WO2018070300A1 - 反射防止材 - Google Patents
反射防止材 Download PDFInfo
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- WO2018070300A1 WO2018070300A1 PCT/JP2017/035957 JP2017035957W WO2018070300A1 WO 2018070300 A1 WO2018070300 A1 WO 2018070300A1 JP 2017035957 W JP2017035957 W JP 2017035957W WO 2018070300 A1 WO2018070300 A1 WO 2018070300A1
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- resin composition
- inorganic filler
- porous inorganic
- weight
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/852—Encapsulations
- H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
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- H10W74/10—
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- H10W74/40—
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- H10W74/00—
Definitions
- the present invention relates to an antireflection material.
- the present invention also relates to an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.
- the present invention also relates to a resin composition suitable for the production of the antireflection material, and a method for producing the antireflection material using the resin composition.
- a light emitting device using an optical semiconductor element (LED element) as a light source
- LED element optical semiconductor element
- an optical semiconductor device in general, an optical semiconductor device in which an optical semiconductor element is mounted on a substrate (substrate for mounting an optical semiconductor element) and the optical semiconductor element is sealed with a transparent sealing material is widespread. is doing.
- the sealing material in such an optical semiconductor device is subjected to antireflection treatment on its surface in order to prevent a decrease in visibility due to total reflection of incident light such as illumination light from outside and sunlight. Yes.
- Patent Document 1 when the method of Patent Document 1 is applied to a resin for sealing an optical semiconductor, it is difficult to ensure the total luminous flux of the light source while providing a sufficient antireflection function. That is, when a sufficient amount of inorganic filler is added to obtain a sufficient antireflection function, the total luminous flux of the light source is greatly reduced, while the inorganic filler is reduced in order to prevent a decrease in the total luminous flux of the light source. In this case, it was revealed that there was a trade-off relationship that sufficient antireflection performance could not be obtained.
- an object of the present invention is to provide an antireflection material that can prevent a decrease in the total luminous flux of a light source while having a sufficient antireflection function, and has high heat resistance, in particular, hot water resistance.
- the other object of this invention is to provide the said antireflection material for optical semiconductor sealing.
- another object of the present invention is to provide an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.
- Another object of the present invention is to provide a resin composition suitable for the production of the antireflection material, and a method for producing the antireflection material using the resin composition.
- the present invention is an antireflective material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein unevenness for suppressing reflection is formed on the surface of the cured product.
- An antireflection material is provided.
- the hydrophobic porous inorganic filler is preferably uniformly dispersed over the entire cured product, and has irregularities that suppress reflection on the surface.
- the hydrophobic porous inorganic filler is obtained by subjecting the surface of the porous inorganic filler to a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m 2 / g or more. There may be.
- the hydrophobic porous inorganic filler may have an average particle size of 1 ⁇ m to 20 ⁇ m.
- the content of the hydrophobic porous inorganic filler with respect to the total amount (100% by weight) of the antireflection material may be 4 to 40% by weight.
- the resin composition may be made of a transparent curable resin composition.
- the curable resin composition may be composed of a composition containing an epoxy resin.
- the antireflection material may be for optical semiconductor sealing.
- the present invention also provides an optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material.
- the present invention also provides a resin composition in which a hydrophobic porous inorganic filler is dispersed, which is used for producing the antireflection material.
- the resin composition may be liquid.
- the amount of components that volatilize during curing relative to the total amount (100% by weight) of the resin composition may be 10% by weight or less.
- the present invention also provides a method for producing an antireflective material in which irregularities for suppressing reflection are formed on the surface, wherein the resin composition is cured.
- the antireflection material of the present invention Since the antireflection material of the present invention has the above-described configuration, a sufficient antireflection function can be obtained even when the amount of the hydrophobic porous inorganic filler is reduced, and a significant decrease in the total luminous flux of the light source is prevented. And has excellent heat resistance, especially hot water resistance. Accordingly, by using the antireflection material of the present invention as a material for sealing an optical semiconductor element in an optical semiconductor device, high quality (for example, sufficient brightness and high durability while suppressing gloss). An optical semiconductor device is obtained. Moreover, since the resin composition of this invention has the said structure, in order to manufacture the said antireflection material, it is very suitable.
- FIG. 1 It is the schematic which shows one Embodiment of the optical semiconductor device containing the reflection preventing material of this invention.
- the left figure (a) is a perspective view
- the right figure (b) is a sectional view.
- the antireflection material of the present invention is composed of a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, and the hydrophobic porous inorganic filler forms irregularities that suppress reflection on the surface of the cured product. It is characterized by. Further, the resin composition of the present invention is characterized in that a hydrophobic porous inorganic filler is dispersed, and is used for producing the antireflection material.
- the apparent volume for the resin composition is increased compared to the non-porous filler. It can be uniformly dispersed, and uniform fine irregularities can be formed on the surface of the cured product.
- the resin composition soaks into the porous structure, and the apparent specific gravity difference between the hydrophobic porous inorganic filler and the resin composition decreases, so that the dispersion state becomes stable and the hydrophobic porous inorganic filler Since the interaction between the surfaces of the resin is suppressed and it becomes difficult to aggregate, the hydrophobic porous inorganic filler can be uniformly distributed throughout the resin composition or its cured product, so that uniform and fine irregularities are formed on the surface of the cured product.
- the hydrophobic porous inorganic filler is hydrophobic, a cured product containing it exhibits high heat resistance that hardly deteriorates even under severe heating conditions such as boiling water, and is excellent in durability.
- the addition amount (use amount) of the hydrophobic porous inorganic filler is small (small) means that it is small in terms of weight and does not mean that it is small in terms of capacity (volume). Absent.
- the hydrophobic porous inorganic filler in the antireflection material or resin composition of the present invention is uniformly dispersed throughout the resin composition or the cured product thereof, and as a result of the stable dispersion state, the surface of the cured product is stabilized.
- the existing hydrophobic porous inorganic filler has a function of forming irregularities for scattering incident light.
- the hydrophobic porous inorganic filler that can be used in the antireflective material or resin composition of the present invention is an inorganic filler that has an apparent specific gravity smaller than the true specific gravity of the filler and has a porous structure therein, and its surface Means one that has been hydrophobically treated.
- porous inorganic filler constituting the hydrophobic porous inorganic filler (porous inorganic filler before the surface is subjected to hydrophobic treatment)
- a known or conventional one can be used, and is not particularly limited.
- Inorganic glass eg, borosilicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, quartz, etc.
- silica eg, borosilicate glass, borosilicate soda glass, sodium silicate glass, aluminum silicate glass, quartz, etc.
- silica alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, phosphor Sterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline syenite, cristobalite, wollastonite, diatomaceous earth, talc and the like having a porous structure, or molded products thereof (for
- the hydrophobic porous inorganic filler is a known or commonly used hydrophobic surface treating agent [for example, metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyol for the porous inorganic filler before the hydrophobization treatment described above. , Hydrophobic surface treatment agents such as organosilicon compounds, etc.].
- the hydrophobic surface treating agent may be an organosilicon compound (for example, trimethylchlorosilane, hexamethyldisiloxane).
- organosilicon compound for example, trimethylchlorosilane, hexamethyldisiloxane.
- hydrophobic porous inorganic filler the viewpoint that it can be uniformly dispersed throughout the resin composition or its cured product, and can efficiently form irregularities on the surface of the cured product and exhibits excellent heat resistance.
- hydrophobic porous inorganic glass or hydrophobic porous silica hydrophobic porous silica filler is preferable.
- the hydrophobic porous silica is not particularly limited.
- a known or commonly used porous silica such as fused silica, crystalline silica, high-purity synthetic silica, colloidal silica or the like is treated with the hydrophobic surface treatment agent.
- the hydrophobic porous inorganic filler includes an inorganic substance constituting the hydrophobic porous inorganic filler, a styrene resin, an acrylic resin, a silicone resin, an acrylic-styrene resin, a vinyl chloride resin, and a vinylidene chloride type.
- Hydrophobic porous material composed of organic hybrid materials such as resin, amide resin, urethane resin, phenol resin, styrene-conjugated diene resin, acrylic-conjugated diene resin, olefin resin, cellulose resin, etc.
- Inorganic inorganic-organic fillers can also be used.
- the hydrophobic porous inorganic filler may be composed of a single material, or may be composed of two or more materials.
- the resin composition or the cured product can be uniformly dispersed throughout the cured product to efficiently form irregularities on the surface of the cured product, and has high heat resistance, and From the viewpoint of availability and ease of production, hydrophobic porous silica (hydrophobic porous silica filler) is more preferable.
- the shape of the hydrophobic porous inorganic filler is not particularly limited, and examples thereof include powder, spherical shape, crushed shape, fibrous shape, needle shape, and scale shape. Among them, from the viewpoint that the hydrophobic porous inorganic filler is dispersed uniformly throughout the resin composition or the entire cured product, and it becomes easy to form a uniform fine irregular shape on the surface of the cured product, or spherical, or A crushed hydrophobic porous inorganic filler is preferred.
- the average particle size (center particle size) of the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the cured product thereof, From the viewpoint that it is easy to form a uniform fine uneven shape on the surface, the thickness is preferably 1 to 20 ⁇ m, more preferably 2 to 15 ⁇ m.
- the said average particle diameter (center particle diameter) means the volume particle diameter (median volume diameter) in the integrated value 50% in the particle size distribution measured by the laser diffraction and the scattering method.
- Hydrophobic porous inorganic filler porous structure can be specified by various parameters such as specific surface area, oil absorption, etc., and each grade of hydrophobic porous material having parameters suitable for the antireflection material or resin composition of the present invention
- the porous inorganic filler can be selected without particular limitation.
- the said parameter can also be evaluated with the parameter of the porous inorganic filler before hydrophobic processing.
- the specific surface area of the porous inorganic filler constituting the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler is a resin composition or 200 m 2 / g or more is preferable from the viewpoint of spreading uniformly over the entire cured product, facilitating formation of uniform and fine uneven shapes on the surface of the cured product, and preventing reflection efficiently. It is more preferably from 2000 to 2000 m 2 / g, further preferably from 200 to 1500 m 2 / g, particularly preferably from 200 to 1000 m 2 / g.
- the specific surface area is 200 m 2 / g or more, the hydrophobic porous inorganic filler tends to spread uniformly throughout the resin composition or the cured product thereof, and the antireflection function on the surface of the cured product tends to be improved. is there.
- the specific surface area is 2000 m 2 / g or less, the viscosity increase and thixotropy of the resin composition containing the hydrophobic porous inorganic filler are suppressed, and the fluidity when producing the antireflection material is ensured. There is a tendency to.
- the specific surface area of the porous inorganic filler before the surface is treated with hydrophobicity is determined from nitrogen adsorption isotherm at ⁇ 196 ° C. based on the BET equation in accordance with JIS K6430 Annex E. It means adsorption specific surface area.
- the amount of oil absorption of the hydrophobic porous inorganic filler is not particularly limited, but the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the cured product thereof, and the surface of the cured product is uniform and fine. From the viewpoint of facilitating formation of the uneven shape and efficiently preventing reflection, the amount is preferably 10 to 2000 mL / 100 g, more preferably 100 to 1000 mL / 100 g. If the amount of oil absorption is 10 mL / 100 g or more, the hydrophobic porous inorganic filler tends to form a concavo-convex shape on the surface of the cured product by being uniformly dispersed throughout the resin composition or its cured product. There is.
- the oil supply amount of the hydrophobic porous inorganic filler is the amount of oil absorbed by 100 g of the filler, and can be measured according to JIS K5101.
- the hydrophobic porous inorganic filler can be used singly or in combination of two or more.
- the hydrophobic porous inorganic filler can also be produced by a known or conventional production method.
- Aerosil series such as “Aerosil RX200” and “Aerosil RX300” (above, manufactured by Evonik Degussa)
- Sance such as “Sunsphere H-121-ET” and “Sunsphere H-51-ET”
- Commercial products such as the Fair ET series (above, manufactured by AGC S-Tech) can also be used
- the content (blending amount) of the hydrophobic porous inorganic filler in the antireflection material or resin composition of the present invention is not particularly limited, but is preferably relative to the total amount (100% by weight) of the antireflection material or resin composition. Is 4 to 40% by weight, more preferably 4 to 35% by weight, still more preferably 4 to 30% by weight.
- the content of the hydrophobic porous inorganic filler is 4% by weight or more, the hydrophobic porous inorganic filler spreads throughout the resin composition or the entire cured product constituting the antireflection material, and is cured. It becomes easy to form a uniform uneven shape on the entire surface of the object.
- the content of the hydrophobic porous inorganic filler is 40% by weight or less
- the antireflection material or the resin composition of the present invention is used as, for example, a sealing material for an optical semiconductor device, the total luminous flux is remarkable. There is a tendency that sufficient illumination can be secured by preventing the decrease.
- the content (blending amount) of the hydrophobic porous inorganic filler in the antireflection material or the resin composition of the present invention is usually 5 to 80 weights with respect to the resin composition (100 parts by weight) constituting the antireflection material. Part, preferably 5 to 70 parts by weight, more preferably 5 to 60 parts by weight.
- the content of the hydrophobic porous inorganic filler is 5 parts by weight or more, the hydrophobic porous inorganic filler spreads uniformly throughout the resin composition constituting the antireflection material or its cured product, and cured. It becomes easy to form a uniform uneven shape on the entire surface of the object.
- the content of the hydrophobic porous inorganic filler is 80 parts by weight or less
- the antireflection material or the resin composition of the present invention is used as, for example, a sealing material for an optical semiconductor device, the total luminous flux is remarkable. There is a tendency that sufficient illumination can be secured by preventing the decrease.
- the resin composition constituting the cured product in the antireflection material of the present invention is not particularly limited, but is suitable as a sealing material for an optical semiconductor element in an optical semiconductor device, that is, a resin composition for optical semiconductor sealing.
- a resin composition for optical semiconductor sealing can be preferably used, for example, cured by heat or light, has high transparency, durability (for example, characteristics that transparency is not easily lowered by heating, high temperature heat and thermal shock are applied)
- a curable resin composition that gives a cured product that is also excellent in cracks and properties that do not easily peel off from the adherend can be used.
- a known or commonly used resin composition having thermosetting property or photo-curing property can be used without particular limitation.
- an epoxy resin (epoxy compound) (“epoxy resin ( A) ”), a silicone resin (silicone compound) (referred to as“ silicone resin (B) ”), and an acrylic resin (acrylic compound) (referred to as“ acrylic resin (C) ”).
- a composition containing at least one curable compound is preferred.
- examples of such a curable resin composition include a composition containing an epoxy resin (A) (curable epoxy resin composition), a composition containing a silicone resin (B) (curable silicone resin composition), and an acrylic resin.
- the composition (curable acrylic resin composition) containing resin (C) is mentioned.
- the curable resin composition of these embodiments is not limited to the composition of the following aspects.
- the antireflection material of the present invention is not limited to the use of the resin composition for sealing an optical semiconductor, and can be applied to, for example, various optical members described later, and is a resin suitable for each use. (For example, it is applicable also to polyolefin resin, polyester resin, polyamide resin, polyurethane resin, etc.).
- the resin composition constituting the cured product in the antireflection material of the present invention include a curable epoxy resin composition, a curable silicone resin composition, and a curable acrylic resin composition that are excellent in heat resistance, transparency, durability, and the like.
- a curable epoxy resin composition is more preferable.
- the curable epoxy resin composition (sometimes referred to as “the curable epoxy resin composition of the present invention”) is a curable composition containing the epoxy resin (A) as an essential component.
- the curable epoxy resin composition of the present invention further contains a curing agent (D) and a curing accelerator (E) or a curing catalyst (F) as essential components. That is, the curable epoxy resin composition of the present invention is a composition containing an epoxy resin (A), a curing agent (D), and a curing accelerator (E) as essential components, or an epoxy resin (A) and a curing catalyst. It is a composition containing (F) as an essential component.
- the curable epoxy resin composition of the present invention may contain other components other than the essential components described above.
- Epoxy resin (A) The epoxy resin (A) in the curable epoxy resin composition of the present invention is a compound having one or more epoxy groups (oxirane rings) in the molecule, and is arbitrarily selected from known or commonly used epoxy compounds. Can do.
- the epoxy resin (A) include an aromatic epoxy compound (aromatic epoxy resin), an aliphatic epoxy compound (aliphatic epoxy resin), an alicyclic epoxy compound (alicyclic epoxy resin), and a heterocyclic epoxy compound. (Heterocyclic epoxy resin), siloxane derivatives having one or more epoxy groups in the molecule, and the like.
- aromatic epoxy compound examples include aromatic glycidyl ether type epoxy resins [for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenol type epoxy resins, novolac type epoxy resins (for example, phenol novolac type epoxy resins, Cresol novolac type epoxy resin, bisphenol A cresol novolac type epoxy resin), naphthalene type epoxy resin, epoxy resin obtained from trisphenol methane, etc.].
- aromatic glycidyl ether type epoxy resins for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenol type epoxy resins, novolac type epoxy resins (for example, phenol novolac type epoxy resins, Cresol novolac type epoxy resin, bisphenol A cresol novolac type epoxy resin), naphthalene type epoxy resin, epoxy resin obtained from trisphenol methane, etc.].
- aliphatic epoxy compound examples include aliphatic glycidyl ether-based epoxy compounds [for example, aliphatic polyglycidyl ether and the like].
- the alicyclic epoxy compound is a compound having one or more alicyclic rings (aliphatic hydrocarbon rings) and one or more epoxy groups in the molecule (provided that one epoxy group is present in the molecule).
- the siloxane derivative having the above is excluded).
- the alicyclic epoxy compound include (i) at least one alicyclic epoxy group (an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring) in the molecule (preferably (Ii) a compound having an epoxy group bonded directly to the alicyclic ring with a single bond; (iii) a compound having an alicyclic ring and a glycidyl group.
- numerator has, In particular, it is a cyclohexene oxide group (adjacent which comprises a cyclohexane ring from a sclerosing
- the compound having at least one alicyclic epoxy group in the molecule is preferably a compound having two or more cyclohexene oxide groups in the molecule from the viewpoint of transparency and heat resistance of the cured product.
- a compound represented by the following formula (1) is preferable.
- X represents a single bond or a linking group (a divalent group having one or more atoms).
- the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.
- a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring (alicyclic epoxy group) in the formula (1).
- Examples of the compound in which X in the formula (1) is a single bond include (3,4,3 ′, 4′-diepoxy) bicyclohexyl.
- Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.
- Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.
- alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group , 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms (including alkapolyenylene group).
- the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
- the linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation.
- Representative examples of the compound represented by the above formula (1) include 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) ether, , 2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, the following formula (1-1) And compounds represented by (1-10).
- l and m each represents an integer of 1 to 30.
- R in the following formula (1-5) is an alkylene group having 1 to 8 carbon atoms, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene.
- linear or branched alkylene groups such as a group, a heptylene group, and an octylene group.
- linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable.
- N1 to n6 in the following formulas (1-9) and (1-10) each represents an integer of 1 to 30.
- Examples of the compound (ii) having an epoxy group bonded directly to the alicyclic ring with a single bond include compounds represented by the following formula (2).
- R ′ is a group obtained by removing p hydroxyl groups (—OH) from a p-valent alcohol (p-valent organic group) in the structural formula, and p and q each represent a natural number.
- the p-valent alcohol [R ′ (OH) p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol.
- p is preferably 1 to 6, and q is preferably 1 to 30.
- q in each () (inside the parenthesis) may be the same or different.
- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.
- Examples of the compound (iii) having an alicyclic ring and a glycidyl group include 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5 -Dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] propane, hydrogenated bisphenol A type epoxy resin (hydrogenated bisphenol A type epoxy resin), etc .; bis [2- (2,3-epoxy Propoxy) cyclohexyl] methane, [2- (2,3-epoxypropoxy) cyclohexyl] [4- (2,3-epoxypropoxy) cyclohexyl] methane, bis [4- (2,3-epoxy Propoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,3-epoxypropoxy) cyclohexyl] methane, bisphenol F type epoxy Hydrogenated resin (hydrogenated bisphenol F
- alicyclic epoxy compound examples include 1,2,8,9-diepoxy limonene.
- heterocyclic epoxy compound examples include heterocycles other than an epoxy group (oxirane ring) in the molecule [for example, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring, chroman ring, isochroman ring, tetrahydrothiophene ring, tetrahydrothiopyran.
- Ring aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, indoline ring, 2,6-dioxabicyclo [3.3.0] octane ring, 1,3,5-triazacyclohexane ring, 1,3,5 -Non-aromatic heterocycles such as triazacyclohexa-2,4,6-trione ring (isocyanuric ring); Aromatic heterocycles such as thiophene ring, pyrrole ring, furan ring, pyridine ring, etc.] and epoxy And a compound having a group.
- isocyanurate having one or more epoxy groups in the molecule (hereinafter sometimes referred to as “epoxy group-containing isocyanurate”) can be preferably used.
- the number of epoxy groups in the molecule of the epoxy group-containing isocyanurate is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3.
- Examples of the epoxy group-containing isocyanurate include compounds represented by the following formula (3).
- R X , R Y , and R Z are the same or different and represent a hydrogen atom or a monovalent organic group.
- at least one of R X to R Z is a monovalent organic group containing an epoxy group.
- the monovalent organic group include a monovalent aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group); a monovalent aromatic hydrocarbon group (for example, an aryl group); A cyclic group; a monovalent group formed by combining two or more of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- the monovalent organic group may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom).
- a substituent for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom.
- the monovalent organic group containing an epoxy group include monovalent groups containing an epoxy group described later such as an epoxy group, a glycidyl group, a 2-methylepoxypropyl group, and a cyclohexene oxide group.
- the epoxy group-containing isocyanurate includes a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3). And the like.
- R 1 and R 2 are the same or different, A hydrogen atom or an alkyl group having 1 to 8 carbon atoms is shown.
- the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, octyl and the like. Examples thereof include a chain or branched alkyl group.
- R 1 and R 2 are particularly preferably hydrogen atoms.
- Representative examples of the compound represented by the above formula (3-1) include monoallyl diglycidyl isocyanurate, 1-allyl-3,5-bis (2-methylepoxypropyl) isocyanurate, 1- (2 -Methylpropenyl) -3,5-diglycidyl isocyanurate, 1- (2-methylpropenyl) -3,5-bis (2-methylepoxypropyl) isocyanurate and the like.
- Representative examples of the compound represented by the above formula (3-2) include diallyl monoglycidyl isocyanurate, 1,3-diallyl-5- (2-methylepoxypropyl) isocyanurate, 1,3-bis ( 2-methylpropenyl) -5-glycidyl isocyanurate, 1,3-bis (2-methylpropenyl) -5- (2-methylepoxypropyl) isocyanurate and the like.
- Representative examples of the compound represented by the above formula (3-3) include triglycidyl isocyanurate, tris (2-methylepoxypropyl) isocyanurate, and the like.
- the epoxy group-containing isocyanurate may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.
- siloxane derivative having one or more epoxy groups in the molecule (sometimes referred to as “epoxy group-containing siloxane derivative”), a siloxane skeleton composed of siloxane bonds (Si—O—Si) in the molecule is used. And a compound having at least one epoxy group.
- the siloxane skeleton include a cyclic siloxane skeleton; a linear or branched silicone (linear or branched polysiloxane), a polysiloxane skeleton such as a cage-type or ladder-type polysilsesquioxane, and the like. Can be mentioned.
- the number of epoxy groups in the molecule of the epoxy group-containing siloxane derivative is not particularly limited, but is preferably 2 to 4, more preferably 3 or 4.
- the epoxy group which the said epoxy group containing siloxane derivative has is not specifically limited, at least 1 piece is a point which can harden a curable epoxy resin composition efficiently and the hardened
- An alicyclic epoxy group is preferred, and among them, at least one of the epoxy groups is particularly preferably a cyclohexene oxide group.
- Examples of the epoxy group-containing siloxane derivative include a compound (cyclic siloxane) represented by the following formula (4).
- R ⁇ 3 > is the same or different and shows the monovalent
- at least one (preferably at least two) of R 3 in the compound represented by the formula (4) is a monovalent organic group containing an epoxy group (in particular, 1 containing an alicyclic epoxy group). Valent organic group).
- p represents an integer of 3 or more (preferably an integer of 3 to 6).
- the plurality of R 3 may be the same or different.
- Examples of the monovalent organic group containing the epoxy group include an epoxy group, a glycidyl group, a methylglycidyl group, and a group represented by —A—R 4
- A represents an alkylene group
- R 4 represents an alicyclic epoxy group. Indicates a group.
- Examples of A (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. It is done.
- Examples of R 4 include a cyclohexene oxide group.
- examples of the epoxy group-containing siloxane derivative include 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,4,6, 6,8,8-Hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,2,4,6,6,8 -Hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -6,8-dipropyl-2,4,6,8-tetramethyl -Cyclotetrasiloxane, 4,8-di [2- (3- ⁇ oxabicyclo [4.1.0] heptyl ⁇ ) ethyl] -2,6-dipropyl-2,4,6,8-tetramethyl-cyclo Tet
- epoxy group-containing siloxane derivative examples include compounds represented by the following formula (5) (chain polysiloxane).
- R 5 and R 6 are the same or different and are a monovalent organic group containing an epoxy group, an alkoxy group (for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group) Etc.), an alkyl group (eg, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group), or an aryl group (eg, an aryl group having 6 to 12 carbon atoms such as a phenyl group or a naphthyl group).
- an alkoxy group for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group
- an alkyl group eg, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group
- an aryl group eg, an aryl group having 6 to 12 carbon atoms such as a pheny
- At least one (preferably at least two) of R 5 and R 6 in the compound represented by the formula (5) is a monovalent organic group containing an epoxy group.
- the monovalent organic group containing an epoxy group include the same groups as those in the above formula (4).
- q in the formula (5) represents an integer of 1 or more (for example, an integer of 1 to 500).
- the structures in parentheses marked with q may be the same or different.
- the additional form is not particularly limited, and may be a random type or a block type.
- epoxy group-containing siloxane derivative examples include, for example, a silicone resin having an epoxy group (for example, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169), and a silsesquioxy having an epoxy group.
- Sun for example, an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422) and the like.
- the epoxy resin (A) bisphenol A type epoxy resin, isocyanurate having one or more epoxy groups in the molecule
- a novolak type epoxy resin, an alicyclic epoxy compound, an aliphatic epoxy compound, and a siloxane derivative having one or more epoxy groups in the molecule are preferable.
- the curable epoxy resin composition of the present invention is an epoxy resin (A) and an alicyclic epoxy compound as an essential component in that a cured product excellent in transparency and durability can be obtained with high productivity. It is preferable to include.
- the alicyclic epoxy compound is particularly preferably a compound having a cyclohexene oxide group in the molecule (particularly a compound having two or more cyclohexene oxide groups in the molecule), more preferably represented by the formula (1). (Especially a compound represented by formula (1-1)).
- the epoxy resin (A) can be used alone or in combination of two or more.
- an epoxy resin (A) can also be manufactured by a well-known thru
- the content (blending amount) of the epoxy resin (A) in the curable epoxy resin composition of the present invention is not particularly limited, but is 25 to 99.99 with respect to the total amount (100% by weight) of the curable epoxy resin composition. It is preferably 8% by weight (for example, 25 to 95% by weight), more preferably 30 to 90% by weight, still more preferably 35 to 85% by weight, and particularly preferably 40 to 60% by weight.
- the content of the epoxy resin (A) is not particularly limited, but is 25 to 99.99 with respect to the total amount (100% by weight) of the curable epoxy resin composition. It is preferably 8% by weight (for example, 25 to 95% by weight), more preferably 30 to 90% by weight, still more preferably 35 to 85% by weight, and particularly preferably 40 to 60% by weight.
- the content of the epoxy resin (A) is 99.8% by weight or less, the strength of the cured product tends to be further improved.
- the content (blending amount) of the alicyclic epoxy compound in the curable epoxy resin composition of the present invention is not particularly limited, but is 20 to 99.99% with respect to the total amount (100 wt%) of the curable epoxy resin composition. 8% by weight is preferable, more preferably 40 to 95% by weight (for example, 40 to 60% by weight), still more preferably 50 to 95% by weight, particularly preferably 60 to 90% by weight, and most preferably 70 to 85% by weight. It is.
- the content of the alicyclic epoxy compound is 20% by weight or more, curing can proceed more efficiently, and the transparency and durability of the cured product tend to be further improved.
- the content of the alicyclic epoxy compound is 99.8% by weight or less, the strength of the cured product tends to be further improved.
- the ratio of the alicyclic epoxy compound to the total amount of the epoxy compound contained in the curable epoxy resin composition of the present invention (total epoxy compound; for example, total amount of epoxy resin (A)) (100% by weight) is not particularly limited. 40 to 100% by weight (for example, 40 to 90% by weight), more preferably 80 to 100% by weight, still more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight.
- the curing agent (D) which is one of the essential components of the curable epoxy resin composition of the present invention is a compound having a function of curing the curable epoxy resin composition by reacting with the epoxy compound.
- the curing agent (D) is not particularly limited, and those well known and commonly used as curing agents for epoxy resins can be used. For example, acid anhydrides (acid anhydride-based curing agents), amines (amine-based) Curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenol curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, and the like. .
- acid anhydrides as the curing agent (D)
- known or commonly used acid anhydride curing agents can be used, and are not particularly limited.
- methyltetrahydrophthalic anhydride (4 -Methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.
- methylhexahydrophthalic anhydride such as 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride
- dodecenyl succinic anhydride methyl Endomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, anhydrous Nadic
- acid anhydrides for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.
- a solid acid anhydride at 25 ° C. for example, by dissolving in a liquid acid anhydride at 25 ° C. to form a liquid mixture, the curing agent (D in the curable epoxy resin composition of the present invention (D ) Tends to be improved.
- saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.
- amines (amine-based curing agent) as the curing agent (D) a known or conventional amine-based curing agent can be used, and is not particularly limited.
- ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine Aliphatic polyamines such as dipropylenediamine, diethylaminopropylamine, polypropylenetriamine; mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-amino Cycloaliphatic polyamines such as ethylpiperazine, 3,9-bis (3-aminopropyl) -3,4,8,10-tetraoxaspiro [5,5] undecane; m-phenylenediamine, p-phenylenediamine, Len-2
- phenols phenolic curing agents
- known or conventional phenolic curing agents can be used, and are not particularly limited.
- novolac type phenol resins novolac type cresol resins
- paraxylylene-modified phenols examples thereof include aralkyl resins such as resins, paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.
- Examples of the polyamide resin as the curing agent (D) include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
- imidazole (imidazole curing agent) as the curing agent (D), a known or conventional imidazole curing agent can be used, and is not particularly limited.
- Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (D) include liquid polymercaptan and polysulfide resin.
- polycarboxylic acids examples include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxy group-containing polyester, and the like.
- acid anhydrides are preferable from the viewpoints of curability, heat resistance of the cured product, and transparency.
- curing agent (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- a commercial item can also be used as a hardening
- commercially available acid anhydrides include trade names “Licacid MH-700” and “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi Chemical Industries). Etc.).
- the content (blending amount) of the curing agent (D) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy
- the total amount of the resin (A) is preferably 50 to 200 parts by weight, more preferably 75 to 150 parts by weight, and still more preferably 100 to 120 parts by weight with respect to 100 parts by weight. More specifically, when acid anhydrides are used as the curing agent (D), 0.5 to 1. per epoxy group equivalent in all epoxy compounds contained in the curable epoxy resin composition of the present invention. It is preferable to use it at a ratio of 5 equivalents.
- the curing accelerator (E) which is one of the essential components of the curable epoxy resin composition of the present invention, has a reaction rate of the reaction of the epoxy compound (particularly the reaction between the epoxy resin (A) and the curing agent (D)). It is a compound having a function to promote.
- the curing accelerator (E) those well known and commonly used as curing accelerators for epoxy resins can be used, and are not particularly limited.
- DBU 1,8-diazabicyclo [5.4.0] undecene-7
- salts thereof eg, phenol salts, octylates, p-toluenesulfonates, formates, tetraphenylborate salts, etc.
- salts thereof eg, phenol salt, octylate, p-toluenesulfonate, formate, tetraphenylborate salt
- one type of curing accelerator (E) can be used alone, or two or more types can be used in combination.
- Examples of the curing accelerator (E) in the curable epoxy resin composition of the present invention include, for example, trade names “U-CAT SA 506”, “U-CAT SA 102”, “U-CAT 5003”, “U-CAT”. 18X ",” 12XD "(developed product) (San Apro Co., Ltd.); trade names" TPP-K “,” TPP-MK “(Hokuko Chemical Co., Ltd.); trade names” PX- Commercially available products such as “4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can be used.
- the content (blending amount) of the curing accelerator (E) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, The total amount of the epoxy resin (A)) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 100 parts by weight. 0.25 to 2.5 parts by weight.
- the content of the curing accelerator (E) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 100 parts by weight. 0.25 to 2.5 parts by weight.
- the curing catalyst (F) which is one of the essential components of the curable epoxy resin composition of the present invention, is curable by initiating and / or accelerating the curing reaction (polymerization reaction) of a cationically polymerizable compound such as an epoxy compound. It is a compound having a function of curing the epoxy resin composition.
- a curing catalyst (F) for example, the cationic polymerization initiator (thermal cation polymerization initiator) which generate
- examples of the curing catalyst (F) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”, “CP-77” (manufactured by ADEKA); trade name “FC-509” (manufactured by 3M); trade name “UVE1014” (manufactured by GE); trade names “Sun Aid SI-60L”, “Sun Aid” "SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-150L” (manufactured by Sanshin Chemical Industry Co., Ltd.); trade name “CG-24-61” (BASF Corporation) (Commercially available products) can be preferably used.
- the curing catalyst (F) for example, a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or a diketone and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid
- a compound of a chelate compound with a diketone and a phenol such as bisphenol S is also included.
- Lewis acid / amine complex as the curing catalyst (F), a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
- a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
- Bronsted acid salts as the curing catalyst (F), known or commonly used Bronsted acid salts can be used, and are not particularly limited.
- imidazole as the curing catalyst (F), known or conventional imidazoles can be used, and are not particularly limited.
- one type of curing catalyst (F) can be used alone, or two or more types can be used in combination.
- a curing catalyst (F) a commercial item can be used, for example.
- the content (blending amount) of the curing catalyst (F) in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy
- the total amount of the resin (A)) is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0 to 100 parts by weight. .05 to 8 parts by weight.
- the curable epoxy resin composition of the present invention may substantially contain a photocationic polymerization initiator that generates a cationic polymerization initiating species (such as an acid) by light irradiation.
- a photocationic polymerization initiator that generates a cationic polymerization initiating species (such as an acid) by light irradiation.
- the content thereof is, for example, the total amount of epoxy compounds contained in the curable epoxy resin composition (total epoxy compounds; for example, epoxy resin (A )) To 100 parts by weight, for example, about 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.
- the curable epoxy resin composition of the present invention may contain a polyhydric alcohol.
- the curable epoxy resin composition of the present invention includes a curing agent (D) and a curing accelerator (E), it further includes a polyhydric alcohol in that curing can proceed more efficiently. It is preferable.
- the polyhydric alcohol known or commonly used polyhydric alcohols can be used, and are not particularly limited.
- ethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol examples include 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol.
- the polyhydric alcohol is preferably an alkylene glycol having 1 to 6 carbon atoms, more preferably carbon in terms of being able to control curing well and easily obtaining a cured product that is less prone to cracking and peeling. It is an alkylene glycol of formula 2-4.
- the polyhydric alcohol can be used alone or in combination of two or more.
- the content (blending amount) of the polyhydric alcohol in the curable epoxy resin composition of the present invention is not particularly limited, but the total amount of the epoxy compound contained in the curable epoxy resin composition (total epoxy compound; for example, epoxy resin (The total amount of A) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 100 parts by weight. ⁇ 2.5 parts by weight.
- the content of the polyhydric alcohol is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, still more preferably 0.2 to 3 parts by weight, particularly preferably 0.25 to 100 parts by weight. ⁇ 2.5 parts by weight.
- the curable epoxy resin composition of the present invention may contain a phosphor.
- a phosphor When the curable epoxy resin composition of the present invention contains a phosphor, it is particularly preferably used as an optical semiconductor device sealing application (sealing material application) in an optical semiconductor device, that is, an optical semiconductor sealing resin composition. it can.
- the phosphor a known or commonly used phosphor (in particular, a phosphor used for sealing an optical semiconductor element) can be used, and is not particularly limited.
- the general formula A 3 B 5 O 12 M [Wherein, A represents one or more elements selected from the group consisting of Y, Gd, Tb, La, Lu, Se, and Sm, and B is selected from the group consisting of Al, Ga, and In.
- YAG phosphor fine particles represented by the following formula: M represents one or more elements selected from the group consisting of Ce, Pr, Eu, Cr, Nd, and Er] (For example, Y 3 Al 5 O 12 : Ce phosphor fine particles, (Y, Gd, Tb) 3 (Al, Ga) 5 O 12 : Ce phosphor fine particles, etc.), silicate type phosphor fine particles (for example, (Sr, Ca, Ba) 2 SiO 4 : Eu and the like.
- the surface of the phosphor may be modified with an organic group (for example, a long-chain alkyl group, a phosphate group, etc.) to improve dispersibility, for example.
- the phosphor may be used alone or in combination of two or more.
- a commercial item can be used as a fluorescent substance.
- the phosphor content (blending amount) in the curable epoxy resin composition of the present invention is not particularly limited, and is 0.5 to 20% by weight relative to the total amount (100% by weight) of the curable epoxy resin composition. It can select suitably in the range of.
- the curable epoxy resin composition of the present invention may contain other components other than those described above within a range that does not adversely affect the curability and transparency.
- the other components include a silicone resin having a linear or branched chain, a silicone resin having an alicyclic ring, a silicone resin having an aromatic ring, a cage type / ladder type / random type silsesquioxane, Examples thereof include silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, silicone-based and fluorine-based antifoaming agents, and the like.
- the content (blending amount) of the other components is not particularly limited, but is preferably 5% by weight or less (for example, 0 to 3% by weight) with respect to the total amount (100% by weight) of the curable epoxy resin composition. .
- the curable epoxy resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing each of the above-described components in a heated state as necessary.
- the curable epoxy resin composition of the present invention may be a one-component composition that uses a mixture of all the components in advance, or, for example, a component divided into two or more. It may be a multi-liquid composition (for example, a two-liquid system) used by mixing at a predetermined ratio immediately before use.
- the method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum.
- the curable silicone resin composition (sometimes referred to as “the curable silicone resin composition of the present invention”) is a curable composition containing a silicone resin (B) as an essential component as a curable compound. It is a thing.
- the curable silicone resin composition of the present invention may contain components other than the silicone resin (B).
- silicone resin (B) examples include —Si—O—Si— (siloxane bond) as a main chain, and —Si—R A —Si— (silalkylene bond: R A represents an alkylene group). Included polyorganosiloxysilalkylene; curable polysiloxanes such as polyorganosiloxane that does not contain the above-mentioned silalkylene bond as the main chain.
- the silicone resin (B) a known or commonly used curable silicone resin (curable polysiloxane) can be used as the curable compound, and is not particularly limited.
- the curable silicone resin composition of the present invention contains the former, it can be used as an addition reaction curable silicone resin composition, and when it contains the latter, it can be used as a condensation reaction curable silicone resin composition. it can.
- the addition reaction curable silicone resin composition and the condensation reaction curable silicone resin composition will be described.
- the curable silicone resin composition of the present invention is not limited thereto.
- an addition type silicone resin and It may be a silicone resin composition that contains both condensation type silicone resins and cures by addition reaction and condensation reaction. That is, curing of the curable silicone resin composition in the curing step may proceed by at least one reaction selected from the group consisting of an addition reaction and a condensation reaction.
- the addition reaction curable silicone resin composition contains, for example, a polysiloxane (B1) having two or more alkenyl groups in the molecule as the silicone resin (B), and further required.
- a curable silicone resin composition containing polysiloxane having one or more (preferably two or more) hydrosilyl groups in the molecule, a metal curing catalyst, or the like may be mentioned.
- the polysiloxane (B1) is classified into a polyorganosiloxane (B1-1) and a polyorganosiloxysilalkylene (B1-2).
- polyorganosiloxysilalkylene (B1-2) has two or more alkenyl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si Polysiloxane containing —R A —Si— (silalkylene bond: R A represents an alkylene group).
- the polyorganosiloxane (B1-1) in the present specification is a polysiloxane having two or more alkenyl groups in the molecule and not containing the silalkylene bond as a main chain.
- Examples of the polyorganosiloxane (B1-1) include those having a molecular structure of linear or branched (linear, partially branched, network, etc. having a partial branch).
- the polyorganosiloxane (B1-1) can be used alone or in combination of two or more. Two or more polyorganosiloxanes (B1-1) having different molecular structures can be used in combination, for example, linear polyorganosiloxane (B1-1) and branched polyorganosiloxane (B1-). 1) can be used in combination.
- alkenyl group that the polyorganosiloxane (B1-1) has in the molecule examples include substituted or unsubstituted alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, and hexenyl group.
- substituent examples include a halogen atom, a hydroxy group, and a carboxy group.
- alkenyl group a vinyl group is preferable.
- the polyorganosiloxane (B1-1) may have only one alkenyl group or may have two or more alkenyl groups.
- the alkenyl group of the polyorganosiloxane (B1-1) is not particularly limited, but is preferably bonded to a silicon atom.
- the group bonded to the silicon atom other than the alkenyl group of the polyorganosiloxane (B1-1) is not particularly limited, and examples thereof include a hydrogen atom and a monovalent organic group.
- the monovalent organic group include alkyl groups [eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.], cycloalkyl groups [eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, etc.
- the “group bonded to a silicon atom” usually means a group not containing a silicon atom.
- the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.
- the properties of the polyorganosiloxane (B1-1) are not particularly limited, and may be liquid or solid.
- R 7 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the specific examples described above (for example, alkyl group, alkenyl group, aryl group, aralkyl group, halogenated carbonization) Hydrogen group, etc.).
- a part of R 7 is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule.
- the ratio of the alkenyl group to the total amount of R 7 (100 mol%) is preferably 0.1 to 40 mol%.
- R 7 other than the alkenyl group an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
- Z is a hydrogen atom or an alkyl group.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
- a1 is 0 or positive number
- a2 is 0 or positive number
- a3 is 0 or positive number
- a4 is 0 or positive number
- a5 is 0 or positive number
- (a1 + a2 + a3) is positive Is a number.
- the polyorganosiloxysilalkylene (B1-2) is a polyorganosiloxane having two or more alkenyl groups in the molecule and containing a silalkylene bond as a main chain in addition to a siloxane bond.
- the alkylene group in the silalkylene bond is preferably a C 2-4 alkylene group (particularly an ethylene group).
- the polyorganosiloxysilalkylene (B1-2) is less likely to form a low molecular weight ring in the production process than the polyorganosiloxane (B1-1), and decomposes by heating or the like to produce silanol groups (—SiOH).
- the surface tackiness (tackiness) of the cured product of the curable silicone resin composition tends to be low, and it tends to be more difficult to yellow.
- polyorganosiloxysilalkylene (B1-2) examples include those having a molecular structure such as a straight chain or a branched chain (a linear chain having a partial branch, a branched chain, a network, etc.).
- Polyorganosiloxysilalkylene (B1-2) can be used alone or in combination of two or more.
- two or more types of polyorganosiloxysilalkylene (B1-2) having different molecular structures can be used in combination, for example, a linear polyorganosiloxysilalkylene (B1-2) and a branched polyorganoorgano Siloxysilalkylene (B1-2) can also be used in combination.
- alkenyl group that polyorganosiloxysilalkylene (B1-2) has in the molecule include the specific examples described above, and among them, a vinyl group is preferable. Further, the polyorganosiloxysilalkylene (B1-2) may have only one alkenyl group, or may have two or more alkenyl groups.
- the alkenyl group of polyorganosiloxysilalkylene (B1-2) is not particularly limited, but is preferably bonded to a silicon atom.
- the group bonded to the silicon atom other than the alkenyl group of polyorganosiloxysilalkylene (B1-2) is not particularly limited, and examples thereof include a hydrogen atom and a monovalent organic group.
- a monovalent organic group the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example.
- an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
- the group bonded to the silicon atom may have a hydroxy group or an alkoxy group.
- the properties of the polyorganosiloxysilalkylene (B1-2) are not particularly limited, and may be liquid or solid.
- polyorganosiloxysilalkylene (B1-2) As polyorganosiloxysilalkylene (B1-2), the following average unit formula: (R 8 2 SiO 2/2 ) b 1 (R 8 3 SiO 1/2 ) b 2 (R 8 SiO 3/2 ) b 3 (SiO 4/2 ) b 4 (R A ) b 5 (ZO 1/2 ) b 6
- R 8 is the same or different and is a monovalent substituted or unsubstituted hydrocarbon group, and the above specific examples (for example, alkyl group, alkenyl group, aryl group, aralkyl group, alkyl halide) Group).
- a part of R 8 is an alkenyl group (particularly a vinyl group), and the ratio thereof is controlled within a range of 2 or more in the molecule.
- the ratio of the alkenyl group to the total amount of R 8 (100 mol%) is preferably 0.1 to 40 mol%.
- R 8 other than an alkenyl group is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
- R A is an alkylene group as described above.
- An ethylene group is particularly preferable.
- Z is a hydrogen atom or an alkyl group as described above.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
- b1 is a positive number
- b2 is a positive number
- b3 is 0 or a positive number
- b4 is 0 or a positive number
- b5 is a positive number
- b6 is 0 or a positive number.
- b1 is preferably 1 to 200
- b2 is preferably 1 to 200
- b3 is preferably 0 to 10
- b4 is preferably 0 to 5
- b5 is preferably 1 to 100.
- (b3 + b4) is a positive number, the mechanical strength of the cured product tends to be further improved.
- the addition reaction curable silicone resin composition further comprises a polysiloxane having one or more (preferably two or more) hydrosilyl groups (Si—H) in the molecule (“hydrosilyl group-containing polysiloxane”). May be included).
- the hydrosilyl group-containing polysiloxane is classified into a hydrosilyl group-containing polyorganosiloxane and a hydrosilyl group-containing polyorganosiloxysil alkylene.
- the hydrosilyl group-containing polyorganosiloxysilalkylene has one or more hydrosilyl groups in the molecule, and in addition to —Si—O—Si— (siloxane bond) as a main chain, —Si—R A polysiloxane containing A-Si- (silalkylene bond: R A represents an alkylene group).
- R A represents an alkylene group
- the hydrosilyl group containing polyorganosiloxane in this specification is a polysiloxane which has 1 or more hydrosilyl groups in a molecule
- R A (alkylene group) as described above, for example, a linear or branched C 1-12 alkylene group may be mentioned, and preferably a linear or branched C 2-4 alkylene group ( In particular, ethylene group).
- hydrosilyl group-containing polyorganosiloxane examples include those having a molecular structure of a straight chain or a branched chain (a linear chain having a partial branch, a branched chain, a network, etc.).
- the said hydrosilyl group containing polyorganosiloxane can also be used individually by 1 type, and can also be used in combination of 2 or more type. Two or more hydrosilyl group-containing polyorganosiloxanes having different molecular structures can be used in combination.
- a linear hydrosilyl group-containing polyorganosiloxane and a branched hydrosilyl group-containing polyorganosiloxane may be used in combination. it can.
- groups other than hydrogen atoms are not particularly limited.
- the monovalent substituted or unsubstituted hydrocarbon group described above more specifically, an alkyl group , Aryl group, aralkyl group, halogenated hydrocarbon group and the like.
- an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
- the said hydrosilyl group containing polyorganosiloxane may have an alkenyl group (for example, vinyl group) as a group couple
- the properties of the hydrosilyl group-containing polyorganosiloxane are not particularly limited, and may be liquid or solid. In particular, it is preferably a liquid, and more preferably a liquid having a viscosity at 25 ° C. of 0.1 to 1,000,000 mPa ⁇ s.
- the hydrosilyl group-containing polyorganosiloxane has the following average unit formula: (R 9 SiO 3/2 ) c 1 (R 9 2 SiO 2/2 ) c 2 (R 9 3 SiO 1/2 ) c 3 (SiO 4/2 ) c 4 (ZO 1/2 ) c 5
- R 9 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and a hydrogen atom, the above-mentioned specific examples (for example, alkyl group, alkenyl group, aryl Group, aralkyl group, halogenated alkyl group and the like).
- a part of R 9 is a hydrogen atom (hydrogen atom constituting a hydrosilyl group), and the ratio thereof is controlled in a range in which one or more (preferably two or more) hydrosilyl groups are present in the molecule.
- the ratio of hydrogen atoms to the total amount of R 9 (100 mol%) is preferably 0.1 to 40 mol%.
- R 9 other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
- Z is a hydrogen atom or an alkyl group as described above.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
- c1 is 0 or positive
- c2 is 0 or positive
- c3 is 0 or positive
- c4 is 0 or positive
- c5 is 0 or positive
- (c1 + c2 + c3) is positive Is a number.
- the hydrosilyl group-containing polyorganosiloxysilalkylene is a polyorganosiloxane having one or more hydrosilyl groups in the molecule and containing a silalkylene bond as a main chain in addition to a siloxane bond.
- a silalkylene bond as an alkylene group in the said silalkylene bond, a C2-4 alkylene group (especially ethylene group) is preferable, for example.
- the hydrosilyl group-containing polyorganosiloxysilalkylene is less likely to produce a low molecular weight ring in the production process than the hydrosilyl group-containing polyorganosiloxane, and is not easily decomposed by heating or the like to produce a silanol group (—SiOH). Therefore, when the above hydrosilyl group-containing polyorganosiloxysilalkylene is used, the surface tackiness of the cured product of the curable silicone resin composition tends to be low, and it tends to be more difficult to yellow.
- hydrosilyl group-containing polyorganosiloxysil alkylene examples include those having a molecular structure of linear or branched (linear, partially branched, network, etc. having a partial branch).
- the said hydrosilyl group containing polyorganosiloxy silalkylene can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- Two or more hydrosilyl group-containing polyorganosiloxysil alkylenes having different molecular structures can be used in combination, for example, a linear hydrosilyl group-containing polyorganosiloxysil alkylene and a branched hydrosilyl group-containing polyorganosiloxysil alkylene. Can also be used in combination.
- the group bonded to the silicon atom other than the hydrogen atom of the hydrosilyl group-containing polyorganosiloxysilalkylene is not particularly limited, and examples thereof include a monovalent organic group.
- a monovalent organic group the above-mentioned monovalent substituted or unsubstituted hydrocarbon group etc. are mentioned, for example. Of these, an alkyl group (particularly a methyl group) and an aryl group (particularly a phenyl group) are preferable.
- the properties of the hydrosilyl group-containing polyorganosiloxysilalkylene are not particularly limited, and may be liquid or solid.
- hydrosilyl group-containing polyorganosiloxysilalkylene examples include the following average unit formula: (R 10 2 SiO 2/2) d1 (R 10 3 SiO 1/2) d2 (R 10 SiO 3/2) d3 (SiO 4/2) d4 (R A) d5 (ZO 1/2) d6
- R 10 2 SiO 2/2) d1 R 10 3 SiO 1/2
- d2 R 10 SiO 3/2)
- SiO 4/2 d4
- R A d5 (ZO 1/2) d6
- a polyorganosiloxysilalkylene represented by the formula is preferred.
- R 10 is the same or different and is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group, and the hydrogen atom and the above-described specific examples (for example, an alkyl group, an alkenyl group, an aryl group) Aralkyl group, halogenated alkyl group, etc.).
- a part of R 10 is a hydrogen atom, and the ratio thereof is controlled within a range of 1 or more (preferably 2 or more) in the molecule.
- the proportion of hydrogen atoms with respect to the total amount of R 10 (100 mol%) is preferably 0.1 to 50 mol%, more preferably 5 to 35 mol%.
- R 10 other than a hydrogen atom is preferably an alkyl group (particularly a methyl group) or an aryl group (particularly a phenyl group).
- the ratio of aryl groups (particularly phenyl groups) to the total amount (100 mol%) of R 10 is preferably 5 mol% or more (eg, 5 to 80 mol%), more preferably 10 mol% or more.
- R A is an alkylene group as described above.
- An ethylene group is particularly preferable.
- Z is a hydrogen atom or an alkyl group as described above.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is particularly preferable.
- d1 is a positive number
- d2 is a positive number
- d3 is 0 or a positive number
- d4 is 0 or a positive number
- d5 is a positive number
- d6 is 0 or a positive number.
- d1 is preferably 1 to 50
- d2 is preferably 1 to 50
- d3 is preferably 0 to 10
- d4 is preferably 0 to 5
- d5 is preferably 1 to 30.
- hydrosilyl group-containing polysiloxane in the addition reaction curable silicone resin composition only the hydrosilyl group-containing polyorganosiloxane can be used, or only the hydrosilyl group-containing polyorganosiloxysil alkylene can be used, Moreover, hydrosilyl group-containing polyorganosiloxane and hydrosilyl group-containing polyorganosiloxysilalkylene can be used in combination. When the hydrosilyl group-containing polyorganosiloxane and the hydrosilyl group-containing polyorganosiloxysilalkylene are used in combination, these ratios are not particularly limited and can be set as appropriate.
- the addition reaction curable silicone resin composition is not particularly limited, but is a composition (formulation composition) in which the alkenyl group is 0.2 to 4 moles with respect to 1 mole of the hydrosilyl group present in the curable resin composition. ), More preferably 0.5 to 1.5 mol, still more preferably 0.8 to 1.2 mol.
- the cured product has more heat resistance, transparency, thermal shock resistance, reflow resistance, and barrier property against corrosive gas (for example, SOx gas). There is a tendency to improve.
- the addition reaction curable silicone resin composition may contain a metal curing catalyst as described above.
- metal curing catalysts include well-known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
- a platinum vinylmethylsiloxane complex a platinum-carbonylvinylmethyl complex, or a complex of chloroplatinic acid and an alcohol or aldehyde is preferable because the reaction rate is good.
- a metal curing catalyst (hydrosilylation catalyst) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content (blending amount) of the metal curing catalyst (hydrosilylation catalyst) in the addition reaction curable silicone resin composition is not particularly limited, but the total amount of alkenyl groups contained in the addition reaction curable silicone resin composition is 1 mol. On the other hand, it is preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 2 mol, more preferably 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 3 mol. By setting the content to 1 ⁇ 10 ⁇ 8 mol or more, there is a tendency that a cured product can be formed more efficiently. On the other hand, when the content is 1 ⁇ 10 ⁇ 2 mol or less, there is a tendency that a cured product having a more excellent hue (less coloring) can be obtained.
- the addition reaction curable silicone resin composition may contain components other than those described above.
- the condensation reaction curable silicone resin composition includes, for example, two or more silanol groups (Si-OH) or silalkoxy groups (Si-OR) in the molecule as the silicone resin (B). And a curable silicone resin composition containing a metal curing catalyst and the like, if necessary.
- the polysiloxane (B2) may have only one of a silanol group and a silalkoxy group, or may have both a silanol group and a silalkoxy group. When it has both a silanol group and a silalkoxy group, the total number of these should just be 2 or more in a molecule
- polysiloxane (B2) the polyorganosiloxane represented by the following average compositional formula is mentioned, for example.
- R 11 is the same or different and represents a monovalent organic group having 1 to 20 carbon atoms.
- R 12 are the same or different and each represents a monovalent organic group having 1 to 4 carbon atoms.
- e is a number from 0.8 to 1.5
- f is a number from 0 to 0.3
- g is a number from 0 to 0.5.
- f + g is a number from 0.001 to less than 1.2.
- E + f + g is a number of 0.801 or more and less than 2.
- Examples of the monovalent organic group as R 11 in the average composition formula include, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.); a monovalent aromatic hydrocarbon group (for example, Aryl groups, etc.); monovalent heterocyclic groups; monovalent groups formed by combining two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, and the like. .
- These monovalent organic groups may have a substituent (for example, a substituent such as a hydroxy group, a carboxy group, or a halogen atom).
- R 11 is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
- the monovalent organic group as R 12 in the average composition formula include, for example, a monovalent aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.) that may have a substituent. Is mentioned.
- R 12 is preferably an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms.
- polysiloxane (B2) in the above condensation reaction curable silicone resin composition, can be used alone or in combination of two or more.
- the condensation reaction curable silicone resin composition may contain a metal curing catalyst as described above.
- metal curing catalysts include known or conventional condensation reaction catalysts, such as organic titanate esters, organic titanium chelate compounds, organic aluminum compounds, organic zirconium compounds, organic tin compounds, and metal salts of organic carboxylic acids. Amine compounds or salts thereof, quaternary ammonium salts, lower fatty acid salts of alkali metals, dialkylhydroxylamines, guanidyl group-containing organosilicon compounds, and the like.
- an organic zirconium compound is preferable from the viewpoint of reactivity. These can also be used individually by 1 type and can also be used in combination of 2 or more type.
- the content (blending amount) of the metal curing catalyst (condensation reaction catalyst) in the condensation reaction curable silicone resin composition is not particularly limited, but is, for example, about 0.1 part by weight relative to 100 parts by weight of the total amount of polysiloxane (B2). It can be appropriately selected within the range of 01 to 20 parts by weight.
- the condensation reaction curable silicone resin composition may contain components other than those described above.
- the curable silicone resin composition of the present invention may contain other components.
- what was illustrated as a component which the curable epoxy resin composition of this invention may contain, etc. are mentioned, for example.
- the content is not particularly limited, and can be appropriately selected.
- the curable silicone resin composition of the present invention is a resin composition for encapsulating an optical semiconductor, it is preferable that the phosphor described above is included.
- the phosphor content (blending amount) in the curable silicone resin composition of the present invention is not particularly limited, and is 0.5 to 20% by weight based on the total amount (100% by weight) of the curable silicone resin composition. It can select suitably in the range of.
- the curable silicone resin composition of the present invention is not particularly limited, and can be prepared, for example, by stirring and mixing the above-described components while being heated as necessary.
- the curable silicone resin composition of the present invention may be a one-component composition that uses a mixture of all the components in advance, or, for example, a component divided into two or more. It may be a multi-liquid composition (for example, a two-liquid system) used by mixing at a predetermined ratio immediately before use.
- the method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum. Moreover, as a curable silicone resin composition of this invention or its component, a commercial item can also be used as it is.
- the curable acrylic resin composition (sometimes referred to as “the curable acrylic resin composition of the present invention”) includes a curable composition containing an acrylic resin (C) as an essential component. It is a thing.
- the curable acrylic resin composition of the present invention may contain components other than the acrylic resin (C).
- acrylic resin (C) examples include compounds having at least one (meth) acryloyl group (at least one group selected from the group consisting of an acryloyl group and a methacryloyl group) in the molecule.
- acrylic resin (C) examples include (meth) acryloyl compounds having only one (meth) acryloyl group in the molecule; polyfunctional (meth) acryloyl compounds having two or more (meth) acryloyl groups in the molecule. It is done.
- the (meth) acryloyl compound having only one (meth) acryloyl group in the molecule includes a monofunctional (meth) acryloyl compound having no polymerizable functional group other than the (meth) acryloyl group, In addition to the acryloyl group, a polyfunctional (meth) acryloyl compound having one or more other polymerizable functional groups such as an epoxy group, an oxetanyl group, a vinyl group, and a vinyloxy group.
- Acrylic resin (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- content of the acrylic resin (C) in the curable acrylic resin composition of this invention is not specifically limited, It can select suitably.
- the curable acrylic resin composition of the present invention may contain, for example, an initiator for causing the polymerization reaction of the acrylic resin (C) to proceed.
- an initiator for causing the polymerization reaction of the acrylic resin (C) to proceed.
- the initiator include known or conventional polymerization initiators such as a thermal polymerization initiator. These can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the content of the initiator is not particularly limited, and can be appropriately selected.
- the curable acrylic resin composition of the present invention may contain other components. As another component, what was illustrated as a component which the curable epoxy resin composition of this invention may contain, etc. are mentioned, for example.
- the content is not particularly limited, and can be appropriately selected.
- the curable acrylic resin composition of the present invention is a resin composition for encapsulating an optical semiconductor, it is preferable that the phosphor described above is included.
- the phosphor content (blending amount) in the curable acrylic resin composition of the present invention is not particularly limited, and is 0.5 to 20% by weight relative to the total amount (100% by weight) of the curable acrylic resin composition. It can select suitably in the range of.
- the curable acrylic resin composition of the present invention is not particularly limited, but can be prepared, for example, by stirring and mixing the above-described components in a heated state as necessary.
- the curable acrylic resin composition of the present invention may be a one-component composition that uses a mixture of all the components in advance, or, for example, a component divided into two or more. It may be a multi-liquid composition (for example, a two-liquid system) used by mixing at a predetermined ratio immediately before use.
- the method of stirring and mixing is not particularly limited, and for example, known or conventional stirring and mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under reduced pressure or under vacuum. Moreover, as a curable acrylic resin composition of this invention, or its structural component, it is also possible to use a commercial item as it is.
- the hydrophobic porous inorganic filler is uniformly dispersed throughout the resin composition or the cured product thereof, and is present on the surface of the cured product as a result of stable dispersion.
- the hydrophobic porous inorganic filler forms an uneven shape and exhibits an antireflection function by scattering incident light. Further, the porous structure on the surface of the hydrophobic porous inorganic filler can also scatter incident light, and the antireflection function is further improved.
- the cured product containing it exhibits high heat resistance that is not easily deteriorated even under severe heating conditions such as boiling water, in particular, hot water resistance and durability. Excellent.
- the method for spreading the hydrophobic porous inorganic filler throughout the cured product is not particularly limited.
- the method is a method in which the hydrophobic porous inorganic filler is uniformly dispersed in the resin composition constituting the cured product and then cured. Etc.
- a method in which the hydrophobic porous inorganic filler is uniformly dispersed and then cured is preferable.
- one embodiment of the method for producing an antireflection material of the present invention will be described, but the present invention is not limited thereto.
- the mixing / stirring method is not particularly limited.
- known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used.
- defoaming may be performed under reduced pressure or under vacuum.
- the properties of the resin composition before curing of the present invention are not particularly limited, but are preferably liquid.
- the resin composition before curing that forms the antireflection material of the present invention can exhibit an antireflection function with a small amount of addition by using a hydrophobic porous inorganic filler, so that a solvent such as toluene is not used. Both of them are liable to become liquid and are preferable.
- the antireflection material of the present invention is obtained by curing a resin composition in which the hydrophobic porous inorganic filler is uniformly dispersed to obtain a cured product (hereinafter sometimes referred to as “cured product of the present invention”). Can do.
- the amount of the component that volatilizes during curing relative to the total amount (100% by weight) of the resin composition before curing is not particularly limited, but is preferably 10% by weight or less, more preferably 8% by weight or less, Preferably it is 5 weight% or less. When the amount of the component that volatilizes during curing is 10% by weight or less, the dimensional stability of the cured product is increased, which is preferable.
- the resin composition before curing of the present invention can exhibit an antireflection function with a small amount of addition by using a hydrophobic porous inorganic filler, it is liquid without using a volatile component of a solvent (toluene or the like). The amount of components that volatilize during curing can be reduced.
- the temperature for curing by heating is not particularly limited, but is preferably 45 to 200 ° C, more preferably 50 to 190 ° C, and still more preferably 55 to 180 ° C.
- the heating time (curing time) for curing is not particularly limited, but is preferably 30 to 600 minutes, more preferably 45 to 540 minutes, and further preferably 60 to 480 minutes.
- the curing conditions depend on various conditions, for example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing time can be appropriately increased. Moreover, hardening can also be performed in one step and can also be performed in two or more steps.
- light (radiation) including i-line (365 nm), h-line (405 nm), g-line (436 nm), etc. is irradiated at an illuminance of 10 to 1200 mW / cm 2 .
- the antireflection material of the present invention can be obtained by irradiating with a light amount of 20 to 2500 mJ / cm 2 .
- the irradiation light amount is preferably 20 to 600 mJ / cm 2 , more preferably 20 to 300 mJ / cm 2 .
- a high-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, laser light, or the like can be used as an irradiation source.
- the antireflection material of the present invention has high heat resistance (particularly, hot water resistance) in addition to high transparency and an excellent antireflection function. Therefore, the antireflection material for optical materials (used for forming optical materials) is used. Can be suitably used as a resin.
- An optical material is a material that exhibits various optical functions such as light diffusibility, light transmission, and light reflectivity.
- optical member examples include a member that expresses various optical functions such as light diffusibility, light transmittance, and light reflectivity, and a member that constitutes a device or an apparatus using the optical function.
- optical semiconductor devices organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optics
- Examples thereof include known or conventional optical members used in various applications such as lenses, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.
- the antireflection material of the present invention has a fine and uniform uneven shape formed by the hydrophobic porous inorganic filler on its surface as a result of the hydrophobic porous inorganic filler being uniformly dispersed throughout the cured product, Since the incident light is scattered by the uneven shape and total reflection does not occur, the gloss can be suppressed and the visibility can be improved.
- the arithmetic average surface roughness Ra of the concavo-convex shape formed on the antireflection material of the present invention is preferably in the range of 0.1 to 1.0 ⁇ m, and more preferably in the range of 0.2 to 0.8 ⁇ m.
- the arithmetic average surface roughness Ra of the concavo-convex shape is in this range, there is a tendency that a sufficient antireflection function can be exhibited without significantly impairing the total luminous flux.
- the arithmetic average surface roughness Ra is a numerical value defined by JIS B 0601-2001, and means a value measured and calculated by a method described in Examples described later.
- the resin composition constituting the antireflection material of the present invention can be preferably used as, for example, a resin composition for optical semiconductor encapsulation. That is, the resin composition of the present invention can be preferably used as a composition for sealing an optical semiconductor element in an optical semiconductor device (an optical semiconductor element sealing material in an optical semiconductor device). An optical semiconductor device in which an optical semiconductor element is sealed with an antireflection material manufactured using the resin composition (resin composition for optical semiconductor encapsulation) of the present invention (for example, 104 in FIG. 1 is the antireflection of the present invention). An optical semiconductor device made of a material is obtained.
- the sealing of the optical semiconductor element can be performed, for example, by injecting a resin composition in which a hydrophobic porous inorganic filler is uniformly dispersed into a predetermined molding die, and heat curing or photocuring under predetermined conditions.
- the curing temperature, curing time, photocuring conditions, and the like can be set as appropriate within the same range as in the preparation of the antireflection material.
- the optical semiconductor device of the present invention can exhibit an excellent antireflection function without lowering the total luminous flux and has high heat resistance (particularly, hot water resistance).
- the “optical semiconductor device of the present invention” means that the antireflective material of the present invention is used for at least a part of constituent members (for example, a sealing material, a die bonding material, etc.) of the optical semiconductor device.
- An optical semiconductor device is meant.
- the unit of the component which comprises the resin composition shown to Table 1, 2 is a weight part.
- Production Example 1 100 parts by weight of a curing agent (trade name “Licacid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.), 0.5 part by weight of a curing accelerator (trade name “U-CAT 18X”, manufactured by Sun Apro Co., Ltd.), and 1 part by weight of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) is mixed using a self-revolving stirrer (trade name “Awatori Nertaro AR-250”, manufactured by Shinky Co., Ltd., the same shall apply hereinafter) An epoxy curing agent (K agent) was produced.
- a curing agent trade name “Licacid MH-700”, manufactured by Shin Nippon Rika Co., Ltd.
- a curing accelerator trade name “U-CAT 18X”, manufactured by Sun Apro Co., Ltd.
- ethylene glycol manufactured by Wako Pure Chemical Industries, Ltd.
- Example 1 100 parts by weight of an alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) and 101.5 parts by weight of the epoxy curing agent obtained in Production Example 1 were mixed using a self-revolving stirrer, Defoaming was carried out to produce a curable epoxy resin composition.
- 100 parts by weight of the curable epoxy resin composition obtained above and 20 parts by weight of a hydrophobic porous inorganic filler (trade name “Silo Hovic 702”, manufactured by Fuji Silysia Chemical Co., Ltd.)
- a curable epoxy resin composition obtained by mixing and defoaming was cast into an optical semiconductor lead frame (InGaN element, 3.5 mm ⁇ 2.8 mm) shown in FIG.
- FIG. 1 100 is a reflector, 101 is a metal wiring, 102 is an optical semiconductor element, 103 is a bonding wire, and 104 is a sealing material (antireflection material).
- 100 is a reflector
- 101 is a metal wiring
- 102 is an optical semiconductor element
- 103 is a bonding wire
- 104 is a sealing material (antireflection material).
- Examples 2 to 13 and Comparative Examples 1 to 13 Except having changed the composition of the curable epoxy resin composition, the hydrophobic porous inorganic filler, and the porous inorganic filler (not hydrophobized) as shown in Tables 1 and 2, the same as in Example 1 An optical semiconductor device was manufactured.
- Hot water resistance test heat resistance in boiling water After immersing the optical semiconductor devices obtained in Examples and Comparative Examples in boiling water for 30 minutes, the appearance was visually evaluated. The case where the appearance was the same as that before the test was marked with ⁇ , and the case where the appearance became cloudy was marked with ⁇ .
- Silo Hovic 702 Trade name “Silo Hovic 702”, manufactured by Fuji Silysia Chemical Co., Ltd., porous silica filler that has been subjected to hydrophobic surface treatment with polydimethylsiloxane, volume average particle diameter: 4.1 ⁇ m; hydrophobic surface treatment Specific surface area of porous silica filler before being applied: 350 m 2 / g; oil absorption: 170 mL / 100 g
- Silo Hovic 4004 trade name “Silo Hovic 4004”, manufactured by Fuji Silysia Chemical Ltd., porous silica filler treated with a hydrophobic surface with polydimethylsiloxane, volume average particle size: 8.0 ⁇ m; hydrophobic surface treatment Specific surface area of porous silica filler before being applied: 350 m 2 / g; oil absorption: 165 m
- Silicia 430 trade name “Cylicia 430”, manufactured by Fuji Silysia Chemical Ltd., volume average particle size: 4.1 ⁇ m; specific surface area: 350 m 2 / g; average pore size: 17 nm; pore volume: 1.25 mL / g Oil absorption: 230 mL / 100 g Pyrosphere C-1504: Trade name “Cyrosphere C-1504”, manufactured by Fuji Silysia Chemical Ltd., volume average particle size: 4.5 ⁇ m; specific surface area: 520 m 2 / g; average pore size: 12 nm; pore volume : 1.5 mL / g; Oil absorption: 290 mL / 100 g Sunsphere H-52: trade name “Sunsphere H-52” manufactured by AGC S-Tech Co., Ltd., volume average particle diameter: 5 ⁇ m; specific surface area: 700 m 2 / g; average pore diameter: 10 n
- Celoxide 2021P Trade name “Celoxide 2021P” [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate], manufactured by Daicel Corporation
- YD-128 Trade name “YD-128” [Bisphenol A type epoxy Resin], manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- TEPIC-VL trade name “TEPIC-VL” [triglycidyl isocyanurate], manufactured by Nissan Chemical Industries, Ltd.
- 152 trade name “152” [phenol novolac type epoxy resin ], Manufactured by Mitsubishi Chemical Corporation YL7410: trade name “YL7410” [aliphatic epoxy compound], manufactured by Mitsubishi Chemical Corporation X-22-169AS: trade name “X-22-169AS” [modified silicone oil (both ends) Polydimethylsiloxane having a cyclohexene oxide group)], Shin Chemical Industry Co., Ltd.
- X-40-2670 trade name "X-40-2670” [cyclic siloxanes having a cyclohexene oxide group], manufactured by Shin-Etsu Chemical Co., Ltd.
- U-CAT 18X Trade name “U-CAT 18X "[curing accelerator], manufactured by San Apro Co., Ltd.
- Ethylene glycol manufactured by Wako Pure Chemical Industries, Ltd.
- the hot water resistance test is ⁇
- the reflection of the fluorescent lamp is ⁇ Or ⁇
- arithmetic average surface roughness Ra is in the range of 0.10 to 1.0 ⁇ m
- total luminous flux is in the range of 0.60 lm or more
- excellent antireflection function and illuminance excellent heat resistance, especially hot water resistance
- the hot water resistance test is x. Yes, it was inferior in hot water resistance.
- An antireflection material comprising a cured product of a resin composition in which a hydrophobic porous inorganic filler is dispersed, wherein irregularities that suppress reflection are formed on the surface of the cured product.
- Prevention material [2] The antireflection material according to the above [1], wherein the hydrophobic porous inorganic filler is uniformly dispersed throughout the cured product, and irregularities that suppress reflection are formed on the surface.
- the porous inorganic filler constituting the hydrophobic porous inorganic filler is an inorganic glass [for example, borosilicate glass, borosilicate soda glass, sodium silicate glass , Aluminum silicate glass, quartz, etc.], silica, alumina, zircon iron oxide, zinc oxide, zirconium oxide, magnesium oxide, titanium oxide, aluminum oxide, fosterite, steatite, spinel, clay, kaolin, dolomite, hydroxyapatite, nepheline It is at least one powder selected from the group consisting of cynite, cristobalite, wollastonite, diatomaceous earth, and talc, and has a porous structure, or a molded body thereof (for example, spherical beads).
- inorganic glass for example, borosilicate glass, borosilicate soda glass, sodium silicate glass , Aluminum silicate glass, quartz, etc.
- silica alumina
- zircon iron oxide zinc
- the hydrophobic porous inorganic filler is at least one selected from the group consisting of a metal oxide, a silane coupling agent, a titanium coupling agent, an organic acid, a polyol, and an organosilicon compound.
- the antireflection material according to [4], wherein the hydrophobic surface treatment agent is an organosilicon compound.
- the organic silicon compound is at least one selected from the group consisting of trimethylchlorosilane, hexamethyldisiloxane, dimethyldichlorosilane, octamethylcyclotetrasilane, polydimethylsiloxane, hexadecylsilane, methacrylsilane, and silcorn oil.
- the antireflection material according to [5] above, which is a seed (preferably polydimethylsiloxane).
- the hydrophobic porous inorganic filler is at least one selected from the group consisting of hydrophobic porous inorganic glass and hydrophobic porous silica (hydrophobic porous silica filler) (preferably, hydrophobic porous The antireflection material according to any one of the above [1] to [6], which is a silica filler).
- At least one porous silica selected from the group consisting of fused silica, crystalline silica, high-purity synthetic silica, and colloidal silica is treated with the hydrophobic surface treating agent.
- the antireflection material according to [7], wherein [9] The shape of the hydrophobic porous inorganic filler is at least one selected from the group consisting of powder, spherical shape, crushed shape, fibrous shape, needle shape, and scale shape (preferably spherical shape or crushed shape).
- the hydrophobic porous inorganic filler is obtained by subjecting the surface of the porous inorganic filler to a hydrophobic treatment, and the specific surface area of the porous inorganic filler before the hydrophobic treatment is 200 m 2 / g or more (preferably 200
- the content of the hydrophobic porous inorganic filler with respect to the total amount (100% by weight) of the antireflection material is 4 to 40% by weight (preferably 4 to 35% by weight, more preferably 4 to 30% by weight).
- the antireflection material according to any one of [1] to [12] above.
- the content (blending amount) of the hydrophobic porous inorganic filler with respect to the resin composition (100 parts by weight) constituting the antireflection material is 5 to 80 parts by weight (preferably 5 to 70 parts by weight, more preferably Is 5 to 60 parts by weight), and the antireflection material according to any one of [1] to [13] above.
- the curable resin composition comprises a composition comprising at least one curable compound selected from the group consisting of an epoxy resin (A), a silicone resin (B), and an acrylic resin (C).
- the curable resin composition is composed of a composition (curable epoxy resin composition) containing an epoxy resin (A).
- the epoxy resin (A) is a bisphenol A type epoxy resin, an isocyanurate having one or more epoxy groups in the molecule, a novolac type epoxy resin, an alicyclic epoxy compound, an aliphatic epoxy compound, and a molecule.
- the alicyclic epoxy compound includes a compound having a cyclohexene oxide group in the molecule (preferably a compound having two or more cyclohexene oxide groups in the molecule). Wood.
- the compound represented by the formula (1) is 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, and the following formulas (1-1) to (
- the antireflection material according to [20] above which is at least one alicyclic epoxy compound selected from the group consisting of compounds represented by 1-10).
- l and m each represents an integer of 1 to 30.
- R in the formula (1-5) is an alkylene group having 1 to 8 carbon atoms.
- N1 to n6 in the following formulas (1-9) and (1-10) each represents an integer of 1 to 30.
- the content (blending amount) of the epoxy resin (A) is 25 to 99.8% by weight (for example, 25 to 95% by weight) with respect to the total amount (100% by weight) of the curable epoxy resin composition.
- the antireflection material according to any one of the above [17] to [22] .
- the content (blending amount) of the alicyclic epoxy compound is 20 to 99.8% by weight (preferably 40 to 95% by weight) with respect to the total amount (100% by weight) of the curable epoxy resin composition. (For example, 40 to 60% by weight), more preferably 50 to 95% by weight, still more preferably 60 to 90% by weight, and most preferably 70 to 85% by weight), any of the above [18] to [23]
- the antireflection material as described in any one.
- the ratio of the alicyclic epoxy compound to the total amount (100 wt%) of the epoxy compound contained in the curable epoxy resin composition is 40 to 100 wt% (for example, 40 to 90 wt%) (preferably 80 wt%).
- the curable epoxy resin composition further comprises a curing agent (D) and a curing accelerator (E), or a curing catalyst (F) (preferably, the curing agent (D) and the curing accelerator (E).
- the antireflection material according to any one of the above [17] to [25].
- the curing agent (D) is an acid anhydride (acid anhydride curing agent), an amine (amine curing agent), a polyamide resin, an imidazole (imidazole curing agent), a polymercaptan (polyethylene). Mercaptan-based curing agent), phenols (phenol-based curing agent), polycarboxylic acids, dicyandiamides, and at least one selected from the group consisting of organic acid hydrazides (preferably acid anhydride-based curing agents), [26] The antireflection material according to [26].
- the acid anhydride curing agent is a liquid mixture obtained by dissolving a liquid acid anhydride at 25 ° C or a solid acid anhydride at 25 ° C in a liquid acid anhydride at 25 ° C.
- the antireflection material according to [27] above.
- the content (blending amount) of the curing agent (D) is 50 to 200 parts by weight (preferably 75 to 150 parts by weight) with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition. Part, more preferably 100 to 120 parts by weight), the antireflection material according to any one of the above [26] to [28].
- the content (blending amount) of the curing accelerator (E) is 0.05 to 5 parts by weight (preferably 0 with respect to 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition). 1 to 3 parts by weight, more preferably 0.2 to 3 parts by weight, still more preferably 0.25 to 2.5 parts by weight), according to any one of [26] to [29] above Anti-reflective material.
- the content (blending amount) of the polyhydric alcohol is 0.05 to 5 parts by weight (preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of epoxy compounds contained in the curable epoxy resin composition). 3 parts by weight, more preferably 0.2 to 3 parts by weight, and still more preferably 0.25 to 2.5 parts by weight).
- the reflection according to [33], wherein the content (blending amount) of the phosphor is 0.5 to 20% by weight with respect to the total amount (100% by weight) of the curable epoxy resin composition. Prevention material.
- the arithmetic mean surface roughness Ra of the uneven shape formed on the antireflection material is in the range of 0.1 to 1.0 ⁇ m (preferably in the range of 0.2 to 0.8 ⁇ m). 1] to [34] The antireflection material according to any one of [34]. [36] The antireflection material according to any one of [1] to [35], which is used for sealing an optical semiconductor. [37] An optical semiconductor device in which an optical semiconductor element is sealed with the antireflection material according to [36].
- [38] A resin composition in which a hydrophobic porous inorganic filler is dispersed, which is used for producing the antireflection material according to any one of [1] to [36].
- a method for producing an antireflection material wherein the resin composition according to any one of the above [38] to [40] is cured, wherein unevenness for suppressing reflection is formed on a surface.
- the antireflection material of the present invention has high heat resistance, in particular, hot water resistance, in addition to high transparency and an excellent antireflection function, and thus is suitable as a resin for optical materials (used for forming optical materials).
- the optical member include a member that expresses various optical functions such as light diffusibility, light transmittance, and light reflectivity, and a member that constitutes a device or an apparatus using the optical function.
- optical semiconductor devices organic EL devices, adhesives, electrical insulating materials, laminates, coatings, inks, paints, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optics
- optical members include known or conventional optical members used in various applications such as lenses, optical modeling, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.
- Reflector resin composition for light reflection
- Metal wiring electrode
- Optical semiconductor element 103
- Bonding wire 104: Sealing material (antireflection material)
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Abstract
Description
従来、樹脂層の表面に反射防止機能を付与する方法としては、樹脂にガラスビーズ、シリカ等の無機フィラーを分散させることによって入射光を散乱させる方法が知られている(例えば、特許文献1参照)。
また、本発明の他の目的は、光半導体封止用である、上記反射防止材を提供することである。
さらに、本発明の他の目的は、上記反射防止材により光半導体素子が封止された光半導体装置を提供することである。
また、本発明の他の目的は、上記反射防止材の製造に適した樹脂組成物、並びに当該樹脂組成物を用いた上記反射防止材の製造方法を提供することである。
本発明者は上記課題を解決するために鋭意検討した結果、反射防止材を構成する樹脂層中のフィラーとして疎水性多孔質無機フィラーを配合したところ、少量の添加でも十分な反射防止機能が付与され、さらに高い耐熱性も有することを見出した。これにより、光源の全光束を大幅に低下させることなく十分な反射防止機能と優れた耐熱性を兼ね備えた反射防止材が提供され、光半導体装置における光半導体素子を封止するための材料として極めて適していることを見出し、本発明を完成するに至った。
また、本発明の樹脂組成物は上記構成を有するため、上記反射防止材を製造するために、極めて適している。
本発明の反射防止材は、疎水性多孔質無機フィラーが分散された樹脂組成物の硬化物から構成され、当該疎水性多孔質無機フィラーが当該硬化物の表面に反射を抑える凹凸を形成することを特徴とするものである。
また、本発明の樹脂組成物は、疎水性多孔質無機フィラーが分散されていることを特徴とし、上記反射防止材を製造するために使用されるものである。
また、疎水性多孔質無機フィラーはその表面が疎水性を示すため、これを含む硬化物は煮沸水等の過酷な加熱条件でも劣化しにくい高い耐熱性を示し、耐久性に優れる。
なお、本明細書において、疎水性多孔質無機フィラーの添加量(使用量)が少量(少ない)とは、重量換算で少ないことを意味し、容量(体積)換算で少ないことを意味するものではない。
以下、各構成要素について詳細に説明する。
本発明の反射防止材又は樹脂組成物における疎水性多孔質無機フィラーは、樹脂組成物又は、その硬化物全体に行き渡って均一に分散しており、分散状態が安定した結果、硬化物の表面に存在する疎水性多孔質無機フィラーが入射光を散乱させるための凹凸を形成する働きを有する。
樹脂組成物の成分との相溶性や分散性が向上すると共に、硬化物の耐熱性を向上させるという観点から、疎水性表面処理剤としては、有機ケイ素化合物(例えば、トリメチルクロロシラン、ヘキサメチルジシロキサン、ジメチルジクロロシラン、オクタメチルシクロテトラシラン、ポリジメチルシロキサン、ヘキサデシルシラン、メタクリルシラン、シルコーンオイル等)が好ましく、ポリジメチルシロキサン等がより好ましい。
中でも、疎水性多孔質無機フィラーとしては、樹脂組成物又は、その硬化物全体に行き渡って均一に分散して、硬化物の表面に凹凸を効率的に形成できると共に優れた耐熱性を示すという観点で、疎水性多孔質無機ガラス又は疎水性多孔質シリカ(疎水性多孔質シリカフィラー)が好ましい。
本発明の反射防止材における硬化物を構成する樹脂組成物は、特に限定されるものではないが、光半導体装置における光半導体素子の封止材、即ち、光半導体封止用樹脂組成物として適したものが好ましく使用可能であり、例えば、熱又は光により硬化して、高い透明性を有し、耐久性(例えば、加熱によっても透明性が低下しにくい特性、高温の熱や熱衝撃が加えられてもクラックや被着体からの剥離が生じにくい特性等)にも優れる硬化物を与える硬化性樹脂組成物を好適に使用できる。
また、本発明の反射防止材は、光半導体封止用樹脂組成物の用途に限定されるものではなく、例えば、後述の各種光学部材等にも適用可能であり、それぞれの用途に適した樹脂(例えば、ポリオレフィン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂など)にも適用可能である。
本発明の反射防止材における硬化物を構成する樹脂組成物としては、耐熱性、透明性、耐久性等に優れる硬化性エポキシ樹脂組成物、硬化性シリコーン樹脂組成物、硬化性アクリル樹脂組成物が好ましく、硬化性エポキシ樹脂組成物がより好ましい。
上記硬化性エポキシ樹脂組成物(「本発明の硬化性エポキシ樹脂組成物」と称する場合がある)は、エポキシ樹脂(A)を必須成分として含む硬化性組成物である。本発明の硬化性エポキシ樹脂組成物は、さらに、硬化剤(D)及び硬化促進剤(E)、又は、硬化触媒(F)を必須成分として含む。即ち、本発明の硬化性エポキシ樹脂組成物は、エポキシ樹脂(A)と硬化剤(D)と硬化促進剤(E)とを必須成分として含む組成物、又は、エポキシ樹脂(A)と硬化触媒(F)とを必須成分として含む組成物である。本発明の硬化性エポキシ樹脂組成物は、上述の必須成分以外のその他の成分を含んでいてもよい。
本発明の硬化性エポキシ樹脂組成物におけるエポキシ樹脂(A)は、分子内に1個以上のエポキシ基(オキシラン環)を有する化合物であり、公知乃至慣用のエポキシ化合物から任意に選択して用いることができる。エポキシ樹脂(A)としては、例えば、芳香族エポキシ化合物(芳香族エポキシ樹脂)、脂肪族エポキシ化合物(脂肪族エポキシ樹脂)、脂環式エポキシ化合物(脂環式エポキシ樹脂)、複素環式エポキシ化合物(複素環式エポキシ樹脂)、分子内にエポキシ基を1個以上有するシロキサン誘導体等が挙げられる。
本発明の硬化性エポキシ樹脂組成物の必須成分のひとつである硬化剤(D)は、エポキシ化合物と反応することにより硬化性エポキシ樹脂組成物を硬化させる働きを有する化合物である。硬化剤(D)としては、特に限定されず、エポキシ樹脂用硬化剤として周知慣用のものを使用することができ、例えば、酸無水物類(酸無水物系硬化剤)、アミン類(アミン系硬化剤)、ポリアミド樹脂、イミダゾール類(イミダゾール系硬化剤)、ポリメルカプタン類(ポリメルカプタン系硬化剤)、フェノール類(フェノール系硬化剤)、ポリカルボン酸類、ジシアンジアミド類、有機酸ヒドラジド等が挙げられる。
本発明の硬化性エポキシ樹脂組成物の必須成分のひとつである硬化促進剤(E)は、エポキシ化合物の反応(特に、エポキシ樹脂(A)と硬化剤(D)との反応)の反応速度を促進する機能を有する化合物である。硬化促進剤(E)としては、エポキシ樹脂用硬化促進剤として周知慣用のものを使用することができ、特に限定されないが、例えば、1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)、及びその塩(例えば、フェノール塩、オクチル酸塩、p-トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等);1,5-ジアザビシクロ[4.3.0]ノネン-5(DBN)、及びその塩(例えば、フェノール塩、オクチル酸塩、p-トルエンスルホン酸塩、ギ酸塩、テトラフェニルボレート塩等);ベンジルジメチルアミン、2,4,6-トリス(ジメチルアミノメチル)フェノール、N,N-ジメチルシクロヘキシルアミン等の3級アミン;2-エチル-4-メチルイミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール等のイミダゾール;リン酸エステル、トリフェニルホスフィン等のホスフィン類;テトラフェニルホスホニウムテトラ(p-トリル)ボレート等のホスホニウム化合物;オクチル酸スズ、オクチル酸亜鉛等の有機金属塩;金属キレート等が挙げられる。
本発明の硬化性エポキシ樹脂組成物の必須成分のひとつである硬化触媒(F)は、エポキシ化合物等のカチオン重合性化合物の硬化反応(重合反応)を開始及び/又は促進させることにより、硬化性エポキシ樹脂組成物を硬化させる働きを有する化合物である。硬化触媒(F)としては、特に限定されないが、例えば、熱によりカチオン種を発生して、重合を開始させるカチオン重合開始剤(熱カチオン重合開始剤)や、ルイス酸・アミン錯体、ブレンステッド酸塩類、イミダゾール類等が挙げられる。
本発明の硬化性エポキシ樹脂組成物は、多価アルコールを含んでいてもよい。特に、本発明の硬化性エポキシ樹脂組成物が硬化剤(D)及び硬化促進剤(E)を含む場合には、硬化をより効率的に進行させることができる点で、さらに多価アルコールを含むことが好ましい。多価アルコールとしては、公知乃至慣用の多価アルコールを使用することができ、特に限定されないが、例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、ネオペンチルグリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。
本発明の硬化性エポキシ樹脂組成物は、蛍光体を含んでいてもよい。本発明の硬化性エポキシ樹脂組成物が蛍光体を含む場合には、光半導体装置における光半導体素子の封止用途(封止材用途)、即ち、光半導体封止用樹脂組成物として特に好ましく使用できる。上記蛍光体としては、公知乃至慣用の蛍光体(特に、光半導体素子の封止用途において使用される蛍光体)を使用でき、特に限定されないが、例えば、一般式A3B5O12:M[式中、Aは、Y、Gd、Tb、La、Lu、Se、及びSmからなる群より選択された1種以上の元素を示し、Bは、Al、Ga、及びInからなる群より選択された1種以上の元素を示し、Mは、Ce、Pr、Eu、Cr、Nd、及びErからなる群より選択された1種以上の元素を示す]で表されるYAG系の蛍光体微粒子(例えば、Y3Al5O12:Ce蛍光体微粒子、(Y,Gd,Tb)3(Al,Ga)5O12:Ce蛍光体微粒子等)、シリケート系蛍光体微粒子(例えば、(Sr,Ca,Ba)2SiO4:Eu等)等が挙げられる。なお、蛍光体は、例えば、分散性向上のために、有機基(例えば、長鎖アルキル基、リン酸基等)等により表面が修飾されたものであってもよい。本発明の硬化性エポキシ樹脂組成物において蛍光体は、1種を単独で使用することもできるし、2種以上を組み合わせて使用することもできる。また、蛍光体としては市販品を使用することができる。
本発明の硬化性エポキシ樹脂組成物は、硬化性や透明性等に大きな悪影響が及ばない範囲で、上記以外のその他の成分を含んでいてもよい。上記その他の成分としては、例えば、直鎖又は分岐鎖を有するシリコーン系樹脂、脂環を有するシリコーン系樹脂、芳香環を有するシリコーン系樹脂、かご型/ラダー型/ランダム型のシルセスキオキサン、γ-グリシドキシプロピルトリメトキシシラン等のシランカップリング剤、シリコーン系やフッ素系の消泡剤等が挙げられる。上記その他の成分の含有量(配合量)は、特に限定されないが、硬化性エポキシ樹脂組成物の全量(100重量%)に対して、5重量%以下(例えば、0~3重量%)が好ましい。
上記硬化性シリコーン樹脂組成物(「本発明の硬化性シリコーン樹脂組成物」と称する場合がある)は、硬化性化合物としてシリコーン樹脂(B)を必須成分として含む硬化性組成物である。本発明の硬化性シリコーン樹脂組成物は、シリコーン樹脂(B)以外の成分を含んでいてもよい。
上記付加反応硬化性シリコーン樹脂組成物としては、例えば、シリコーン樹脂(B)として分子内に2個以上のアルケニル基を有するポリシロキサン(B1)を含有し、さらに必要に応じて、分子内に1個以上(好ましくは2個以上)のヒドロシリル基を有するポリシロキサンや金属硬化触媒等を含む硬化性シリコーン樹脂組成物が挙げられる。
(R7SiO3/2)a1(R7 2SiO2/2)a2(R7 3SiO1/2)a3(SiO4/2)a4(ZO1/2)a5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、R7は、同一又は異なって、1価の置換又は無置換炭化水素基であり、上述の具体例(例えば、アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン化炭化水素基等)が挙げられる。但し、R7の一部はアルケニル基(特にビニル基)であり、その割合は、分子内に2個以上となる範囲に制御される。例えば、R7の全量(100モル%)に対するアルケニル基の割合は、0.1~40モル%が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のR7としては、アルキル基(特にメチル基)、アリール基(特にフェニル基)が好ましい。
(R8 2SiO2/2)b1(R8 3SiO1/2)b2(R8SiO3/2)b3(SiO4/2)b4(RA)b5(ZO1/2)b6
で表されるポリオルガノシロキシシルアルキレンが好ましい。上記平均単位式中、R8は、同一又は異なって、1価の置換又は無置換炭化水素基であり、上述の具体例(例えば、アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン化アルキル基等)が挙げられる。但し、R8の一部はアルケニル基(特にビニル基)であり、その割合は、分子内に2個以上となる範囲に制御される。例えば、R8の全量(100モル%)に対するアルケニル基の割合は、0.1~40モル%が好ましい。アルケニル基の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、アルケニル基以外のR8としては、アルキル基(特にメチル基)、アリール基(特にフェニル基)が好ましい。
(R9SiO3/2)c1(R9 2SiO2/2)c2(R9 3SiO1/2)c3(SiO4/2)c4(ZO1/2)c5
で表されるポリオルガノシロキサンが好ましい。上記平均単位式中、R9は、同一又は異なって、水素原子、又は、1価の置換若しくは無置換炭化水素基であり、水素原子、上述の具体例(例えば、アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン化アルキル基等)が挙げられる。但し、R9の一部は水素原子(ヒドロシリル基を構成する水素原子)であり、その割合は、ヒドロシリル基が分子内に1個以上(好ましくは2個以上)となる範囲に制御される。例えば、R9の全量(100モル%)に対する水素原子の割合は、0.1~40モル%が好ましい。水素原子の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、水素原子以外のR9としては、アルキル基(特にメチル基)、アリール基(特にフェニル基)が好ましい。
(R10 2SiO2/2)d1(R10 3SiO1/2)d2(R10SiO3/2)d3(SiO4/2)d4(RA)d5(ZO1/2)d6
で表されるポリオルガノシロキシシルアルキレンが好ましい。上記平均単位式中、R10は、同一又は異なって、水素原子、又は1価の置換若しくは無置換炭化水素基であり、水素原子及び上述の具体例(例えば、アルキル基、アルケニル基、アリール基、アラルキル基、ハロゲン化アルキル基等)が挙げられる。但し、R10の一部は水素原子であり、その割合は、分子内に1個以上(好ましくは2個以上)となる範囲に制御される。例えば、R10の全量(100モル%)に対する水素原子の割合は、0.1~50モル%が好ましく、より好ましくは5~35モル%である。水素原子の割合を上記範囲に制御することにより、硬化性シリコーン樹脂組成物の硬化性がより向上する傾向がある。また、水素原子以外のR10としては、アルキル基(特にメチル基)、アリール基(特にフェニル基)が好ましい。特に、R10の全量(100モル%)に対するアリール基(特にフェニル基)の割合は、5モル%以上(例えば、5~80モル%)が好ましく、より好ましくは10モル%以上である。
上記縮合反応硬化性シリコーン樹脂組成物としては、例えば、シリコーン樹脂(B)として分子内に2個以上のシラノール基(Si-OH)又はシルアルコキシ基(Si-OR)を有するポリシロキサン(B2)を含有し、さらに必要に応じて金属硬化触媒等を含む硬化性シリコーン樹脂組成物が挙げられる。なお、ポリシロキサン(B2)は、シラノール基とシルアルコキシ基のいずれか一方のみを有するものであってもよいし、シラノール基とシルアルコキシ基の両方を有するものであってもよい。シラノール基とシルアルコキシ基の両方を有する場合、これらの合計数が分子内に2個以上であればよい。
R11 eSi(OR12)f(OH)gO(4-e-f-g)/2
[上記平均組成式中、R11は、同一又は異なって、炭素数1~20の1価の有機基を示す。R12は、同一又は異なって、炭素数1~4の1価の有機基を示す。eは0.8~1.5の数、fは0~0.3の数、gは0~0.5の数を示す。f+gは0.001以上1.2未満の数である。また、e+f+gは、0.801以上2未満の数である。]
上記硬化性アクリル樹脂組成物(「本発明の硬化性アクリル樹脂組成物」と称する場合がある)は、硬化性化合物としてアクリル樹脂(C)を必須成分として含む硬化性組成物である。本発明の硬化性アクリル樹脂組成物は、アクリル樹脂(C)以外の成分を含んでいてもよい。
本発明の反射防止材は、上記疎水性多孔質無機フィラーが上記樹脂組成物又は、その硬化物全体に行き渡って均一に分散しており、分散状態が安定した結果、硬化物の表面に存在する疎水性多孔質無機フィラーが凹凸形状を形成して、入射光を散乱させることにより反射防止機能を発揮する。また、疎水性多孔質無機フィラー表面の多孔質構造も入射光を散乱させることができ、さらに反射防止機能が向上する。
また、疎水性多孔質無機フィラーはその表面が疎水性を示すため、これを含む硬化物は煮沸水等の過酷な加熱条件でも劣化しにくい高い耐熱性、特に、耐熱水性を示し、耐久性に優れる。
上記疎水性多孔質無機フィラーを上記硬化物全体に行き渡らせる方法は、特に限定させず、例えば、硬化物を構成する樹脂組成物に疎水性多孔質無機フィラーを均一に分散させた後に硬化させる方法等が挙げられる。本発明の反射防止材を効率的に製造するためには、疎水性多孔質無機フィラーを均一に分散させた後に硬化させる方法が好ましい。
以下に、本発明の反射防止材の製造方法の一態様を説明するが、本発明はこれに限定されるものではない。
疎水性多孔質無機フィラーが均一に分散した樹脂組成物を硬化させて硬化物(以下、「本発明の硬化物」と称する場合がある)とすることにより、本発明の反射防止材を得ることができる。
硬化前の樹脂組成物の全量(100重量%)に対する、硬化中に揮発する成分の量は、特に限定されないが、好ましくは10重量%以下であり、より好ましくは8重量%以下であり、さらに好ましくは5重量%以下である。硬化中に揮発する成分の量が10重量%以下であることにより、硬化物の寸法安定性が高くなり、好ましい。本発明の硬化前の樹脂組成物は、疎水性多孔質無機フィラーを用いることで少量の添加で反射防止機能を発現することができるため、溶剤(トルエン等)の揮発成分を使用しなくとも液状になりやすく、硬化中に揮発する成分の量を少なくすることができる。
また、光照射により硬化させる場合は、例えば、i-線(365nm)、h-線(405nm)、g-線(436nm)等を含む光(放射線)を、照度10~1200mW/cm2、照射光量20~2500mJ/cm2で照射することにより本発明の反射防止材を得ることができる。放射線による硬化物の劣化を抑える観点と、生産性の観点から、好ましくは放射線の照射光量20~600mJ/cm2、より好ましくは照射光量20~300mJ/cm2が望ましい。照射には、高圧水銀ランプ、キセノンランプ、カーボンアークランプ、メタルハライドランプ、レーザー光等を照射源として使用することができる。
本発明の反射防止材は、上述の通り、高い透明性と優れた反射防止機能に加え、高い耐熱性(特に、耐熱水性)を兼ね備えるため、光学材料用の(光学材料を形成する用途に用いられる)樹脂として好適に使用することができる。光学材料とは、光拡散性、光透過性、光反射性等の各種の光学的機能を発現する材料である。本発明の反射防止材を使用することで、本発明の硬化物(光学材料)を少なくとも含む光学部材が得られる。なお、当該光学部材は、本発明の反射防止材のみから構成されたものであってもよいし、本発明の反射防止材が一部のみに使用されたものであってもよい。光学部材としては、光拡散性、光透過性、光反射性等の各種の光学的機能を発現する部材や、上記光学的機能を利用した装置や機器を構成する部材等が挙げられ、特に限定されず、例えば、光半導体装置、有機EL装置、接着剤、電気絶縁材、積層板、コーティング、インク、塗料、シーラント、レジスト、複合材料、透明基材、透明シート、透明フィルム、光学素子、光学レンズ、光造形、電子ペーパー、タッチパネル、太陽電池基板、光導波路、導光板、ホログラフィックメモリ、光ピックアップセンサー等の各種用途において使用される公知乃至慣用の光学部材が例示される。
なお、本発明において算術平均表面粗さRaは、JIS B 0601-2001により定義される数値であり、後述の実施例に記載の方法により測定、算出されたものを意味するものとする。
硬化剤(商品名「リカシッドMH-700」、新日本理化(株)製)100重量部、硬化促進剤(商品名「U-CAT 18X」、サンアプロ(株)製)0.5重量部、及びエチレングリコール(和光純薬工業(株)製)1重量部を、自公転式撹拌装置(商品名「あわとり練太郎 AR-250」、(株)シンキー製、以下同じ)を用いて混合し、エポキシ硬化剤(K剤)を製造した。
脂環式エポキシ化合物(商品名「セロキサイド2021P」、(株)ダイセル製)100重量部、製造例1で得られたエポキシ硬化剤101.5重量部を自公転式撹拌装置を用いて混合し、脱泡して、硬化性エポキシ樹脂組成物を製造した。
上記で得られた硬化性エポキシ樹脂組成物100重量部、及び疎水性多孔質無機フィラー(商品名「サイロホービック702」、富士シリシア化学(株)製)20重量部を自公転式撹拌装置を用いて混合し、脱泡して得られた硬化性エポキシ樹脂組成物を図1に示す光半導体のリードフレーム(InGaN素子、3.5mm×2.8mm)に注型した後、150℃の樹脂硬化オーブンで5時間加熱することで、本発明の反射防止材により光半導体素子が封止された光半導体装置を製造した。なお、図1において、100はリフレクター、101は金属配線、102は光半導体素子、103はボンディングワイヤ、104は封止材(反射防止材)を示し、104の全体に渡り疎水性多孔質無機フィラーが均一に分散しており、そのうちの上部表面に存在する疎水性多孔質無機フィラーにより均一で微細な凹凸形状が形成されている(凹凸形状は図示略)。
硬化性エポキシ樹脂組成物、疎水性多孔質無機フィラー、多孔質無機フィラー(疎水化処理されていないもの)の組成を表1、2に示すように変更したこと以外は実施例1と同様にして、光半導体装置を製造した。
上記で製造した光半導体装置について、下記の評価を行った。結果を表1、2のそれぞれに示す。
実施例、比較例で得られた光半導体装置を、沸騰した水に30分間浸漬した後、外観を目視で評価した。外観が試験前と同様な場合を○、白濁した場合を×とした。
実施例、比較例で得られた光半導体装置の上面(図1の封止材104の上面)に点灯した蛍光灯を当てて反射を見た際に、反射防止材に映る蛍光灯の鮮明さを目視で3段階評価した。
蛍光灯の輪郭が認識できない場合を○、輪郭が不鮮明ながら認識できる場合を△、輪郭が鮮明に認識できる場合を×とした。
(3)算術平均表面粗さRa
実施例、比較例で得られた光半導体装置の上面(図1の封止材104の上面)を、レーザー顕微鏡(商品名「形状測定レーザマイクロスコープ VK-8710」、キーエンス社製)を用いて測定した。
実施例、比較例で得られた各光半導体装置について、5V、20mAの条件で通電した際の全光束を、全光束測定機(商品名「マルチ分光放射測定システム OL771」、オプトロニックラボラトリーズ社製)を用いて測定した。
実施例、比較例で得られた各光半導体装置について、下記(a)~(d)を全て満足する場合を○(良好である)、下記(a)~(d)のいずれかを満足しない場合を×(不良である)と判定した。
(a)上記(1)において測定された耐熱水性が、○である。
(b)上記(2)において測定された蛍光灯の映り込みが、○又は△である。
(c)上記(3)において測定された算術平均表面粗さRaが0.10~1.0μmである。
(d)上記(4)において測定された全光束が0.60lm以上である。
(疎水性多孔質無機フィラー)
サイロホービック702:商品名「サイロホービック702」、富士シリシア化学(株)製、ポリジメチルシロキサンで疎水性表面処理された多孔質シリカフィラー、体積平均粒子径:4.1μm;疎水性表面処理される前の多孔質シリカフィラーの比表面積:350m2/g;吸油量:170mL/100g
サイロホービック4004:商品名「サイロホービック4004」、富士シリシア化学(株)製、ポリジメチルシロキサンで疎水性表面処理された多孔質シリカフィラー、体積平均粒子径:8.0μm;疎水性表面処理される前の多孔質シリカフィラーの比表面積:350m2/g;吸油量:165mL/100g
サイロホービック505:商品名「サイロホービック505」、富士シリシア化学(株)製、ポリジメチルシロキサンで疎水性表面処理された多孔質シリカフィラー、体積平均粒子径:3.9μm;疎水性表面処理される前の多孔質シリカフィラーの比表面積:500m2/g;吸油量:110mL/100g
サイリシア430:商品名「サイリシア430」、富士シリシア化学(株)製、体積平均粒子径:4.1μm;比表面積:350m2/g;平均細孔径:17nm;細孔容積:1.25mL/g;吸油量:230mL/100g
サイロスフェアC-1504:商品名「サイロスフェアC-1504」、富士シリシア化学(株)製、体積平均粒子径:4.5μm;比表面積:520m2/g;平均細孔径:12nm;細孔容積:1.5mL/g;吸油量:290mL/100g
サンスフェアH-52:商品名「サンスフェアH-52」、AGCエスアイテック(株)製、体積平均粒子径:5μm;比表面積:700m2/g;平均細孔径:10nm;細孔容積:2mL/g;吸油量:300mL/100g
セロキサイド2021P:商品名「セロキサイド2021P」[3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート]、(株)ダイセル製
YD-128:商品名「YD-128」[ビスフェノールA型エポキシ樹脂]、新日鐡住金化学(株)製
TEPIC-VL:商品名「TEPIC-VL」[トリグリシジルイソシアヌレート]、日産化学工業(株)製
152:商品名「152」[フェノールノボラック型エポキシ樹脂]、三菱化学(株)製
YL7410:商品名「YL7410」[脂肪族エポキシ化合物]、三菱化学(株)製
X-22-169AS:商品名「X-22-169AS」[変性シリコーンオイル(両末端にシクロヘキセンオキシド基を有するポリジメチルシロキサン)]、信越化学工業(株)製
X-40-2670:商品名「X-40-2670」[シクロヘキセンオキシド基を有する環状シロキサン]、信越化学工業(株)製
MH-700:商品名「リカシッドMH-700」[4-メチルヘキサヒドロ無水フタル酸/ヘキサヒドロ無水フタル酸=70/30]、新日本理化(株)製
U-CAT 18X:商品名「U-CAT 18X」[硬化促進剤]、サンアプロ(株)製
エチレングリコール:和光純薬工業(株)製
一方、表2に示されるように、疎水化処理されていない多孔質無機フィラーを配合した比較例の光半導体装置は、優れた反射防止機能と照度を示すものの、耐熱水性試験はいずれも×であり、耐熱水性に劣るものであった。
[1]疎水性多孔質無機フィラーが分散された樹脂組成物の硬化物からなる反射防止材であって、当該硬化物の表面に反射を抑える凹凸が形成されていることを特徴とする、反射防止材。
[2]前記疎水性多孔質無機フィラーが前記硬化物全体に渡って均一に分散しており、表面に反射を抑える凹凸を形成している、上記[1]に記載の反射防止材。
[3]疎水性多孔質無機フィラーを構成する多孔質無機フィラー(表面が疎水性処理される前の多孔質無機フィラー)が、無機ガラス[例えば、硼珪酸ガラス、硼珪酸ソーダガラス、珪酸ソーダガラス、アルミ珪酸ガラス、石英等]、シリカ、アルミナ、ジルコン酸化鉄、酸化亜鉛、酸化ジルコニウム、酸化マグネシウム、酸化チタン、酸化アルミニウム、フォステライト、ステアタイト、スピネル、クレー、カオリン、ドロマイト、ヒドロキシアパタイト、ネフェリンサイナイト、クリストバライト、ウォラストナイト、珪藻土、及びタルクからなる群から選ばれる少なくとも一種の粉体であって多孔質構造を有するもの、又はこれらの成型体(例えば、球形化したビーズ等)である、上記[1]又は[2]に記載の反射防止材。
[4]前記疎水性多孔質無機フィラーが、前記多孔質無機フィラーに、金属酸化物、シランカップリング剤、チタンカップリング剤、有機酸、ポリオール、及び有機ケイ素化合物からなる群から選ばれる少なくとも1種の疎水性表面処理剤による表面処理が施されたものである、上記[3]に記載の反射防止材。
[5]前記疎水性表面処理剤が、有機ケイ素化合物である、上記[4]に記載の反射防止材。
[6]前記有機ケイ素化合物が、トリメチルクロロシラン、ヘキサメチルジシロキサン、ジメチルジクロロシラン、オクタメチルシクロテトラシラン、ポリジメチルシロキサン、ヘキサデシルシラン、メタクリルシラン、及びシルコーンオイルからなる群から選ばれる少なくとも1種(好ましくは、ポリジメチルシロキサン)である、上記[5]に記載の反射防止材。
[7]前記疎水性多孔質無機フィラーが、疎水性多孔質無機ガラス、及び疎水性多孔質シリカ(疎水性多孔質シリカフィラー)からなる群から選ばれる少なくとも1種(好ましくは、疎水性多孔質シリカフィラー)である、上記[1]~[6]のいずれか1つに記載の反射防止材。
[8]前記疎水性多孔質シリカフィラーが、溶融シリカ、結晶シリカ、高純度合成シリカ、及びコロイド状シリカからなる群から選ばれる少なくとも1種の多孔質シリカが前記疎水性表面処理剤で処理されたものである、上記[7]に記載の反射防止材。
[9]前記疎水性多孔質無機フィラーの形状が、粉体、球状、破砕状、繊維状、針状、及び鱗片状からなる群から選ばれる少なくとも1種(好ましくは球状、又は破砕状)である、上記[1]~[8]のいずれか1つに記載の反射防止材。
[10]前記疎水性多孔質無機フィラーが、多孔質無機フィラーの表面が疎水性処理されたものであり、疎水性処理前の多孔質無機フィラーの比表面積が200m2/g以上(好ましくは200~2000m2/g、より好ましくは200~1500m2/g、さらに好ましくは200~1000m2/g)である、上記[1]~[9]のいずれか1つに記載の反射防止材。
[11]前記疎水性多孔質無機フィラーの平均粒子径が、1~20μm(好ましくは2~15μm)である、上記[1]~[10]のいずれか1つに記載の反射防止材。
[12]前記疎水性多孔質無機フィラーの吸油量が、10~2000mL/100g(好ましくは100~1000mL/100g)である、上記[1]~[11]のいずれか1つに記載の反射防止材。
[13]前記反射防止材全量(100重量%)に対する前記疎水性多孔質無機フィラーの含有量が、4~40重量%(好ましくは4~35重量%、より好ましくは4~30重量%)である、上記[1]~[12]のいずれか1つに記載の反射防止材。
[14]反射防止材を構成する樹脂組成物(100重量部)に対する前記疎水性多孔質無機フィラーの含有量(配合量)が、5~80重量部(好ましくは5~70重量部、より好ましくは5~60重量部)である、上記[1]~[13]のいずれか1つに記載の反射防止材。
[16]前記硬化性樹脂組成物が、エポキシ樹脂(A)、シリコーン樹脂(B)、及びアクリル樹脂(C)からなる群より選択される少なくとも1種の硬化性化合物を含む組成物からなる、上記[15]に記載の反射防止材。
[17]前記硬化性樹脂組成物が、エポキシ樹脂(A)を含む組成物(硬化性エポキシ樹脂組成物)からなる、上記[16]に記載の反射防止材。
[18]前記エポキシ樹脂(A)が、ビスフェノールA型エポキシ樹脂、分子内にエポキシ基を1個以上有するイソシアヌレート、ノボラック型エポキシ樹脂、脂環式エポキシ化合物、脂肪族エポキシ化合物、及び分子内にエポキシ基を1個以上有するシロキサン誘導体からなる群から選ばれる少なくとも1種(好ましくは、脂環式エポキシ化合物)である、上記[16]又は[17]に記載の反射防止材。
[19]前記脂環式エポキシ化合物が、分子内にシクロヘキセンオキシド基を有する化合物(好ましくは、分子内に2個以上のシクロヘキセンオキシド基を有する化合物)を含む、上記[18]に記載の反射防止材。
[20]前記脂環式エポキシ化合物が、下記式(1)で表される化合物を含む、上記[19]に記載の反射防止材。
[21]前記式(1)で表される化合物が、2,2-ビス(3,4-エポキシシクロヘキサン-1-イル)プロパン、ビス(3,4-エポキシシクロヘキシルメチル)エーテル、1,2-ビス(3,4-エポキシシクロヘキサン-1-イル)エタン、1,2-エポキシ-1,2-ビス(3,4-エポキシシクロヘキサン-1-イル)エタン、及び下記式(1-1)~(1-10)で表される化合物からなる群から選ばれる少なくとも1種の脂環式エポキシ化合物である、上記[20]に記載の反射防止材。
[22]前記脂環式エポキシ化合物が、上記式(1-1)で表される化合物を含む、上記[21]に記載の反射防止材。
[23]前記エポキシ樹脂(A)の含有量(配合量)が、硬化性エポキシ樹脂組成物の全量(100重量%)に対して、25~99.8重量%(例えば、25~95重量%)(好ましくは30~90重量%、より好ましくは35~85重量%、さらに好ましくは40~60重量%)である、上記[17]~[22]のいずれか1つに記載の反射防止材。
[24]前記脂環式エポキシ化合物の含有量(配合量)が、硬化性エポキシ樹脂組成物の全量(100重量%)に対して、20~99.8重量%(好ましくは40~95重量%(例えば、40~60重量%)、より好ましくは50~95重量%、さらに好ましくは60~90重量%、最も好ましくは70~85重量%)である、上記[18]~[23]のいずれか1つに記載の反射防止材。
[25]前記硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量(100重量%)に対する脂環式エポキシ化合物の割合が、40~100重量%(例えば、40~90重量%)(好ましくは80~100重量%、より好ましくは90~100重量%、さらに好ましくは95~100重量%)である、上記[18]~[24]のいずれか1つに記載の反射防止材。
[26]前記硬化性エポキシ樹脂組成物が、さらに、硬化剤(D)及び硬化促進剤(E)、又は、硬化触媒(F)(好ましくは、硬化剤(D)及び硬化促進剤(E))を含む、上記[17]~[25]のいずれか1つに記載の反射防止材。
[27]前記硬化剤(D)が、酸無水物類(酸無水物系硬化剤)、アミン類(アミン系硬化剤)、ポリアミド樹脂、イミダゾール類(イミダゾール系硬化剤)、ポリメルカプタン類(ポリメルカプタン系硬化剤)、フェノール類(フェノール系硬化剤)、ポリカルボン酸類、ジシアンジアミド類、及び有機酸ヒドラジドからなる群から選ばれる少なくとも1種(好ましくは、酸無水物系硬化剤)である、上記[26]に記載の反射防止材。
[28]前記酸無水物系硬化剤が、25℃で液状の酸無水物、又は25℃で固体状の酸無水物を25℃で液状の酸無水物に溶解させた液状の混合物である、上記[27]に記載の反射防止材。
[29]前記硬化剤(D)の含有量(配合量)が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量100重量部に対して、50~200重量部(好ましくは75~150重量部、より好ましくは100~120重量部)である、上記[26]~[28]のいずれか1つに記載の反射防止材。
[30]前記硬化促進剤(E)の含有量(配合量)が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量100重量部に対して、0.05~5重量部(好ましくは0.1~3重量部、より好ましくは0.2~3重量部、さらに好ましくは0.25~2.5重量部)である、上記[26]~[29]のいずれか1つに記載の反射防止材。
[31]前記硬化性エポキシ樹脂組成物が、多価アルコール(好ましくは炭素数2~4のアルキレングリコール)を含む、上記[17]~[30]のいずれか1つに記載の反射防止材。
[32]前記多価アルコールの含有量(配合量)が、硬化性エポキシ樹脂組成物に含まれるエポキシ化合物の全量100重量部に対して、0.05~5重量部(好ましくは0.1~3重量部、より好ましくは0.2~3重量部、さらに好ましくは0.25~2.5重量部)である、上記[31]に記載の反射防止材。
[33]前記硬化性エポキシ樹脂組成物が、蛍光体を含む、上記[1]~[32]のいずれか1つに記載の反射防止材。
[34]前記蛍光体の含有量(配合量)が、硬化性エポキシ樹脂組成物の全量(100重量%)に対して、0.5~20重量%である、上記[33]に記載の反射防止材。
[36]光半導体封止用である、上記[1]~[35]のいずれか1つに記載の反射防止材。
[37]上記[36]に記載の反射防止材により光半導体素子が封止された光半導体装置。
[39]液状である、上記[38]に記載の樹脂組成物。
[40]前記樹脂組成物の全量(100重量%)に対する硬化中に揮発する成分の量が、10重量%以下である、上記[38]又は[39]に記載の樹脂組成物。
[41]上記[38]~[40]のいずれか1つに記載の樹脂組成物を硬化させることを特徴とする、表面に反射を抑える凹凸が形成されている反射防止材の製造方法。
101:金属配線(電極)
102:光半導体素子
103:ボンディングワイヤ
104:封止材(反射防止材)
Claims (13)
- 疎水性多孔質無機フィラーが分散された樹脂組成物の硬化物からなる反射防止材であって、当該硬化物の表面に反射を抑える凹凸が形成されていることを特徴とする、反射防止材。
- 前記疎水性多孔質無機フィラーが前記硬化物全体に渡って均一に分散しており、表面に反射を抑える凹凸を形成している、請求項1に記載の反射防止材。
- 前記疎水性多孔質無機フィラーが、多孔質無機フィラーの表面が疎水性処理されたものであり、疎水性処理前の多孔質無機フィラーの比表面積が200m2/g以上である、請求項1又は2に記載の反射防止材。
- 前記疎水性多孔質無機フィラーの平均粒子径が1μm~20μmである、請求項1~3のいずれか1項に記載の反射防止材。
- 反射防止材全量(100重量%)に対する前記疎水性多孔質無機フィラーの含有量は4~40重量%である、請求項1~4のいずれか1項に記載の反射防止材。
- 前記樹脂組成物は、透明な硬化性樹脂組成物からなる、請求項1~5のいずれか1項に記載の反射防止材。
- 前記硬化性樹脂組成物はエポキシ樹脂を含む組成物からなる、請求項6に記載の反射防止材。
- 光半導体封止用である、請求項1~7のいずれか1項に記載の反射防止材。
- 請求項8に記載の反射防止材により光半導体素子が封止された光半導体装置。
- 請求項1~8のいずれか1項に記載の反射防止材の製造のために用いられることを特徴とする疎水性多孔質無機フィラーが分散された樹脂組成物。
- 液状である、請求項10に記載の樹脂組成物。
- 前記樹脂組成物の全量(100重量%)に対する硬化中に揮発する成分の量は、10重量%以下である、請求項10又は11に記載の樹脂組成物。
- 請求項10~12のいずれか1項に記載の樹脂組成物を硬化させることを特徴とする、表面に反射を抑える凹凸が形成されている反射防止材の製造方法。
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| WO2024048406A1 (ja) * | 2022-08-31 | 2024-03-07 | 三菱瓦斯化学株式会社 | 防眩性積層体 |
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- 2017-10-03 WO PCT/JP2017/035957 patent/WO2018070300A1/ja not_active Ceased
- 2017-10-03 JP JP2018544967A patent/JP7481802B2/ja active Active
- 2017-10-03 CN CN201780063069.0A patent/CN109804276A/zh active Pending
- 2017-10-11 TW TW106134742A patent/TWI829625B/zh active
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| WO2024048406A1 (ja) * | 2022-08-31 | 2024-03-07 | 三菱瓦斯化学株式会社 | 防眩性積層体 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190059969A (ko) | 2019-05-31 |
| TW201827510A (zh) | 2018-08-01 |
| JPWO2018070300A1 (ja) | 2019-07-25 |
| CN117849914A (zh) | 2024-04-09 |
| TWI829625B (zh) | 2024-01-21 |
| CN109804276A (zh) | 2019-05-24 |
| JP7481802B2 (ja) | 2024-05-13 |
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