etc..
It as the dosage of reactive diluent, can suitably adjust, such as relative to the epoxidation for being dispersed with rubber particles Closing object (B) 100 parts by weight is 30 parts by weight hereinafter, it is preferred that (for example, 5-25 parts by weight) below 25 parts by weight left and right.Work as reactivity When the usage amount of diluent is more than 30 parts by weight, there is performance needed for being difficult to obtain crack resistance etc. sometimes.
The manufacturing method of the epoxide (B) for being dispersed with rubber particles in the present invention is not particularly limited, and can make With known conventional method, such as rubber particles are dehydrated after forming powder, is mixed and is dispersed in ester ring Method in oxygen resin；And the method etc. that rubber particles lotion and alicyclic epoxy resin are directly mixed and are dehydrated.
As the dosage for the epoxide (B) for being dispersed with rubber particles, the whole for preferably including in resin combination 20~100 weight % of resin containing epoxy group or so, particularly preferably 50~100 weight % or so.If being dispersed with rubber The dosage of the epoxide (B) of micelle is less than 20 weight % of all resins containing epoxy group, obtained solidfied material Resistance to rupture has the tendency that reduction.
Resin combination of the invention at least contains epoxide (B), the anhydride curing agent for being dispersed with rubber particles (C), curing accelerator (D) these three components are closed as necessary component but it is also possible to be by rubber particles dispersion epoxy resinification The embodiment of object (B) and curing catalysts (E) both components as necessary component.
[anhydride curing agent (C)]
Anhydride curing agent (C) has the function of the compound cures for making to have epoxy group.It is solid as the acid anhydrides in the present invention Agent (C), can be used as hardener for epoxy resin and known conventional curing agent.As the anhydride-cured in the present invention Agent (C) is the acid anhydrides of liquid preferably at 25 DEG C, such as can enumerate: methyl tetrahydrophthalic anhydride, methyl hexahydro neighbour's benzene Dicarboxylic acid anhydride, dodecenylsuccinic anhydride, methylendomethylene tetrabydrophthalic anhydride etc..Furthermore, it is possible to by by adjacent benzene Dicarboxylic acid anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride etc. are under room temperature (25 DEG C) For solid acid anhydrides is dissolved in the acid anhydrides for being liquid under room temperature (25 DEG C) and mixture is made, and it is used as in the present invention Anhydride curing agent (C).
In addition, in the present invention, as anhydride curing agent (C), can be used: trade name " RICASID MH-700 " (new day The manufacture of this physics and chemistry Co., Ltd.), the commercially available products such as trade name " HN-5500 " (Hitachi Chemical Co., Ltd.'s manufacture).
As the dosage of anhydride curing agent (C), relative to including all containing the chemical combination of epoxy group in resin combination 100 parts by weight of object, for example, 50~150 parts by weight, preferably 52~145 parts by weight, particularly preferably 55~140 parts by weight are left It is right.More specifically, in the whole compounds containing epoxy group contained in above-mentioned resin combination, preferably with respect to 1 The epoxy group of equivalent, anhydride curing agent (C) are used with the ratio of 0.5~1.5 equivalent.If the dosage of anhydride curing agent (C) is small In 50 parts by weight, then effect is insufficient, and the toughness of solidfied material has the tendency that reduction, on the other hand, when the use of anhydride curing agent (C) When amount is more than 150 parts by weight, then solidfied material colours sometimes and form and aspect are deteriorated.
[curing accelerator (D)]
Curing accelerator (D) is that have to promote when the compound with epoxy group is solidified by anhydride curing agent (C) Into the compound of the function of solidification rate.As curing accelerator (D) of the invention, known conventional epoxy resin can be used With curing accelerator, such as can enumerate: 1,8- diazabicyclo [5.4.0] endecatylene -7 (DBU) and its salt are (for example, phenol Salt, caprylate, tosilate, formates, tetraphenyl borate salts etc.)；1,5- diazabicyclo [4.3.0] nonene -5 (DBN) and its salt (Li such as , phosphonium salt, sulfonium salt, quaternary ammonium salt, salt compounded of iodine)；Benzyldimethylamine, 2,4, (the dimethylamino first of 2,4,6- tri- Base) phenol, N, the tertiary amines such as N- dimethyl cyclohexyl amine；2-ethyl-4-methylimidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole Equal imidazoles；The phosphines such as phosphate, triphenylphosphine；Tetraphenylphosphoniphenolate (p-methylphenyl) borate Deng phosphonium compounds；Tin octoate, zinc octoate Equal organic metal salts；Metallo-chelate etc..They may be used alone, can also be used in combination two or more.
In addition, in the present invention, as curing accelerator (D), following commercially available products: trade name " U-CAT SA can be used 506 ", " U-CAT SA 102 ", " U-CAT 5003 ", " U-CAT 18X ", " 12XD " (development) are (above by San Apro Co., Ltd. manufacture)；Trade name " TPP-K ", " TPP-MK " (being manufactured above by Hokko Chemical Industry Co., Ltd.)；Quotient Name of an article " PX-4ET " (being manufactured by Nippon Chemical Ind) etc..
Relative to all 100 parts by weight of compound containing epoxy group for including in resin combination, curing accelerator (D) Dosage be, for example, 0.05~5 parts by weight or so, preferably 0.1~3 parts by weight or so, particularly preferably 0.2~3 parts by weight are left The right side, most preferably 0.25~2.5 parts by weight or so.When the dosage of curing accelerator (D) is less than 0.05 parts by weight, solidify sometimes Facilitation effect is insufficient；On the other hand, when the dosage of curing accelerator (D) be more than 5 parts by weight when, sometimes solidfied material coloring and Form and aspect are deteriorated.
[curing catalysts (E)]
Curing catalysts (E) in the present invention, which have, to be caused in the above-mentioned epoxide (B) for being dispersed with rubber particles The effect of the polymerization of epoxide.Curing catalysts (E) in the present invention are preferably cationic polymerization initiators, pass through purple Outside line irradiation or heat treatment and generate cationic seed, and cause be dispersed with rubber particles epoxide (B) occur it is poly- It closes.
As the cationic polymerization initiators for generating cationic seed are irradiated by ultraviolet light, can enumerate, such as: hexafluoro Stibate, five fluorine hydroxyl stibates, hexafluorophosphate, hexafluoro arsenate etc..Following commercially available products: trade name can be suitably used " UVACURE1590 " (being manufactured by Daicel Cytech Co., Ltd.), trade name " CD-1010 ", " CD-1011 ", " CD- 1012 " (by US Sartomar company manufacture), trade name " IRGACURE264 " (by Chiba Japan Co., Ltd. manufacture), Trade name " CIT-1682 " (being manufactured by Tso Tat Co., Ltd., Japan) etc..
As the cationic polymerization initiators for generating cationic seed by heat treatment, can enumerate: aryl diazonium salts, Aryl salt, aryl sulfonium salt, allene-ionic complex etc., can be suitably used following commercially available products: trade name " PP-33 ", " CP-66 ", " CP-77 " (being manufactured above by ADEKA Corp.)；Trade name " FC-509 " (is manufactured) by 3M Co., Ltd.； Trade name " UVE 1014 " (being manufactured by G.E.)；Trade name " Sun Aid SI-60L ", " Sun Aid SI-80L ", " Sun Aid SI-100L ", " Sun Aid SI-110L ", " Sun Aid SI-150L " are (above by three new chemical industry Co. Ltd. systems It makes)；Trade name " CG-24-61 " (is manufactured) by BASF Co., Ltd..Furthermore, it is possible to be: the metals such as aluminium or titanium and acetoacetate or The compound or the metals such as aluminium or titanium of chelate compound and the formation such as tri-phenyl-silane alcohol that diones are formed and acetoacetate or The compound etc. that the phenols such as chelate compound and bisphenol S that diones are formed are formed.
In curing catalysts (E) of the invention, go out from the viewpoint of hypotoxicity, tractability and excellent versatility Hair, preferably hexafluorophosphate.
As the usage amount of curing catalysts (E), relative to including all containing the change of epoxy group in resin combination 100 parts by weight of object, for example, 0.01~15 parts by weight or so, preferably 0.01~12 parts by weight or so are closed, particularly preferably 0.05~10 parts by weight or so, most preferably 0.1~10 parts by weight or so.By being carried out in the range using available Heat resistance, the transparency, the solidfied material having excellent weather resistance.
[nonporous packing (F)]
The resin combination for constituting antireflection material of the invention can contain nonporous packing (F).When antireflection of the invention When resin combination in material contains nonporous packing (F), the thermal shock resistance of cured solidfied material is further increased.
The nonporous packing (F) of antireflection material for use in the present invention refers to do not have porous structure and specific surface area For 10m2/ g is below inorganic or organic filler.Hereinafter, being referred to as sometimes " inorganic nonporous packing (F1) " and " organic non-porous to fill out Expect (F2) ".
As the inorganic nonporous packing (F1) of antireflection material for use in the present invention, can be used well-known or conventional Filler is not particularly limited, such as can enumerate: unorganic glass [such as pyrex, sodium borosilicate glass, water soda glass, Aluminum silicate glass, quartz etc.], silica, aluminium oxide, zircon, calcium silicates, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, nitrogen SiClx, boron nitride, aluminium hydroxide, iron oxide, zinc oxide, zirconium oxide, magnesia, titanium oxide, aluminium oxide, calcium sulfate, barium sulfate, Forsterite, talcum, spinelle, clay, kaolin, dolomite, hydroxyapatite, nepheline dodge feldspar, christobalite, wollastonite, The powder such as diatomite, talcum or their formed body (such as spherical bead etc.) etc..In addition, as inorganic nonporous packing (F1), it can Enumerate: it is known or it is conventional in above-mentioned inorganic filler surface treatment [for example, metal oxide, silane coupling agent, titanium coupling agent, The surface treatment that the surface treating agents such as organic acid, polyalcohol, siloxanes carry out] used in substance etc..By carrying out in this way Surface treatment, the compatibility and dispersibility between the component of resin combination can be improved.Wherein, it non-porous is filled out as inorganic Expect (F1), from the viewpoint of it can assign the excellent thermal shock resistance of solidfied material, preferably inorganic nonporous glass or non-porous two Silica (non-porous silicas filler).
Non-porous silicas is not particularly limited, and fused silica, crystalline silica, high-purity can be used for example Known to synthetic silica etc. or conventional non-porous silicas.It should be noted that can be used as non-porous silicas By known or conventional surface treatment [for example, metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyalcohol, poly- The hydrophobic surface treatments agent such as siloxanes carry out surface treatment] used in substance.
In addition, the filler with hollow body structure can be used as inorganic nonporous packing (F1).Above-mentioned ducted body is inorganic Nonporous packing is not particularly limited, such as can enumerate: unorganic glass is [for example, borosilicate glass, sodium borosilicate glass, silicic acid Soda-lime glass, aluminosilicate glass, quartz etc.], silica, aluminium oxide, metal oxides, calcium carbonate, barium carbonate, the carbon such as zirconium oxide The inorganic hollow particle (including the natural products such as Shirasuballoon) that the inorganic matters such as the metal salts such as sour nickel, calcium silicates are constituted； The inorganic-organic hollow-particle etc. being made of the mixing material that inorganic matter and organic matter are formed.In addition, the above-mentioned inorganic nothing of ducted body The hollow portion (space inside hollow-particle) of hole filler may be at vacuum state, full medium can also be filled, in particular, being Raising light scattering efficiency, is preferably filled with the medium with low-refraction (for example, the non-active gas such as nitrogen, argon gas or sky Gas etc.) hollow-particle.
When nonporous packing inorganic using ducted body, hollow rate (ratio of voidage and inorganic filler total volume) does not have There are special limitation, preferably 10~90 volume %, more preferably 30~90 volume %.
As organic nonporous packing (F2), known or conventional filler can be used, be not particularly limited, such as can lift Out: styrene resin, acrylic resin, polysiloxanes resinoid, acrylicstyrene resinoid, vinyl chloride resin, Vinylidene chloride like resin, amide resinoid, polyurethane based resin, phenolic resin, styrene-conjugated diene resinoid, propylene Polymer such as acid-conjugated diene resinoid, olefine kind resin, cellulosic resin (crosslinked comprising these polymer) etc. have Organic nonporous packing etc. that machine object is constituted.
In addition it is also possible to non-porous using the inorganic-organic that the mixing material formed by above-mentioned inorganic matter and organic matter is constituted Filler etc..
Above-mentioned nonporous packing (F) can be made of homogenous material, can also be made of two or more materials.Wherein, make For nonporous packing (F), from the viewpoint of it can assign the excellent thermal shock resistance of solidfied material, preferably non-porous nonporous packing (F1), from the viewpoint of availability and ease of manufacturing, more preferable non-porous silicas (non-porous silicas filler).
The shape of nonporous packing (F) is not particularly limited, and the example includes: powder, spherical, broken shape, threadiness, needle Shape, flakey.Wherein, from the viewpoint of being improved the thermal shock resistance of the solidfied material of nonporous packing (F), it is preferably spherical or The nonporous packing (F) of broken shape.
The medium particle diameter of nonporous packing (F) is not particularly limited, and obtains from the thermal shock resistance of the solidfied material of nonporous packing (F) To from the perspective of raising, medium particle diameter is preferably 0.1~100 μm, and more preferably 1~50 μm.It should be noted that among the above Heart partial size refers to that the accumulated value in the size distribution measured by laser diffraction/scattering method is 50% particle volume diameter (intermediate value body Product diameter).
In antireflection material of the invention, nonporous packing (F) may be used alone, can also be used in combination two kinds with On.In addition, can be manufactured by known or conventional manufacturing method as inorganic filler, such as can be used following commercially available Product: the FB such as trade name " FB-910 ", " FB-940 ", " FB-950 " serial (being manufactured above by Deuki Kagaku Kogyo Co., Ltd), Trade name " MSR-2212 ", " MSR-25 " (being manufactured above by Long Sen Co., Ltd.), trade name " HS-105 ", " HS-106 ", " HS-107 " (is manufactured by Micron Co., Ltd.) above.
In addition, can be manufactured by known or conventional manufacturing method as the inorganic nonporous packing of ducted body, such as Can be used following commercially available products: trade name " Sphericel (trade mark) 110P8 ", " Sphericel (trade mark) 25P45 ", " Sphericel (trade mark) 34P30 ", " Sphericel (trade mark) 60P18 ", " Q-CEL (trade mark) 5020 ", " Q-CEL (trade mark) 7014 ", " Q-CEL (trade mark) 7040S " (being manufactured above by Potters-Ballotini Co., Ltd.), trade name " Glass Micro Balloon ", " Fuji Balloon H-40 ", " Fuji Balloon H-35 " are (above by Fuji Silysia Chemical Co., Ltd. manufacture), trade name " Cellstar Z-20 ", " Cellstar Z-27 ", " Cellstar CZ- 31T”、“Cellstar Z-36”、“Cellstar Z-39”、“Cellstar Z-39”、“Cellstar T-36”、 " Cellstar PZ-6000 " (being manufactured above by East Sea Industrial Co., Ltd), trade name " Sylux Fine Balloon " (by Fine Balloon company manufacture), trade name " Super Balloon BA-15 ", " Super Balloon 732C " (above by Showa chemical industry Co., Ltd. manufacture).
When the resin combination in antireflection material of the invention contains nonporous packing (F), content (combined amount) does not have There is special limitation, be preferably 10~200 parts by weight relative to the resin combination (100 parts by weight) for constituting antireflection material, More preferably 20~150 parts by weight.When the content of nonporous packing (F) is 10 parts by weight or more, the solidfied material of antireflection material The tendency that is improved of thermal shock resistance.On the other hand, it when the content of nonporous packing (F) is 200 parts by weight or less, is using Antireflection material of the invention for example as the sealing material of optical semiconductor device in the case where, have following tendency: can be to prevent The only significant reduction of total light flux, it is ensured that sufficient illumination.
When the resin combination in antireflection material of the invention contains nonporous packing (F), above-mentioned porous aggregate (A) and The total content (total combined amount) of nonporous packing (F) is not particularly limited, the total amount (100 weight %) relative to antireflection material Preferably 20~60 weight %.When the total content of porous aggregate (A) and nonporous packing (F) is 20 weight % or more, constitute anti- The thermal shock resistance of the solidfied material of reflecting material has the tendency that further increasing.On the other hand, it when porous aggregate (A) and non-porous fills out When the total content for expecting (F) is 60 parts by weight or less, antireflection material of the invention is being used for example to use as optical semiconductor device Sealing material use in the case where, have following tendency: the significant reduction of total light flux can be prevented, it is ensured that sufficient illumination.
[polyalcohol]
Resin combination of the invention can contain polyalcohol.In particular, consolidating when resin combination of the invention contains acid anhydrides Agent (C) and when curing accelerator (D), from the viewpoint of it can be more effectively carried out solidification, preferably also contains polyalcohol.Make For polyalcohol, known or conventional polyalcohol can be used, be not particularly limited, such as can enumerate: ethylene glycol, propylene glycol, fourth Glycol, 1,4- butanediol, 1,6-HD, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, gathers 1,3 butylene glycol Propylene glycol, polytetramethylene glycol, trimethylolpropane, glycerol, pentaerythrite, dipentaerythritol etc..
Wherein, the viewpoint of the solidfied material of rupture and removing is not likely to produce from can control to solidify and be easy to get well Set out, above-mentioned polyalcohol be preferably carbon atom number be 1~6 aklylene glycol, more preferably carbon atom number be 2~4 alkyl Glycol.
Polyalcohol in resin combination of the invention may be used alone, can also be used in combination two or more.
The content (combined amount) of polyalcohol in resin combination of the invention is not particularly limited, relative to resin group Close total amount (whole epoxides of the epoxide contained in object；For example, the total amount of alicyclic epoxy resin) 100 weight Part preferably 0.05~5 parts by weight, more preferably 0.1~3 parts by weight, further preferably 0.2~3 parts by weight, particularly preferably For 0.25~2.5 parts by weight.By the way that the content of polyalcohol is set as 0.05 parts by weight or more, having can be more effectively carried out admittedly The tendency of change.On the other hand, by the way that the content of polyalcohol is set as 5 parts by weight hereinafter, having easily controllable above-mentioned cured anti- Answer the tendency of rate.
1-6. fluorophor
Resin combination of the invention can contain fluorophor.When resin combination of the invention contains fluorophor, especially It is preferably used as the seal applications (sealant use) of optical semiconductor in optical semiconductor device, that is, close as photosemiconductor Envelope uses resin combination.As above-mentioned fluorophor, known or conventional fluorophor can be used (in particular, for photosemiconductor Fluorophor in the seal applications of element), it is not particularly limited, such as can enumerate: by general formula A3B5O12: [in formula, A indicates choosing to M From the element of one or more of Y, Gd, Tb, La, Lu, Se, Sm, B indicates the element selected from one or more of Al, Ga, In, M Indicate the element selected from one or more of Ce, Pr, Eu, Cr, Nd, Er] the YAG class phosphor particles that indicate (for example, Y3Al5O12: Ce phosphor particles, (Y, Gd, Tb)3(Al,Ga)5O12: Ce phosphor particles etc.), silicate-based phosphors particle (for example, (Sr, Ca, Ba)2SiO4: Eu etc.) etc..It should be noted that in order to improve dispersibility, fluorophor for example can be surface The fluorophor being modified by organic group (for example, chain alkyl, phosphate group etc.) etc..In resin combination of the invention In object, fluorophor can individually a kind of use, can also be applied in combination two or more.In addition, can be used commercially available product as fluorescence Body.
The content (combined amount) of fluorophor in resin combination of the invention is not particularly limited, relative to resin group The total amount (100 weight %) for closing object, can suitably be selected in the range of 0.5~20 weight %.
It, can be containing not other than the epoxide (B) for being dispersed with rubber particles in resin combination of the invention Alicyclic epoxy resin containing rubber particles.As alicyclic epoxy resin, ester ring type epoxy shown in above-mentioned formula (1) can be enumerated Resin.As the dosage of the alicyclic epoxy resin without rubber particles, the whole for preferably smaller than including in resin combination contains There are 70 weight % of the resin of epoxy group, more preferably less than 60 weight %.If being free of the alicyclic epoxy resin of rubber particles Usage amount be more than whole resins containing epoxy group 70 weight %, then the resistance to rupture of the solidfied material obtained has inclining for reduction To.
In addition, resin combination of the invention can contain following components: bisphenol A-type, bisphenol-f type etc. have aromatic rings Glycidyl ether type epoxy compound；Hydrogenated bisphenol A type, aliphatic glycidyl fundamental mode etc. do not have the glycidol of aromatic rings Ether type epoxy compound；Glycidol esters epoxide；Glycidol amine epoxide；Polyol compound, oxygen Epoxy resin other than the alicyclic epoxy resins such as oxetane compounds, vinyl ether compound.As except ester ring type epoxy The dosage of epoxy resin except resin, 70 weights of all resins containing epoxy group for preferably smaller than including in resin combination Measure %, more preferably less than 60 weight %.If the dosage of the epoxy resin except alicyclic epoxy resin is more than all to contain ring 70 weight % of the resin of oxygroup, the then resistance to rupture of the solidfied material obtained have the tendency that reduction.
In addition it is also possible to containing solid epoxide is rendered as under room temperature (25 DEG C), as long as it is in upon mixing It is now liquid.It is rendered as solid epoxide as under room temperature (25 DEG C), such as can be enumerated: solid bisphenol type Bis- (the hydroxyl first of epoxide, novolak type epoxy compounds, ethylene oxidic ester, triglycidyl isocyanurate, 2,2- Base)-n-butyl alcohol 1,2- epoxy -4- (2- Oxyranyle) hexamethylene adduct (trade name " EHPE3150 ", by Daicel Chemical Industries Co., Ltd. manufacture).These epoxides may be used alone, can also be used in combination two Kind or more.
In the present invention, other than above-mentioned anhydride curing agent (C), curing catalysts (E), curing catalysts (E), from can To preferably comprise the glycidol without aromatic rings from the perspective of improving resistance to rupture in the case where not damaging high-fire resistance Ether type epoxy compound and/or the polyol compound (wherein, not including polyether polyol) that liquid is rendered as at 25 DEG C, it is special It is not, from the viewpoint of can be improving crack resistance under not damaging high-fire resistance and sunproof situation, more preferably comprising not Glycidyl ether type epoxy compound with aromatic ring.
[the glycidyl ether type epoxy compound without aromatic ring]
The glycidyl ether type epoxy compound without aromatic ring in the present invention includes: by aliphatic glycidyl ether class Epoxide, aromatic glycidyl ether class epoxide carry out compound obtained by core hydrogenation.Such as it can be suitably used Following commercially available products: trade name " EPICLON703 ", " EPICLON707 ", " EPICLON720 ", " EPICLON725 " are (by DIC plants Formula commercial firm manufacture), trade name " YH-300 ", " YH-315 ", " YH-324 ", " PG-202 ", " PG-207 ", " Santoto ST- 3000 " (being manufactured by Toto Kasei KK), trade names " LICARESIN DME-100 ", " LICARESIN HBE-100 " (being manufactured by New Japan Chem Co., Ltd), trade name " DENACOL EX-212 ", " DENACOL EX-321 " are (by Nagase The manufacture of Chemtex Co., Ltd.), trade name " YX 8000 ", " YX8034 " (by Japan Epoxy Resins Co. Ltd. system It makes).
Relative to 100 parts by weight of alicyclic epoxy resin, as the glycidyl ether type epoxy compound for not having aromatic ring Amount, for example, 10~60 parts by weight or so, preferably 20~50 parts by weight or so.
[polyol compound of liquid is rendered as at 25 DEG C]
In the polyol compound for being rendered as liquid at 25 DEG C in the present invention, including in addition to polyether polyol Polyol compound, for example including the pure and mild polycarbonate polyol of polyester polyols.
As polyester polyol, such as following commercially available products: trade name " PLACCEL 205 ", " PLACCEL can be used 205H”、“PLACCEL 205U”、“PLACCEL 205BA”、“PLACCEL 208”、“PLACCEL 210”、“PLACCEL 210CP”、“PLACCEL 210BA”、“PLACCEL 212”、“PLACCEL 212CP”、“PLACCEL 220”、“PLACCEL 220CPB”、“PLACCEL 220NP1”、“PLACCEL 220BA”、“PLACCEL 220ED”、“PLACCEL 220EB”、 “PLACCEL 220EC”、“PLACCEL 230”、“PLACCEL 230CP”、“PLACCEL 240”、“PLACCEL 240CP”、 “PLACCEL 210N”、“PLACCEL 220N”、“PLACCEL L205AL”、“PLACCEL L208AL”、“PLACCEL L212AL”、“PLACCEL L220AL”、“PLACCEL L230AL”、“PLACCEL 305”、“PLACCEL 308”、 “PLACCEL 312”、“PLACCEL L312AL”、“PLACCEL 320”、“PLACCEL L320AL”、“PLACCEL L330AL”、“PLACCEL 410”、“PLACCEL 410D”、“PLACCEL 610”、“PLACCEL P3403”、“PLACCEL CDE9P " (is manufactured) by Daicel Chemical Industries Co., Ltd..
As polycarbonate polyol, it can be used for example following commercially available products: trade name " PLACCEL CD205PL ", “PLACCEL CD205HL”、“PLACCEL CD210PL”、“PLACCEL CD210HL”、“PLACCEL CD220PL”、 " PLACCEL CD220HL " (being manufactured by Daicel Chemical Industries Co., Ltd.), trade name " UH- CARB50”、“UH-CARB100”、“UH-CARB300”、“UH-CARB90(1/3)”、“UH-CARB90(1/1)”、“UC- CARB100 " (being manufactured by Ube Industries, Ltd), trade name " PCDL T4671 ", " PCDL T4672 ", " PCDL T5650J ", " PCDL T5651 ", " PCDL T5652 " (being manufactured by Asahi Kasei Chemicals Co., Ltd.) etc..
Relative to 100 parts by weight of epoxide (B) for being dispersed with rubber particles, liquid is rendered as at 25 DEG C The dosage of polyol compound, for example, 5~50 parts by weight or so, preferably 10~40 parts by weight or so.
[other components]
In resin combination of the invention, in the range that will not cause biggish adverse effect to curability or transparency etc. It is interior, other components apart from the above can be contained.As above-mentioned other components, such as can enumerate: with linear chain or branched chain Polysiloxanes resinoid, the polysiloxanes resinoid with alicyclic ring, the polysiloxanes resinoid with aromatic rings, cage modle/ladder type/ The silane coupling agents such as silsesquioxane, the γ-glycidoxypropyltrime,hoxysilane of random, polysiloxane-based or fluorine class Defoaming agent, levelling agent, surfactant, filler, fire retardant, colorant, antioxidant, ultraviolet absorbing agent, ion adsorbent, Pigment, release agent etc..The content (combined amount) of above-mentioned other components is not particularly limited, the total amount relative to resin combination (100 weight %), preferably 5 weight % or less (for example, 0~3 weight %).
Resin combination of the invention is not particularly limited, such as can according to need and stir and mix in a heated state It is prepared by above-mentioned each component.It should be noted that curable epoxy resin composition of the invention can be all components The single liquid system: compositions directly used by being pre-mixed are also possible to for example be divided into ingredient more than two and use It is preceding with predetermined ratio mixing come carry out using more liquid systems (for example, Double liquid state system) composition.Stirring and mixed method It is not particularly limited, it is public that it is, for example, possible to use the various mixers such as dissolvers, equal device, kneader, roller, ball mill and autobiographies Known in rotatable agitating device etc. and conventional stirring and mixing arrangement.In addition, after stirring and mixing, it can be in decompression or vacuum Lower degassing.
[solidfied material and concaveconvex shape]
In antireflection material of the invention, above-mentioned porous aggregate (A) is evenly dispersed and spreads over above-mentioned resin combination Or in its entire solidfied material, since dispersity is stablized, the porous aggregate (A) being present on solidfied material surface forms concave-convex Shape, and incident light is scattered to show anti-reflection function.In addition, the porous structure on the surface porous aggregate (A) can also scatter Incident light, and further increase anti-reflection function.
Further, since above-mentioned resin combination contains the epoxide (B) for being dispersed with rubber particles, therefore containing above-mentioned The solidfied material of resin combination has excellent thermal shock resistance.
Disperse by above-mentioned porous aggregate (A) and spread over the method in above-mentioned entire solidfied material to be not particularly limited, such as It can enumerate, it is porous aggregate (A) is evenly dispersed and spread in the resin combination for constituting solidfied material then cured method etc.. In order to be effectively prepared antireflection material of the invention, preferably by porous aggregate (A) it is evenly dispersed after make its cured method.
Hereinafter, being illustrated to an embodiment of the manufacturing method of antireflection material of the invention, but the present invention is not It is limited to this.
Porous aggregate (A) and nonporous packing (F) that is as needed and adding can be added in resin combination, be passed through Mixing and stirring keep its evenly dispersed.Stirring and mixed method are not particularly limited, and it is, for example, possible to use dissolvers, homogenizing Known in the various mixers such as device, kneader, roller, ball mill and autobiography revolution type agitating device etc. and conventional stirring and mixed It attaches together and sets.In addition, after stirring and mixing, it can be in decompression or deaerated under vacuum.
When nonporous packing (F) and porous aggregate (A) is dispersed in solidfied material together, solidfied material can be further improved Thermal shock resistance.
The character of resin combination before curing of the invention is not particularly limited, preferably liquid.By using porous Filler (A) forms the resin combination before curing of antireflection material of the invention, by adding porous aggregate (A) on a small quantity just Anti-reflection function can be shown, therefore is also easy to without using toluene equal solvent as liquid, therefore it is preferred that.
[curing process]
Antireflection material of the invention is obtained by following manner: making the evenly dispersed resin combination for having porous aggregate (A) Object solidification, obtains solidfied material (hereinafter sometimes called " solidfied material of the invention ").
Relative to the total amount (100 weight %) of resin combination before curing, the amount for the component volatilized in solidification does not have Especially limitation, preferably 10 weight % hereinafter, more preferably 8 weight % hereinafter, further preferably 5 weight % or less.When solid When the amount for the component volatilized in change is 10 weight % or less, the dimensional stability enhancing of solidfied material, therefore it is preferred that.Solidification of the invention Preceding resin combination, by being added on a small quantity using porous aggregate (A), so that it may show anti-reflection function, therefore not use The volatile component of solvent (toluene etc.) is also easy to become liquid, can reduce the amount for the component volatilized in solidifying.
As solidification means, known or conventional means, such as heat treatment or photo-irradiation treatment etc. can be used.Pass through Temperature (solidification temperature) when heating is solidified is not particularly limited, preferably 45~200 DEG C, more preferably 50~190 DEG C, Further preferably 55~180 DEG C.In addition, the heating time (curing time) when solidifying is not particularly limited, preferably 30~ 600 minutes, more preferably 45~540 minutes, further preferably 60~480 minutes.If solidification temperature and curing time are low In the lower limit of above range, then solidify it is insufficient, on the contrary, if be higher than above range the upper limit, resin Composition may occur Decomposition, therefore not preferably.Although condition of cure depends on various conditions, such as when solidification temperature increases, can pass through Shorten curing time suitably to be adjusted, when solidification temperature reduces, can suitably be adjusted by extending curing time Section etc..In addition, solidification can be carried out by a step, can also be carried out by multisteps more than two steps.
In addition, in the case where injecting the cured situation of row by illumination, for example, by that will include i- line (365nm), h- line The light (radioactive ray) of (405nm), g- line (436nm) etc. is with 10~1200mW/cm of illumination2, 20~2500mJ/cm of irradiate light quantity2Into Row irradiation is to obtain antireflection material of the invention.The viewpoint of deterioration and production because of caused by radioactive ray from inhibition solidfied material From the perspective of property, the irradiate light quantity of radioactive ray is preferably 20~600mJ/cm2, more preferably 20~300mJ/cm2.In irradiation, High-pressure sodium lamp, xenon lamp, carbon arc lamp, metal halide lamp, laser etc. can be used as irradiation source.
[antireflection material]
As described above, antireflection material of the invention other than with high transparency and excellent anti-reflection function, is gone back High heat resistance impact is had both, therefore (purposes for being used to form optical material) resin of optical material can be preferably used as.Light Learning material is the material for showing the various optical functions such as light diffusing, photopermeability, light reflective.By using of the invention Antireflection material can obtain the optical component including at least solidfied material (optical material) of the invention.It should be noted that should Optical component can be only made of antireflection material of the invention, and antireflection material of the invention can also have been used with only a part Material.As optical component, can enumerate: show the various optical functions such as light diffusing, photopermeability, light reflective component, Device or component of machine of above-mentioned optical function etc. is utilized in composition, is not particularly limited, such as can enumerate for following use The known or conventional optical component on way: optical semiconductor device, organic el device, bonding agent, electrically insulating material, laminated plate, painting Layer, ink, coating, sealant, resist, composite material, transparent substrate, slide, hyaline membrane, optical element, optical lens, Optical mode, Electronic Paper, touch tablet, solar cell substrate, optical waveguide, light guide plate, holographic memory, optical pick off sensor Deng.
Since porous aggregate (A) is evenly dispersed and spreads in entire solidfied material, the surface of antireflection material of the invention Upper to have the subtle and uniform concaveconvex shape formed by porous aggregate (A), incident light is scattered due to the concaveconvex shape But it is not totally reflected, therefore, gloss can be inhibited and improve visuality.What is formed in antireflection material of the invention is recessed The equal surface roughness Ra of the number of convex form is preferably in the range of 0.1~1.0 μm, more preferably in the range of 0.2~0.8 μm. If the equal surface roughness Ra of the number of concaveconvex shape is in the range, there are following tendencies: can be logical in the not significant total light of reduction In the case where amount, sufficient anti-reflection function is shown.
It should be noted that in the present invention, the equal surface roughness Ra of number is the number as defined in JIS B 0601-2001 Value, and refer to the numerical value for measuring and being calculated by the method recorded in aftermentioned embodiment.
The resin combination of antireflection material of the invention is constituted, for example, optical semiconductor sealing tree can be preferably used as Oil/fat composition.That is, resin combination of the invention can be preferably used as sealing the member of the photosemiconductor in optical semiconductor device The composition (sealing material of the optical semiconductor in optical semiconductor device) of part.By using resin combination of the invention The antireflection material that (optical semiconductor sealing resin combination) manufactures, obtains the light that optical semiconductor is sealed and partly leads Body device (for example, 104 in Fig. 1 be the optical semiconductor device being made of antireflection material of the invention).Such as it can will be equal In the specified shaping dies of the even resin combination injection for being dispersed with porous aggregate (A), it is heating and curing in predefined conditions Or photocuring carrys out encapsulating optical semiconductor element.Solidification temperature, curing time, condition of photocuring etc., can with above-mentioned anti-reflective Preparing for material is penetrated to be appropriately configured in identical range.For the optical semiconductor device of aforementioned present invention, especially may be used To show excellent anti-reflection function in the case where not reducing total light flux.Further, since resin combination of the invention Containing the epoxide (B) for being dispersed with rubber particles and as needed depending on nonporous packing (F), therefore contain above-mentioned resin The solidfied material of composition has excellent thermal shock resistance.It should be noted that in the present specification, " light of the invention is partly led Body device " refers to, antireflection material of the invention is used for the component parts of optical semiconductor device (for example, sealing material, chip Grafting material etc.) at least part made of optical semiconductor device.
Embodiment
Hereinafter, will be based on embodiment come the present invention will be described in more detail, but the present invention is not limited to these Examples.It needs Illustrate, the unit of the component of resin combination shown in composition table 1,2 is parts by weight.
It should be noted that use is to survey with dynamic light scattering method for the average grain diameter of rubber particles, maximum particle diameter Determine " the Nanotrack of principleTM" (trade name: " UPA-EX150 " fills strain by day machine to type Nanotrack particle size distribution device Formula commercial firm manufacture), following samples are measured, in resulting size distribution curve, by accumulation curve be 50% when grain The i.e. accumulative evaluation partial size of diameter is as average grain diameter, and when by the frequency of size distribution measurement result (%) more than 0.00% most Big partial size is as maximum particle diameter.
Sample:
The epoxide (B) for being dispersed with rubber particles of 1 parts by weight is dispersed in the tetrahydrofuran of 20 parts by weight and The substance obtained is as sample.
For the refractive index of rubber particles, in a mold by the injection molding of 1g rubber particles, and compressed at 210 DEG C, 4MPa Forming, obtains the plate with a thickness of 1mm, 20mm long × 6mm wide test film is cut out from obtained plate, is using single bromonaphthalene In the state of keeping prism and above-mentioned test film closely sealed each other as intermediate fluid, multi-wavelength Abbe refractometer (trade name " DR- is used M2 " is manufactured by Atago Co., Ltd.), 20 DEG C of measurement, the refractive index under sodium D-line.
Epoxide (B) with regard to being dispersed with rubber particles obtained in Production Example (disperses the rubber particles of 5 parts by weight It is obtained in the CELLOXIDE 2021P (being manufactured by Daicel Chemical Industries Co., Ltd.) of 100 parts by weight Substance) viscosity for, use Digital Viscometer (trade name " DVU-EII type ", manufactured by Tokimec Co., Ltd.), survey Viscosity at 25 DEG C fixed.
Production Example 1
In the 1L aggregation container equipped with reflux condenser, 500g ion exchange water, 0.68g dioctyl succinate acid is added Sodium is stirred under nitrogen flowing, and temperature is risen to 80 DEG C.Here, it will be equivalent to be used to form core part the desired amount of about 5 The monomer mixture that 9.5g butyl acrylate, 2.57g styrene and the 0.39g divinylbenzene of weight % are constituted is disposable Addition, is stirred 20 minutes and makes its emulsification, and 9.5mg potassium persulfate is then added, stirs 1 hour progress first time seed Then 180.5mg potassium persulfate is added in polymerization, stir 5 minutes.Here, it expends 2 hours and continuously adds the monomer obtained as follows Mixture: 0.95g sodium dioctylsuccinate is dissolved in and is equivalent to residue (about 95 weights for being used to form core part institute necessary amounts Measure %) 180.5g butyl acrylate, 48.89g styrene, 7.33g divinylbenzene, carry out second of seeding polymerization, then Curing 1 hour, obtains core part.
Then, 60mg potassium persulfate is added and stirs 5 minutes, expending 30 minutes, continuous addition thereto is pungent by 0.3g bis- Base sodium succinate is dissolved in 60g methyl methacrylate, 1.5g acrylic acid, in 0.3g allyl methacrylate obtained by monomer Mixture carries out seeding polymerization, the shell of core part is coated within 1 hour followed by aging to be formed.
Then, it is cooled to room temperature (25 DEG C) and is filtered by the plastics net that mesh is 120 μm, to be wrapped Latex containing the particle with core-shell structure.Obtained latex is freezed at -30 DEG C, and carries out dehydration with suction filter and washs, Then diel is dried up at 60 DEG C, obtains rubber particles (1).The average grain diameter of resulting rubber particles (1) is 254nm, most Big partial size is 486nm, refractive index 1.500.
Using dissolvers (1000rpm, 60 minutes), under nitrogen flowing and it is warming up in the state of 60 DEG C, by 5 parts by weight Resulting rubber particles (1) are dispersed in the CELLOXIDE 2021P of 100 parts by weight (by Daicel Chemical The manufacture of Industries Co., Ltd.) in, vacuum outgas is carried out, the epoxide (B-1) (25 for being dispersed with rubber particles is obtained Viscosity at DEG C: 559mPas).
Production Example 2
Other than using 2.7g 2-Hydroxyethyl methacrylate to replace 1.5g acrylic acid, with side identical with Production Example 1 Formula obtains rubber particles (2).The average grain diameter of resulting rubber particles (2) is 261nm, maximum particle diameter 578nm, and refractive index is 1.500。
In addition, obtaining (25 DEG C of epoxide (B-2) for being dispersed with rubber particles in a manner of identical with Production Example 1 Under viscosity: 512mPas).
Production Example 3
In the 1L aggregation container equipped with reflux condenser, 500g ion exchange water, 1.3g sodium dioctylsuccinate is added, It is stirred under nitrogen flowing, and temperature is risen to 80 DEG C.Here, it will be equivalent to be used to form the desired amount of about 5 weight in core part The monomer mixture for measuring 9.5g butyl acrylate, 2.57g styrene and 0.39g the divinylbenzene composition of % disposably adds Add, be stirred 20 minutes and make its emulsification, 12mg potassium persulfate is then added, it is poly- to stir 1 hour progress first time seed It closes, 228mg potassium persulfate is then added, stir 5 minutes.Here, the monomer mixing for continuously adding to obtain as follows for 2 hours is expended Object: 1.2g sodium dioctylsuccinate is dissolved in and is equivalent to the residue for being used to form core part institute necessary amounts (about 95 weight %) 180.5g butyl acrylate, 48.89g styrene, 7.33g divinylbenzene carry out second of seeding polymerization, and followed by aging 1 is small When, obtain core part.
Then, other than the dosage of acrylic acid is become 2.0g from 1.5g, rubber is obtained in a manner of identical with Production Example 1 Micelle (3).The average grain diameter of resulting rubber particles (3) is 108nm, maximum particle diameter 289nm, refractive index 1.500.
In addition, obtaining (25 DEG C of epoxide (B-3) for being dispersed with rubber particles in a manner of identical with Production Example 1 Under viscosity: 1036mPas).
Production Example 4
Using rotation type agitating device (trade name " Awatori practice Taro AR-250 ", is manufactured by Shinky Co., Ltd., It is equally applicable below), by the curing agent (trade name " Rikacid MH-700 ", by New Japan Chem Co., Ltd of 100 parts by weight Manufacture), the curing accelerator of 0.5 parts by weight (trade name " U-CAT 18X " is manufactured by San Apro Co., Ltd.), 1 parts by weight Ethylene glycol (being manufactured by Wako Pure Chemicals Co., Ltd.) mixed, prepare epoxy hardener (K agent).
Embodiment 1
Using rotation type agitating device, the epoxy compound for being dispersed with rubber particles that the Production Example 1 of 100 parts by weight is obtained Object (B-1), 101.5 parts by weight Production Example 4 obtained in epoxy hardener mixed, defoamed, prepare curability asphalt mixtures modified by epoxy resin Oil/fat composition.
Using rotation type agitating device, by the curable epoxy resin composition obtained above of 100 parts by weight, 20 weight Porous aggregate (trade name " SYLYSIA 430 " is manufactured by Fuji Silysia Chemical Co., Ltd.) mixing of part takes off Gas, by obtained curable epoxy resin composition be moulded in photosemiconductor shown in Fig. 1 lead frame (InGaN element, 3.5mm × 2.8mm) in, then heated 5 hours in 150 DEG C of curing furnace, thus manufacture have optical semiconductor by The optical semiconductor device of antireflection material sealing of the invention.It should be noted that in Fig. 1,100 it is reflector, 101 is gold Belong to wiring, 102 be optical semiconductor, 103 be closing line, 104 be sealing material (antireflection material), porous aggregate uniformly divides It dissipates and spreads in entire 104, it is (recessed by forming uniform and subtle concaveconvex shape in the presence of the porous aggregate on surface to its upper Convex form is not shown).
Embodiment 2~15, comparative example 1~15
In addition to the composition of curable epoxy resin composition, porous aggregate, nonporous packing is carried out as shown in table 1,2 Except change, in the same manner as example 1, optical semiconductor device is manufactured.
[evaluation]
Following evaluations are carried out to the optical semiconductor device of above-mentioned manufacture.As a result it is shown in table 1,2.
(1) fluorescent lamp mirrors
The fluorescent lamp lighted is shone to the upper surface (sealing of Fig. 1 of embodiment, the optical semiconductor device obtained in comparative example The upper surface of material 104) and when observing reflection, it observes by the naked eye and three phases is carried out to the clarity for mirroring fluorescent lamp Evaluation.
The case where the case where cannot identifying the profile of fluorescent lamp is zero, and profile is not known but can be identified is △, and wheel is cleaned up Chu and the case where capable of identifying be ×.
(2) the equal surface roughness Ra of number
Use laser microscope (trade name " measuring shape laser microscope VK-8710 ", by Keyence Co. Ltd. system Make), measure the upper surface (upper surface of the sealing material 104 of Fig. 1) of optical semiconductor device obtained in embodiment, comparative example.
(3) total light flux
Use total light flux measuring machine (trade name " more light splitting radioassay system OL771 ", by Optotronic The manufacture of Laboratories company) measurement embodiment, each optical semiconductor device for obtaining in comparative example is under conditions of 5V, 20mA Total light flux when energization.
(4) thermal shock test
For the optical semiconductor device that obtains in embodiment and comparative example, (every kind of curable epoxy resin composition is used 2), the thermal shock of 200 circulations is carried out using heat impact tester, above-mentioned thermal shock is with the exposure 30 under -40 DEG C of atmosphere Minute, then recycled for 1 within exposure 30 minutes under 100 DEG C of atmosphere.Then, the electric current of 10mA is applied to photosemiconductor dress It sets, and measures the quantity of non-lit up optical semiconductor device (not bright optical semiconductor device).It should be noted that it has been confirmed that All optical semiconductor devices are all lighted before thermal shock test.As a result shown in table 1 and 2 in " thermal shock test is [non-lit up Number] " in a column.
(5) refringence is tested
In a mold by the curable epoxy resin composition obtained in embodiment 1~15, comparative example 3~5 injection molding, exist It is heated 5 hours at 150 DEG C.20mm long × 6mm wide × 1mm thickness test film is cut out from obtained solidfied material, is using single bromine In the state that naphthalene keeps prism and above-mentioned test film closely sealed each other as intermediate fluid, multi-wavelength Abbe refractometer (trade name is used " DR-M2 " is manufactured by Atago Co., Ltd.), 20 DEG C of measurement, the refractive index under sodium D-line.And refraction is calculated according to the following formula Rate is poor.As a result shown in table 1 and 2 in " refringence with rubber particles " column in.
Refringence=[refractive index of rubber particles]-[refractive index of solidfied material]
(6) comprehensive judgement
For each optical semiconductor device obtained in embodiment, comparative example, it will all meet the feelings of following (a)~(d) The case where condition is determined as zero (good), is unsatisfactory for any one of following (a)~(d) is determined as × (bad).
(a) reflection of the fluorescent lamp measured in above-mentioned (1) is zero or Δ.
(b) the equal surface roughness Ra of number measured in above-mentioned (2) is 0.10~1.0 μm.
(c) total light flux measured in above-mentioned (3) is 0.60lm or more.
(d) number of the non-lit up optical semiconductor device measured in above-mentioned (4) is 0.
The each component of antireflection material shown in composition table 1,2 is described below.
(epoxide (B) for being dispersed with rubber particles)
B-1: the epoxide (B-1) for being dispersed with rubber particles manufactured in Production Example 1
B-2: the epoxide (B-2) for being dispersed with rubber particles manufactured in Production Example 2
B-3: the epoxide (B-3) for being dispersed with rubber particles manufactured in Production Example 3
(epoxy resin)
CELLOXIDE 2021P: trade name " CELLOXIDE 2021P " [3,4- epoxycyclohexyl-methyl (3,4- epoxy Base) cyclohexane carboxylate], manufactured by Daicel Co., Ltd.
YD-128: trade name " YD-128 " [bisphenol A type epoxy resin] is manufactured by Nippon Steel & Sumitomo Metal Corporation
(epoxy hardener)
MH-700: trade name " RIKACID MH-700 " [4- methylhexahydrophthalic anhydride/hexahydrophthalic anhydride =70/30], manufactured by New Japan Chem Co., Ltd
U-CAT 18X: trade name " U-CAT 18X " (curing accelerator) is manufactured by San Apro Co., Ltd.
Ethylene glycol: it is manufactured by Wako Pure Chemicals Co., Ltd.
SI-100L: trade name " Sun Aid SI-100L " is manufactured by Sun Apro Co., Ltd.
(porous silica filler)
SYLYSIA430: trade name " SYLYSIA430 " is manufactured, body by Fuji Silysia Chemical Co., Ltd. Product average grain diameter: 4.1 μm；Specific surface area: 350m2/g；Average pore size: 17nm；Pore volume: 1.25mL/g；Oil absorption: 230mL/ 100g
SYLOSPHERE C-1504: trade name " SYLOSPHERE C-1504 ", by Chemical plants of Fuji Silysia The manufacture of formula commercial firm, volume average particle size: 4.5 μm；Specific surface area: 520m2/g；Average pore size: 12nm；Pore volume: 1.5mL/g； Oil absorption: 290mL/100g
SUNSPHER H-52: trade name " SUNSPHER H-52 " is manufactured by AGC SITEC Co., Ltd., and volume is average Partial size: 5 μm；Specific surface area: 700m2/g；Average pore size: 10nm；Pore volume: 2mL/g；Oil absorption: 300mL/100g
SYLOPHOBIC702: trade name " SYLOPHOBIC702 ", by Fuji Silysia Chemical Co. Ltd. system It makes, porous silica filler obtained by hydrophobic surface treatments is carried out by dimethyl silicone polymer, volume average particle size: 4.1μm；The specific surface area of porous silica filler before hydrophobic surface treatments: 350m2/g；Oil absorption: 170mL/100g
SYLOPHOBIC4004: trade name " SYLOPHOBIC4004 ", by Fuji Silysia Chemical Co., Ltd. Manufacture carries out porous silica filler obtained by hydrophobic surface treatments by dimethyl silicone polymer, volume average particle size: 8.0μm；The specific surface area of porous silica filler before hydrophobic surface treatments: 350m2/g；Oil absorption: 165mL/100g
SYLOPHOBIC505: trade name " SYLOPHOBIC505 ", by Fuji Silysia Chemical Co. Ltd. system It makes, porous silica filler obtained by hydrophobic surface treatments is carried out by dimethyl silicone polymer, volume average particle size: 3.9μm；The specific surface area of porous silica filler before hydrophobic surface treatments: 500m2/g；Oil absorption: 110mL/100g
(non-porous silicas filler)
Melt preparing spherical SiO 2: the manufacture of You Longsen Co., Ltd., volume average particle size: 5 μm
As shown in table 1, by being added with the porous silica filler of specified amount of the present invention and including to be dispersed with rubber granule The antireflection material of the resin combination manufacture embodiment of the epoxide (B) of son, just has the light of above-mentioned antireflection material For semiconductor device, mirroring for fluorescent lamp is zero or Δ, and the equal surface roughness Ra of number is in 0.10~1.0 μm of range Interior, total light flux is 0.60lm or more, and the quantity of non-lit up optical semiconductor device is also 0 in thermal shock test, really Them accept with excellent anti-reflection function, and shows excellent illumination, and also there is excellent thermal shock resistance.
On the other hand, as shown in table 2, just has the comparative example 1 that the epoxide (B) for being dispersed with rubber particles is not used For the optical semiconductor device of 2 antireflection material, they show excellent anti-reflection function and good illumination, but Thermal shock resistance test in, the quantity of non-lit up optical semiconductor device is 2, it is thus identified that their thermal shock resistance compared with Difference.In addition, the anti-reflective for the comparative example 3 for just having unmixed porous silica filler and being only mixed with non-porous silicas filler Penetrate material optical semiconductor device, with the combined amount for having porous silica filler be lower than present invention provide that range compared with For the optical semiconductor device of the antireflection material of example 4, their anti-reflection function is poor.In comparative example 3, nonporous silica Silicon filling settlement, in comparative example 4, the combined amount of porous silica filler is insufficient, as a result, it is believed that non-shape on the surface At uniform and fine concaveconvex shape.In addition, the combined amount for just having porous silica filler is higher than the specified model of the present invention For the optical semiconductor device of the antireflection material of the comparative example 5 enclosed, good anti-reflection function, but total light flux are shown For 0.48lm or more, the significant decline of illumination., it can be said that light is absorbed since the combined amount of porous silica filler is more.
Hereinafter, the variation of aforementioned present invention will be attached.
[1] a kind of antireflection material, it includes the solidfied materials for the resin combination for being dispersed with porous aggregate (A), wherein
Above-mentioned porous aggregate (A) forms the bumps for inhibiting reflection on the surface of above-mentioned solidfied material,
Above-mentioned resin combination contains: rubber particles are dispersed with rubber particles obtained by being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and curing accelerator (D),
The rubber particles have core-shell structure, by the polymer structure with (methyl) acrylate as necessary monomer component At, and have hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin, above-mentioned rubber granule on surface The average grain diameter of son is 10nm~500nm, and maximum particle diameter is 50nm~1000nm, the refractive index of the rubber particles and the resin group The specific refractivity of the solidfied material of object is closed within ± 0.02,
Porous aggregate (A) is 4~40 weight % relative to the content of antireflection material total amount (100 weight %).
[2] antireflection material recorded according to above-mentioned [1], wherein above-mentioned porous aggregate (A) is evenly dispersed and spreads over whole In a above-mentioned solidfied material, and the bumps for inhibiting reflection are formed on the surface of the solidfied material.
[3] antireflection material above-mentioned according to above-mentioned [1] or [2], wherein above-mentioned porous aggregate (A) is selected from inorganic more At least one of hole filler (A1) and Porous-Organic filler (A2).
[4] antireflection material according to above-mentioned [3], wherein above-mentioned porous aggregate (A) is inorganic porous filler (A1)。
[5] antireflection material according to above-mentioned [3] or [4], wherein inorganic porous filler (A1) is selected from inorganic glass Glass [such as pyrex, sodium borosilicate glass, water soda glass, aluminum silicate glass, quartz etc.], silica, aluminium oxide, Zircon, calcium silicates, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, aluminium hydroxide, iron oxide, zinc oxide, It is zirconium oxide, magnesia, titanium oxide, aluminium oxide, calcium sulfate, barium sulfate, forsterite, talcum, spinelle, clay, kaolin, white The powder that marble, hydroxyapatite, nepheline dodge at least one of feldspar, christobalite, wollastonite, diatomite, talcum etc. has There are the substance or their formed body (such as the spherical bead etc. for having carried out spheroidization) (preferably porous, inorganic glass of porous structure Or porous silica, more preferable porous silica).
[6] antireflection material according to any one of above-mentioned [3]~[5], wherein above-mentioned inorganic porous filler (A1) It is by selected from least one of metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyalcohol, polysiloxanes table The substance that surface treatment agent is surface-treated.
[7] antireflection material according to above-mentioned [5] or [6], wherein above-mentioned porous silica is selected from melting two At least one of silica, crystalline silica, high-purity synthetic silica, colloidal silicon dioxide porous silica.
[8] antireflection material according to any one of above-mentioned [5]~[7], wherein above-mentioned porous silica is logical It crosses and is dredged selected from least one of metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyalcohol, organo-silicon compound Substance obtained by aqueous surface-treating agent (preferably organo-silicon compound) is surface-treated (hydrophobic porous silica).
[9] antireflection material according to above-mentioned [8], wherein above-mentioned hydrophobic surface treatments agent is selected from trimethyl Chlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, prestox ring tetrasilane, dimethyl silicone polymer, cetyl silicon At least one of alkane, methacryl silanes, silicone oil organo-silicon compound (preferably dimethyl silicone polymer).
[10] antireflection material according to any one of above-mentioned [3]~[9], wherein above-mentioned Porous-Organic filler is By being selected from styrene resin, acrylic resin, organic silicon resin, acrylicstyrene resinoid, polyvinyl chloride-base tree Rouge, vinylidene chloride like resin, amide resinoid, polyurethane based resin, phenolic resinoid, styrene-conjugated diene resinoid, Acrylic acid-conjugated diene resinoid, olefine kind resin, in cellulosic resin (crosslinked including these polymer) at least A kind of high-molecular porous sintered body, polymeric foam body, gel porous body that organic matter is constituted.
[11] antireflection material according to any one of above-mentioned [1]~[10], wherein above-mentioned porous aggregate (A) Shape is selected from least one of powder, spherical, broken shape, threadiness, needle-shaped, flakey (preferably spherical or broken shape).
[12] antireflection material according to any one of above-mentioned [1]~[11], wherein above-mentioned porous aggregate (A) Median particle diameter is 0.1~100 μm (preferably 1~50 μm).
[13] antireflection material according to any one of above-mentioned [1]~[12], wherein above-mentioned porous aggregate (A) Specific surface area is 10~2000m2/ g (preferably 100~1000m2/g)。
[14] antireflection material according to any one of above-mentioned [1]~[13], wherein above-mentioned porous aggregate (A) Pore volume is 0.1~10mL/g (preferably 0.2~5mL/g).
[15] antireflection material according to any one of above-mentioned [1]~[14], wherein above-mentioned porous aggregate (A) Oil absorption is 10~2000mL/100g (preferably 100~1000mL/100g).
[16] antireflection material according to any one of above-mentioned [1]~[15], wherein above-mentioned porous aggregate (A) phase Content (combined amount) for the total amount (100 weight %) of antireflection material or resin combination is 4~35 weight % (preferably 4 ~30 weight %).
[17] antireflection material according to any one of above-mentioned [1]~[16], wherein above-mentioned porous aggregate (A) phase For constitute antireflection material resin combination (100 parts by weight) content (combined amount) be 5~80 parts by weight (preferably 5~ 70 parts by weight, more preferable 5~60 parts by weight).
[18] antireflection material according to any one of above-mentioned [1]~[17], wherein above-mentioned resin combination includes Transparent hardening resin composition.
[19] antireflection material according to any one of above-mentioned [1]~[18], wherein the core in above-mentioned core-shell structure Part is made of following components: selected from (methyl) acrylate/aromatic ethenyl, (methyl) acrylate/conjugated diene Bipolymer；Or, (methyl) acrylate/aromatic ethenyl/conjugated diene terpolymer.
[20] antireflection material according to above-mentioned [19], wherein the core part in above-mentioned core-shell structure is by (methyl) Acrylate/aromatic ethenyl bipolymer constitutes (preferably butyl acrylate/styrene).
[21] antireflection material according to above-mentioned [19] or [20], wherein the core part in above-mentioned core-shell structure is also Contain the reactive cross-linking monomer (preferably divinylbenzene) in a monomer with more than two reactive functional groups.
[22] antireflection material according to any one of above-mentioned [1]~[21], wherein the shell in above-mentioned core-shell structure Layer includes the polymer different from the polymer of core part constituted in above-mentioned core-shell structure.
[23] antireflection material according to any one of above-mentioned [1]~[22], wherein the shell in above-mentioned core-shell structure Layer is by being selected from (methyl) acrylate/aromatic vinyl ester/hydroxyalkyl (methyl) acrylate, (methyl) acrylate/fragrance Terpolymer in race's vinyl acetate/alpha, beta-unsaturated acid is selected from (methyl) acrylate/(methyl) acrylic acid hydroxy alkyl Bipolymer (preferably bipolymer) in ester, (methyl) acrylate/alpha, beta-unsaturated acid is constituted.
[24] antireflection material according to above-mentioned [23], wherein the shell in above-mentioned core-shell structure also contains one With the reactive cross-linking monomer (preferably allyl (methyl) acrylate) of more than two reactive functional groups in a monomer.
[25] antireflection material according to any one of above-mentioned [1]~[24], wherein above-mentioned rubber particles are averaged Partial size is 20~400nm.
[26] antireflection material according to any one of above-mentioned [1]~[25], wherein the maximum of above-mentioned rubber particles Partial size is 100~800nm.
[27] antireflection material according to any one of above-mentioned [1]~[26], wherein the refraction of above-mentioned rubber particles Rate is 1.40~1.60 (preferably 1.42~1.58).
[28] antireflection material according to any one of above-mentioned [1]~[27], wherein the refraction of above-mentioned rubber particles The specific refractivity of the solidfied material of rate and above-mentioned resin combination is within ± 0.018.
[29] antireflection material according to any one of above-mentioned [1]~[28], wherein above-mentioned alicyclic epoxy resin Comprising selected from least one of following components: (i) has at least one (preferably more than two) ester ring type epoxy in the molecule The compound of base；(ii) there is the compound of the epoxy group by singly-bound and alicyclic ring Direct Bonding；(iii) there is alicyclic ring and shrink Glyceryl compound.
[30] antireflection material according to above-mentioned [30], wherein above-mentioned (i) has at least one alicyclic ring in the molecule Ester ring oxygroup possessed by the compound of formula epoxy group is cyclohexene oxide base.
[31] antireflection material according to above-mentioned [30], wherein above-mentioned (i) has at least one alicyclic ring in the molecule The compound of formula epoxy group is the compound indicated by following formula (1).
[chemical formula 5]
[in formula (1), X indicates singly-bound or linking group (bivalent group with more than one atom).Substituent group is (excellent Select alkyl) can be with the more than one carbon atom bonding of the alicyclic ring in constitutional formula (1)].
[32] antireflection material according to above-mentioned [31], wherein the compound by above formula (1) expression includes to be selected from 2, Bis- (3,4- 7-oxa-bicyclo[4.1.0-1- base) propane of 2-, bis- (3,4- epoxycyclohexyl-methyl) ethers, bis- (the 3,4- 7-oxa-bicyclo[4.1.0s-of 1,2- 1- yl) ethane, bis- (3,4- 7-oxa-bicyclo[4.1.0-1- base) ethane of 1,2- epoxy-1,2-, by following formula (1-1)~(1-10) indicate At least one of compound.
[chemical formula 6]
[chemical formula 7]
[l, m in formula (1-5), (1-7) respectively indicate 1~30 integer.R in formula (1-5) is carbon atom number 1~8 Alkylidene.N1~n6 in following formula (1-9), (1-10) respectively indicates 1~30 integer.]
[33] antireflection material according to above-mentioned [32], wherein the compound by above-mentioned formula (1) expression is by above-mentioned The compound that formula (1-1) indicates.
[34] antireflection material according to any one of above-mentioned [29]~[33], wherein above-mentioned (ii), which has, to be passed through The compound of the epoxy group of singly-bound and alicyclic ring Direct Bonding is the compound indicated by following formula (2).
[chemical formula 8]
[in formula (2), R ' is the organic group of p valence, and p and q respectively indicate natural number].
[35] antireflection material according to any one of above-mentioned [1]~[34], wherein above-mentioned rubber particles relative to The combined amount for being dispersed with the total amount (100 weight %) of the epoxide (B) of rubber particles is 0.5~30 weight % (preferably from about 1 ~20 weight %).
[36] antireflection material according to any one of above-mentioned [1]~[35], wherein above-mentioned to be dispersed with rubber particles Viscosity of the epoxide (B) at 25 DEG C be 400mPas~50000mPas (preferably 500mPas~ 10000mPa·s)。
[37] antireflection material according to any one of above-mentioned [1]~[36], wherein above-mentioned to be dispersed with rubber particles The dosage of epoxide (B) be 20~100 weight % of all resins containing epoxy group contained in resin combination (preferably 50~100 weight %).
[38] antireflection material according to any one of above-mentioned [1]~[37], wherein above-mentioned anhydride curing agent (C) To be at 25 DEG C the be acid anhydrides of liquid or will be at 25 DEG C solid acid anhydrides be dissolved in the acid anhydrides for being liquid at 25 DEG C and The liquefied mixture obtained.
[39] antireflection material according to any one of above-mentioned [1]~[38], wherein above-mentioned anhydride curing agent (C) Dosage relative to all 100 parts by weight of compound containing epoxy group for including in resin combination is 50~150 parts by weight (preferably 52~145 parts by weight, more preferable 55~140 parts by weight).
[40] antireflection material according to any one of above-mentioned [1]~[39], wherein above-mentioned anhydride curing agent (C) Dosage relative to 1 equivalent epoxy group in all compounds containing epoxy group contained in resin combination be 0.5~1.5 Equivalent.
[41] antireflection material according to any one of above-mentioned [1]~[40], wherein above-mentioned curing accelerator (D) Dosage relative to all 100 parts by weight of compound containing epoxy group contained in resin combination is 0.05~5 parts by weight (preferably 0.1~3 parts by weight, particularly preferred 0.2~3 parts by weight, most preferably 0.25~2.5 parts by weight).
[42] antireflection material according to any one of above-mentioned [1]~[41], wherein above-mentioned resin combination also contains Having specific surface area is 10m2/ g nonporous packing below (F).
[43] antireflection material according to above-mentioned [42], wherein above-mentioned nonporous packing (F) is that non-porous silicas is filled out Material.
[44] antireflection material according to above-mentioned [42] or [43], wherein above-mentioned nonporous packing (F) is relative to composition The content (combined amount) of the resin combination (100 parts by weight) of antireflection material is 10~200 parts by weight (preferably 20~150 weights Measure part).
[45] antireflection material according to any one of above-mentioned [42]~[44], wherein above-mentioned porous aggregate (A) and Above-mentioned nonporous packing (F) is 20~60 weights relative to the total content (total combined amount) of the total amount (100 weight %) of antireflection material Measure %.
[46] antireflection material according to any one of above-mentioned [1]~[45], wherein above-mentioned resin combination contains Polyalcohol (preferably carbon atom number be 2~4 alkyl diol).
[47] antireflection material according to above-mentioned [46], wherein above-mentioned polyalcohol is relative to institute in resin combination The content (combined amount) of 100 parts by weight of total amount of the epoxide contained be 0.05~5 parts by weight (preferably 0.1~3 parts by weight, More preferable 0.2~3 parts by weight, particularly preferred 0.25~2.5 parts by weight).
[48] antireflection material according to any one of above-mentioned [1]~[47], wherein above-mentioned resin combination contains Fluorophor.
[49] antireflection material according to above-mentioned [48], wherein above-mentioned fluorophor is relative to the total of resin combination The content (combined amount) for measuring (100 weight %) is 0.5~20 weight %.
[50] antireflection material according to any one of above-mentioned [1]~[49], wherein in addition to being dispersed with rubber particles Epoxide (B) except, above-mentioned resin combination also includes the alicyclic epoxy resin without rubber particles (preferably by upper The alicyclic epoxy resin that formula (1) indicates).
[51] antireflection material according to above-mentioned [50], wherein the above-mentioned ester ring type asphalt mixtures modified by epoxy resin without rubber particles The dosage of rouge is less than 70 weight % (preferably smaller than 60 weights of whole resin containing epoxy group contained in resin combination Measure %).
[52] antireflection material according to any one of above-mentioned [1]~[51], wherein above-mentioned resin combination contains Epoxy resin (the preferably glycidol ethers ring with aromatic rings such as bisphenol A-type, bisphenol-f type other than alicyclic epoxy resin Oxygen compound).
[53] antireflection material according to above-mentioned [52], wherein the above-mentioned epoxy in addition to alicyclic epoxy resin The dosage of resin is less than 70 weight % (preferably smaller than 60 weights of all resins containing epoxy group in resin combination included Measure %).
[54] antireflection material according to any one of above-mentioned [1]~[53], wherein be formed in above-mentioned antireflection material The equal surface roughness Ra of the number of concaveconvex shape on material is in the range of 0.1~1.0 μm (preferably in 0.2~0.8 μm of range It is interior).
[55] antireflection material according to any one of above-mentioned [1]~[54], is used to seal photosemiconductor.
[56] a kind of optical semiconductor device, wherein optical semiconductor antireflection material described in above-mentioned [55] institute is close Envelope.
[57] a kind of resin combination is used to manufacture the above-mentioned antireflection material in any one of above-mentioned [1]~[55] simultaneously And it is dispersed with porous aggregate (A),
Above-mentioned resin combination contains: rubber particles are dispersed with rubber particles obtained by being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and curing accelerator (D),
The rubber particles have core-shell structure, by the polymer structure with (methyl) acrylate as necessary monomer component At, and have hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin, above-mentioned rubber granule on surface The average grain diameter of son is 10nm~500nm, and maximum particle diameter is 50nm~1000nm, the refractive index of above-mentioned rubber particles and above-mentioned tree The specific refractivity of the solidfied material of oil/fat composition within ± 0.02,
Porous aggregate (A) is 4~40 weight % relative to the content of resin combination total amount (100 weight %).
[58] resin combination according to above-mentioned [57], is liquid.
[59] resin combination according to above-mentioned [57] or [58], wherein the component volatilized in solidification relative to The amount of the total amount (100 weight %) of above-mentioned resin combination is 10 weight % or less.
[60] a kind of manufacturing method of antireflection material is formed on the surface of above-mentioned antireflection material and inhibits reflection Bumps, the above method include: to solidify resin combination described in any one of above-mentioned [57]~[59].
Industrial applicibility
Antireflection material of the invention in addition to high transparency and anti-reflection function it is excellent other than, also have both high heat resistance punching Hitting property, therefore (purposes for being used to form optical material) resin of optical material can be suitable for.As optical component, can arrange It lifts: showing the component of the various optical functions such as light diffusing, optical clarity, light reflective；Above-mentioned optics function is utilized in composition The device of energy or the component of machine；It is not particularly limited, such as can enumerate for known in following purposes or conventional optical section Part: optical semiconductor device, bonding agent, electrically insulating material, laminated plate, coating, ink, coating, sealant, resists organic el device Lose agent, composite material, transparent substrate, slide, hyaline membrane, optical element, optical lens, optical mode, Electronic Paper, touch tablet, Solar cell substrate, optical waveguide, light guide plate, holographic memory, optical pick off sensor etc..
Symbol description
100: reflector (light reflection resin combination)
101: metal line (electrode)
102: optical semiconductor
103: closing line
104: sealing material (antireflection material)

Claims (11)

1. a kind of antireflection material, it includes the solidfied materials for the resin combination for being dispersed with porous aggregate (A), wherein
The porous aggregate (A) forms the bumps for inhibiting reflection on the surface of the solidfied material,
The resin combination contains: rubber particles are dispersed with rubber particles obtained from being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and curing accelerator (D),
The rubber particles have core-shell structure, by the polymer structure with (methyl) acrylate as necessary monomer component At, and have hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin, the rubber granule on surface The average grain diameter of son is 10nm~500nm, and maximum particle diameter is 50nm~1000nm, the refractive index of the rubber particles and the tree The specific refractivity of the solidfied material of oil/fat composition within ± 0.02,
Porous aggregate (A) is 4~40 weight % relative to the content of antireflection material total amount (100 weight %).
2. antireflection material according to claim 1, wherein
The porous aggregate (A) is evenly dispersed and spreads in the entire solidfied material, and on the surface of the solidfied material It is formed with the bumps for inhibiting reflection.
3. antireflection material according to claim 1 or 2, wherein
The resin combination also includes that specific surface area is 10m2/ g nonporous packing below (F), relative to antireflection material total amount The total content of (100 weight %), the porous aggregate (A) and the nonporous packing (F) is 20~60 weight %
4. antireflection material described in any one of claim 1 to 3, wherein
The porous aggregate (A) is inorganic porous filler.
5. antireflection material according to any one of claims 1 to 4, wherein
The resin combination includes transparent hardening resin composition.
6. antireflection material according to any one of claims 1 to 5 is used to seal photosemiconductor.
7. a kind of optical semiconductor device, wherein
Optical semiconductor is sealed by antireflection material as claimed in claim 6.
8. a kind of resin combination is used for antireflection material described in any one of manufacturing claims 1~6 and is dispersed with Porous aggregate (A),
The resin combination contains: rubber particles are dispersed with rubber particles obtained from being dispersed in alicyclic epoxy resin Epoxide (B), acid anhydride type curing agent (C) and curing accelerator (D),
The rubber particles have core-shell structure, by the polymer structure with (methyl) acrylate as necessary monomer component At, and have hydroxyl and/or carboxyl as the functional group that can be reacted with alicyclic epoxy resin, the rubber granule on surface The average grain diameter of son is 10nm~500nm, and maximum particle diameter is 50nm~1000nm, the refractive index of the rubber particles and the tree The specific refractivity of the solidfied material of oil/fat composition within ± 0.02,
Porous aggregate (A) is 4~40 weight % relative to the content of resin combination total amount (100 weight %).
9. resin combination according to claim 8 is liquid.
10. resin combination according to claim 8 or claim 9, wherein
The component volatilized in solidification relative to the total amount (100 weight %) of the resin combination amount be 10 weight % with Under.
11. a kind of manufacturing method of antireflection material, the bumps for inhibiting reflection, institute are formed on the surface of the antireflection material The method of stating includes:
Solidify resin combination described in any one of claim 8~10.
CN201780063063.3A 2016-10-11 2017-10-03 Antireflection material Pending CN109844571A (en)

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CN115322641A (en) * 2022-08-25 2022-11-11 北京星驰恒动科技发展有限公司 High-absorptivity stray light inhibition coating and preparation method and application thereof

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
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EP2472578B1 (en) * 2010-12-28 2020-06-03 Nichia Corporation Light emitting device
US10147853B2 (en) * 2011-03-18 2018-12-04 Cree, Inc. Encapsulant with index matched thixotropic agent
JP6044096B2 (en) * 2012-03-29 2016-12-14 住友ベークライト株式会社 Epoxy resin composition for sealing and method for producing electronic device
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DE102019123890A1 (en) * 2019-09-05 2021-03-11 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung OPTICAL BODY, REFLECTIVE ELEMENT, COMPONENT, METHOD FOR MANUFACTURING AN OPTICAL BODY AND METHOD FOR MANUFACTURING A RERFLEXION ELEMENT

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CN115322641A (en) * 2022-08-25 2022-11-11 北京星驰恒动科技发展有限公司 High-absorptivity stray light inhibition coating and preparation method and application thereof

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Application publication date: 20190604