JP2012063428A - Polymerizable composition for light reflection plate, and light reflection plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition for a light reflection plate that provides a light reflection plate having high optical reflectance, excellent heat-resistance stability, low water absorption property, and excellent solder reflow resistance, and allows the production of the light reflection plate with high production efficiency, as well as a light reflection plate obtained by using the composition.SOLUTION: There are provided: a polymerizable composition for a light reflection plate formed by containing a cycloolefin monomer, a metathesis polymerization catalyst, and an inorganic filler; and a light reflection plate formed by applying a white coating on a surface of a polymerized compact obtained by mass polymerizing the polymerizable composition for a light reflection plate and having optical reflectance of 80% or higher in a wavelength of 450 nm.

Description

  The present invention relates to a polymerizable composition for a light reflecting plate and a light reflecting plate. More specifically, the light reflecting plate has high light reflectance, excellent heat stability, low water absorption, and solder reflow resistance. The present invention relates to a polymerizable composition for a light reflecting plate that can provide an excellent light reflecting plate and can produce the light reflecting plate with excellent production efficiency, and a light reflecting plate obtained using the same.

  In recent years, light emitting devices including light emitting elements such as LEDs (Light Emitting Diodes) that emit light with low power have been used as backlights for liquid crystal displays of portable terminals, personal computers, televisions, and the like, and as light sources for lighting fixtures. Yes. Such a light-emitting device is configured by mounting a light-emitting element on a substrate, arranging a light reflection plate for reflecting light from the light-emitting element around the light-emitting element, and sealing the light-emitting element with a resin. The

  In such a light emitting device, a ceramic material has been conventionally used as a light reflecting plate. However, the ceramic material has a problem that it is inferior in productivity and is expensive. On the other hand, various resin materials have been examined as a material constituting the light reflection plate used in such a light emitting device, instead of the ceramic material.

  For example, Patent Document 1 contains an epoxy resin, a curing agent, a curing catalyst, an inorganic filler, a white pigment, and a coupling agent as a resin material for a light reflecting plate used in an LED device. A thermosetting epoxy resin composition having a light reflectance of 80% or more at a wavelength of 800 nm to 350 nm and a thermal conductivity of 1 to 10 W / mK and capable of being pressure-molded at room temperature before thermosetting. It is disclosed.

  Moreover, in patent document 2, as a resin material for the light reflection plate used for an LED device, a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit, a 1,9-nonanediamine unit and / or 2-methyl- A polyamide resin comprising a diamine unit containing 60 to 100 mol% of 1,8-octanediamine unit, and 5 to 100 parts by mass of titanium oxide and 0.5 mg of magnesium hydroxide with respect to 100 parts by mass of the polyamide resin. A polyamide resin composition containing 20 to 100 parts by mass of at least one reinforcing agent selected from the group consisting of ~ 30 parts by mass and a fibrous filler and an acicular filler is disclosed.

JP 2006-140207 A JP 2006-257314 A

  However, the light reflecting plate obtained using the thermosetting epoxy resin composition of Patent Document 1 has high light reflectance and high thermal conductivity, but has a high water absorption rate. There was a problem of poor stability. Moreover, in the said patent document 1, when shape | molding a thermosetting epoxy resin composition into a desired shape and hardening | curing and setting it as a light reflection board, there also existed a problem that a long time was required for shaping | molding and hardening. Furthermore, although the light reflecting plate obtained by the polyamide resin composition of Patent Document 2 has a high light reflectance, it has poor solder reflow resistance and a high water absorption rate. There was a problem of being inferior. Moreover, since the polyamide resin composition of the above-mentioned Patent Document 2 is blended with a large amount of a filler for increasing the thermal conductivity, the viscosity increases and it becomes difficult to mold, so the filler for increasing the thermal conductivity. Therefore, there is a problem that the obtained light reflection plate has a low thermal conductivity.

  The present invention provides a light reflecting plate having high light reflectance, excellent heat resistance stability, low water absorption, excellent solder reflow resistance, and excellent light reflecting plate. It is an object of the present invention to provide a polymerizable composition for a light reflector that can be produced with high production efficiency, and a light reflector obtained by using the polymerizable composition. Another object of the present invention is to provide a light emitting element mounting substrate and a light emitting device obtained by using this light reflecting plate.

  As a result of intensive studies in view of the above problems, the inventors of the present invention mass-polymerized a polymerizable composition containing a cycloolefin monomer, a metathesis polymerization catalyst, and an inorganic filler, and formed the surface of the resulting polymer molded body. By applying a white paint, a light reflecting plate having high light reflectance, excellent heat stability, low water absorption, and excellent solder reflow resistance can be obtained. When the composition is used, the present inventors have found that the light reflecting plate can be produced with excellent production efficiency, and have completed the present invention based on this finding.

That is, according to the present invention,
[1] A polymerizable composition for a light reflector comprising a cycloolefin monomer, a metathesis polymerization catalyst, and an inorganic filler,
[2] A white paint is applied to the surface of a polymer molded body obtained by bulk polymerization of the polymerizable composition for light reflectors according to [1], and the light reflectance at a wavelength of 450 nm is 80. % Light reflector,
[3] The light reflecting plate according to [2], wherein the thermal conductivity is 0.5 W / m · K or more,
[4] A light emitting element mounting substrate comprising the light reflecting plate according to [2] or [3] above on a base material including wiring for mounting the light emitting element, and
[5] A substrate, a light emitting element mounted on the substrate, a light reflecting plate surrounding the light emitting element, and a sealing agent for sealing the light emitting element, wherein the light reflecting plate is the above [2 ] Or a light emitting device which is a light reflecting plate according to [3],
Is provided.

  According to the present invention, a light reflecting plate having high light reflectance, excellent heat stability, low water absorption, excellent solder reflow resistance, and the light reflecting plate can be provided. A polymerizable composition for a light reflecting plate that can be produced with excellent production efficiency, and a light reflecting plate obtained using the same. The light reflecting plate of the present invention has high light reflectance, excellent heat resistance stability, low water absorption, and excellent solder reflow resistance. Therefore, the light reflecting plate is suitably used for a light emitting element mounting substrate and a light emitting device. can do.

  The polymerizable composition for a light reflector of the present invention is a polymerizable composition comprising a cycloolefin monomer, a metathesis polymerization catalyst, and an inorganic filler, and is used for producing a light reflector. It is a composition.

(Cycloolefin monomer)
The cycloolefin monomer used in the present invention may be any compound as long as it has an alicyclic structure formed of carbon atoms and has a ring-opening polymerizable carbon-carbon double bond in the alicyclic structure. However, norbornene compounds having a norbornene ring structure are preferred.

Cycloolefin monomers include norbornene, norbornadiene and other bicyclics; dicyclopentadiene (cyclopentadiene dimer), dihydrodicyclopentadiene and other tricyclics; tetracyclododecene and other tetracyclics; And pentacycles such as cyclopentadiene tetramers and the like.
These cycloolefin monomers include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an alkenyl group such as a vinyl group; an alkylidene group such as an ethylidene group; an aryl group such as a phenyl group, a tolyl group, and a naphthyl group; And the like.
Furthermore, these cycloolefin monomers may have polar groups such as a carboxy group, an alkoxycarbonyl group, an acyloxy group, an oxy group, a cyano group, and a halogen atom.

  Specific examples of cycloolefin monomers include dicyclopentadiene, tricyclopentadiene, cyclopentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8 Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6 -Ethylidene-1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4-methano-1,4,4a, 5 , 6,7,8,8a-octahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,6,7,8,8a-hexahydro Futaren, ethylenebis (5-norbornene), and the like.

These cycloolefin monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
Among the cycloolefin monomers, tricyclic, tetracyclic or pentacyclic cycloolefin monomers are preferred because they are easily available, have excellent reactivity, and improve the heat resistance of the resulting polymer molded product.

  In addition, it is preferable that the ring-opening polymer to be generated is a thermosetting type. For this purpose, among the cycloolefin monomers, two or more reactive double bonds such as a symmetric cyclopentadiene trimer are used. It is preferable to use at least including the crosslinkable monomer. The ratio of the crosslinkable monomer in the total cycloolefin monomer is preferably 2 to 30% by weight.

  In addition, monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cyclooctene, and cyclododecene, which can be ring-opening copolymerized with a cycloolefin monomer, may be used as a comonomer within a range that does not impair the object of the present invention.

(Polymerization catalyst)
In the present invention, a metathesis polymerization catalyst is used as the polymerization catalyst. The polymerizable composition for a light reflecting plate of the present invention is preferably directly used for bulk polymerization in the production of a light reflecting plate described later, and a metathesis polymerization catalyst is suitable for that purpose.

  Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6 and Group 8 (according to the long-period periodic table; the same shall apply hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum. Examples of the Group 6 atom include molybdenum and tungsten. Examples of the Group 8 atom include Examples thereof include ruthenium and osmium. Of these transition metal atoms, Group 8 ruthenium and osmium are preferred. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the light reflecting plate is obtained by subjecting the polymerizable composition for a light reflecting plate of the present invention to bulk polymerization, an unreacted monomer is present in the resulting light reflecting plate. A light reflecting plate with good productivity and good odor can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.

Examples of the ruthenium carbene complex include those represented by the following general formula (1) or general formula (2).

In the general formula (1) and the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. The C1-C20 hydrocarbon group which may be included is represented.

X ¹ and X ² each independently represents an arbitrary anionic ligand. An anionic ligand is a ligand having a negative charge when pulled away from a central metal atom, such as a halogen atom, a diketonate group, a substituted cyclopentadienyl group, an alkoxyl group, an aryloxy group, Examples thereof include a carboxyl group. Among these, a halogen atom is preferable and a chlorine atom is more preferable.

L ¹ and L ² each independently represent a heteroatom-containing carbene compound or a neutral electron donating compound other than the compound. A hetero atom means an atom of Group 15 and Group 16 of the Periodic Table, and specific examples thereof include N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

Examples of the heteroatom-containing carbene compound include compounds represented by the following general formula (3) or general formula (4).

In the formula, R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms that may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a hydrogen group. R ^{3 to} R ⁶ may be bonded to each other in any combination to form a ring.

  The neutral electron donating compound may be any ligand as long as it has a neutral charge when separated from the central metal. Specific examples thereof include phosphines, ethers and pyridines, and trialkylphosphine is more preferable.

In the general formulas (1) and (2), R ¹ and R ² may be bonded to each other to form a ring, and further R ¹ , R ² , X ¹ , X ² , L ¹ and L ² may be bonded together in any combination to form a multidentate chelating ligand.

  In the present invention, it is preferable to use a ruthenium catalyst having a compound having a heterocyclic structure as a ligand as a metathesis polymerization catalyst from the viewpoint of increasing the production efficiency of the light reflector. Examples of the hetero atom constituting the heterocyclic structure include an O atom and an N atom, and an N atom is preferable. Moreover, as a heterocyclic structure, an imidazoline structure and an imidazolidine structure are preferable.

The ruthenium catalyst having a compound having such a heterocyclic structure as a ligand is represented by the above general formula (1) or (2), and a ligand comprising a heteroatom-containing carbene compound as L ¹ or L ² A ruthenium catalyst having the following can be preferably used. Specific examples of such heteroatom-containing carbene compounds include, for example, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1 , 3-Di (1-phenylethyl) -4-imidazoline-2-ylidene, 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ′, N′-tetraisopropylformamidinylidene, benzylidene (1,3-dimesitylimidazolidin-2-ylidene), 1 , 3-Dimesitylimidazolidin-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, 1,3-diisopropyl- - imidazolin-2-ylidene, 1,3-dimesityl-2,3-dihydro-benzimidazol-2-ylidene and the like.

  Specific examples of the ruthenium catalyst having a ligand composed of a heteroatom-containing carbene compound include benzylidene (1,3-dimesityrylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3 -Dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydro Imidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole -5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) Examples thereof include a ruthenium complex compound in which a hetero atom-containing carbene compound and a neutral electron donating compound other than the compound are bonded as a ligand, such as pyridine ruthenium dichloride.

  In the present invention, the amount of the metathesis polymerization catalyst used is usually 0.01 mmol or more, preferably 0.1 mmol or more and 50 mmol or less, preferably 20 mmol or less with respect to 1 mol of the monomer used in the reaction. is there. If the amount of the metathesis polymerization catalyst used is too small, the polymerization activity is too low and the reaction takes time, resulting in poor production efficiency. If the amount used is too large, the reaction is too intense, so that the catalyst is cured in an insufficiently molded state, or the catalyst Tends to precipitate, and tends to be difficult to store uniformly.

  If necessary, the metathesis polymerization catalyst can be used by dissolving or suspending in a small amount of an inert solvent. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, Alicyclic hydrocarbons such as diethylcyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; and alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, and hydrocarbons having an alicyclic ring and an aromatic ring.

(Inorganic filler)
The inorganic filler used in the present invention is not particularly limited, but from the viewpoint of increasing the thermal conductivity of the obtained light reflector, usually an inorganic filler having a thermal conductivity of 30 W / m · K or more is preferably used. It is done. Examples of the inorganic filler include inorganic oxides such as alumina, magnesium oxide, beryllium oxide, and titanium oxide; inorganic nitrides such as aluminum nitride, boron nitride, and silicon nitride; inorganic carbides such as silicon carbide; copper, Examples thereof include metals or alloys such as silver, iron, aluminum, nickel, and titanium; carbon-based compounds such as diamond, carbon fiber, carbon black, and expanded graphite; and quartz and quartz glass. Among these, at least one selected from the group consisting of inorganic oxides, inorganic nitrides, inorganic carbides, and carbon-based compounds from the viewpoint that the thermal conductivity of the obtained light reflector can be made higher. It is preferable to use seeds, and it is more preferable to use at least one selected from the group consisting of inorganic oxides, inorganic nitrides, and carbon-based compounds. The inorganic oxide is alumina (thermal conductivity: 30 W / m · K), and the inorganic nitride is aluminum nitride (thermal conductivity: 70 to 270 W / m · K) and boron nitride (thermal conductivity 110 W / m · K). K) is preferably expanded graphite (thermal conductivity: 100 to 2400 W / m · K) as the carbon-based compound. The thermal conductivity of the inorganic filler varies somewhat depending on the crystal state and direction of the compound. The thermal conductivity of the inorganic filler can be measured, for example, by a hot disk method.

  In addition, from the viewpoint of increasing the affinity with a polymer formed by polymerizing cycloolefin monomer, the inorganic filler is a known fatty acid, oil or fat, surfactant, polymer, titanate coupling agent, aluminate coupling agent, and The surface treatment may be performed with a surface treatment agent such as a silane coupling agent. Preferably, the titanate coupling agent, the aluminate coupling agent, and the silane coupling agent may be in terms of adhesiveness and affinity with a polymer obtained by polymerizing a cycloolefin monomer. The amount of these surface treatment agents used is usually 5 parts by weight or less with respect to 100 parts by weight of the inorganic filler.

  The particle diameter (average particle diameter) of the inorganic filler may be appropriately selected as desired, but the average value of the lengths in the longitudinal direction and the short direction when the particles are viewed three-dimensionally is usually 0.1. It is -200 micrometers, Preferably it is 0.5-100 micrometers, More preferably, it is the range of 1-50 micrometers.

  The amount of the inorganic filler is preferably 1 to 2000 parts by weight, more preferably 10 to 1500 parts by weight, and still more preferably 50 to 1000 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. The volume fraction in the polymerizable composition of the present invention is usually 1 to 95% by volume, more preferably 5 to 85% by volume, and still more preferably 10 to 80% by volume. The polymerizable composition for a light reflecting plate of the present invention uses a cycloolefin monomer having a relatively low viscosity as a monomer for forming a resin component, and therefore, the amount of the inorganic filler is easily increased. Can do. Accordingly, an inorganic filler having a high thermal conductivity is used as the inorganic filler, and the blending ratio is increased (preferably 30 to 85% by volume in volume fraction), whereby the thermal conductivity of the obtained light reflector is obtained. Can be made higher easily.

(Polymerizable composition for light reflector)
The polymerizable composition for a light reflecting plate of the present invention comprises the above-described cycloolefin monomer, metathesis polymerization catalyst, and inorganic filler. Moreover, the polymerization composition for light reflectors of this invention can add a polymerization regulator, a polymerization reaction retarder, an anti-aging agent, other compounding agents, etc. if desired.

  The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. Examples of the polymerization regulator include trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium. , Tetraalkoxytin, tetraalkoxyzirconium and the like. These polymerization regulators can be used alone or in combination of two or more. The blending amount of the polymerization regulator is a molar ratio (metal atom in the polymerization catalyst: polymerization regulator), preferably 1: 0.05 to 1: 100, more preferably 1: 0.2 to 1:20, Preferably it is the range of 1: 0.5-1: 10.

  The polymerization reaction retarder can suppress an increase in viscosity due to the progress of the polymerization reaction of the polymerizable composition for a light reflecting plate of the present invention. Polymerization reaction retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, styryldiphenylphosphine; Lewis bases such as aniline and pyridine Etc. can be used. What is necessary is just to adjust suitably the compounding quantity of a polymerization reaction retarder in the case of using a polymerization reaction retarder as needed.

  Examples of the anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents, sulfur-based anti-aging agents, and the like, and light obtained by blending these anti-aging agents. The heat resistance of the reflector can be improved to a high degree. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. In the case of using an anti-aging agent, the amount of the anti-aging agent used is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, further preferably 100 parts by weight of the cycloolefin monomer. Is in the range of 0.01 to 2 parts by weight.

  The polymerizable composition for a light reflecting plate of the present invention can contain other compounding agents other than the above-described compounding agents. As other compounding agents, a crosslinking agent, a chain transfer agent, a dispersant, a light stabilizer, a foaming agent, and the like can be used. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The polymerizable composition for a light reflecting plate of the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a metathesis polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and a cycloolefin monomer, an inorganic filler, and, if desired, other The liquid (monomer liquid) which mix | blended the compounding agent can be prepared, this catalyst liquid can be added to this monomer liquid, and it can prepare by stirring.

(Light reflector)
The light reflecting plate of the present invention is obtained by applying a white paint on the surface of a polymer molded body obtained by bulk polymerization of the above-described polymerizable composition for a light reflecting plate of the present invention. As a method for producing the light reflecting plate of the present invention, (a) a method in which a polymerizable composition for a light reflecting plate is applied to a support, subjected to bulk polymerization, and a white paint is applied to the resulting polymer molded body, b) A method in which a polymerizable composition for a light reflecting plate is poured into a mold, bulk polymerization is performed, and a white paint is applied to the obtained polymer molded body.

  Although it does not specifically limit as a support body used for the method of said (a), A metal foil, a resin film, or a metal or resin board is preferable. Examples of the material constituting the metal foil or metal plate include iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver. Moreover, as a material which comprises a resin film or a resin board, a polyethylene terephthalate, a polypropylene, polyethylene, a polycarbonate, a polyethylene naphthalate, a polyarylate, nylon etc. are mentioned, for example. The surfaces of these supports may be plated with, for example, silver, copper, and nickel. In the case of using a metal foil or a resin film as the support, these thicknesses are preferably 1 to 150 μm, more preferably 2 to 100 μm, and still more preferably 3 to 75 μm from the viewpoint of workability and the like. The surface of these supports is preferably smooth. In the case of using a metal plate or a resin plate, the thickness is preferably 50 μm to 5 mm, more preferably 100 to 3 mm, and further preferably 200 μm to 2 mm because of strength. These metal plates or resin plates may be processed by stamping or the like so as to have a desired shape. In addition, the method for applying the polymerizable composition for a light reflecting plate to a support is not particularly limited, and for example, known methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. The application method can be adopted. After applying the polymerizable composition for a light reflecting plate on a support, the polymerizable composition for the light reflecting plate is heated and bulk polymerized to obtain a polymer molded body integrated with the support.

  As the mold used in the method (b), a conventionally known mold can be used. For example, after injecting the polymerizable composition for a light reflecting plate into these voids (cavities), the polymerizable composition for the light reflecting plate is heated and bulk polymerized to obtain a polymer molded body. The shape, material, size, etc. of the mold are not particularly limited. Also, at this time, for example, a metal plate such as aluminum or copper is processed into a desired shape in advance by stamping or the like, if necessary, and then placed in the mold, and then the polymerizable composition for the light reflecting plate is injected. By polymerizing in bulk, a polymer molded body integrated with such a metal plate can be obtained. Alternatively, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and a polymerizable composition for a light reflector is formed in a space formed by sandwiching the spacer between two plate-shaped molds. A polymer molded product can be obtained by injecting the product and heating and polymerizing the polymerizable composition for a light reflector.

  Then, a white paint is applied to the surface of the polymer molded body obtained by bulk polymerization as described above using a known method such as a spray coating method, a dip coating method, a screen printing method, or a transfer method. Thus, the light reflecting plate of the present invention is manufactured.

  The white paint is not particularly limited as long as it is a known white paint used industrially. For example, a paint containing a binder resin and a white pigment can be used.

  Examples of the binder resin include liquid crystal polymer, polyphenylene sulfide, aromatic nylon, epoxy resin, epoxy acrylate, unsaturated polyester, polyester acrylate, urethane acrylate, and high-humidity silicone resin. Among these, since it is excellent in heat resistance, an epoxy resin and epoxy acrylate are preferable. These vanida resins can be used alone or in admixture of two or more.

  Examples of the epoxy resin include alicyclic epoxy resins having an alicyclic structure formed of carbon atoms, and silicone-modified epoxy resins.

上記式（５）中、Ａ^１及びＡ^２は、それぞれ独立に、下記式（６）又は（７）に示す基であり、Ａ^３及びＡ^４は、それぞれ独立に、２価の芳香族残基又は２価の水添芳香族残基であり、Ａ^５は、水素原子又は下記式（６）に示す基である。下記式（７）中、Ｒ^７は水素原子、又はメチル基など炭素数１〜１０個のアルキル基である。繰り返し単位数を示すｎが２以上である場合には、Ａ^３同士、及びＡ^５同士は、同一であってもよいし、互いに異なっていてもよい。また、繰り返し単位数を示すｎは１〜２０であり、好ましくは１〜１５、より好ましくは１〜１０である。

As said epoxy acrylate, what is represented by following formula (5) can be used.

In the above formula (5), A ¹ and A ² are each independently a group represented by the following formula (6) or (7), and A ³ and A ⁴ are each independently a divalent aromatic residue. A group or a divalent hydrogenated aromatic residue, and A ⁵ is a hydrogen atom or a group represented by the following formula (6). In the following formula (7), R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a methyl group. When n indicating the number of repeating units is 2 or more, A ³ and A ⁵ may be the same or different from each other. Moreover, n which shows the number of repeating units is 1-20, Preferably it is 1-15, More preferably, it is 1-10.

上記式（８）、（９）及び（１０）中、Ａ^１、Ａ^２及びＡ^５は、上記式（５）と同様である。 In the present invention, among the epoxy acrylates represented by the above formula (5), those represented by the following formula (8), (9) or (10) are preferable, and are represented by the following formula (8). Those are particularly preferred.

In the above formulas (8), (9) and (10), A ¹ , A ² and A ⁵ are the same as the above formula (5).

  In addition, when using the epoxy acrylate, unsaturated polyester, polyester acrylate, and urethane acrylate having the group shown in the above formula (7) as the binder resin, the white paint can react with these as required. Any reactive monomer may be included. The reactive monomer is not particularly limited, but ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth). Acrylate, dimethylol tricyclodecane di (meth) acrylate, 1,4-butanediol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane acrylate benzoate, hydroxypivalate neopentyl glycol di ( Compounds having two unsaturated bonds such as (meth) acrylate, polytetramethylene glycol di (meth) acrylate, dibutyl phthalate, diallyl phthalate, divinylbenzene; trimethylolpropane tri (meth) acrylate Rate, triallyl cyanurate, triallyl isocyanurate, compounds having three or more unsaturated bonds such as pentaerythritol tri (meth) acrylate; and the like. In the present specification, “(meth) acrylate” represents methacrylate or acrylate.

  The compounding quantity in the case of mix | blending a reactive monomer is about 1-300 weight part normally with respect to 100 weight part of epoxy acrylate, unsaturated polyester, polyester acrylate, or urethane acrylate.

  The white pigment used in the present invention is not particularly limited as long as it is a known white pigment used industrially. Such white pigments typically have a thermal conductivity of less than 30 W / m · K. The thermal conductivity of the white pigment can be measured in the same manner as the inorganic filler. Examples of the white pigment include titanium oxide, zinc oxide, zircon oxide, basic carbonate, basic lead sulfate, lead sulfate, zinc sulfide, antimony oxide, titanium nitride, cerium fluoride, and cerium oxide. For example, the thermal conductivity of zinc oxide is 25.2 W / m · K, and the thermal conductivity of zircon oxide is 22.7 W / m · K. Among these, rutile type titanium oxide is preferable from the viewpoint that the refractive index is high and the light reflectance of the obtained light reflection plate can be increased. More preferably, since it is excellent in heat resistance, those produced by the sulfuric acid method or the chlorine method, particularly the chlorine method are preferred. Specifically, TR-600, TR-700, TR-750, and TR-840 manufactured by Fuji Titanium Industry Co., Ltd .; R-550, R-580, R-630, R-820, CR manufactured by Ishihara Sangyo Co., Ltd. -50, CR-60, and CR-90; KR-270, KR-310, and KR-380 manufactured by Titanium Industry Co., Ltd. can be used. When titanium oxide is used as the white pigment, the content of titanium oxide in the white pigment to be used is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.

The particle diameter (average particle diameter) of the white pigment may be appropriately selected as desired, but is usually 0.01 to 20 μm, preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm. The said particle diameter is defined similarly to the particle diameter of an inorganic filler. If the particle diameter of the white pigment is too small, the particles are likely to aggregate and dispersibility is lowered, and the light reflectance of the obtained light reflecting plate may be lowered. On the other hand, even if the particle diameter of the white pigment is too large, the light reflection characteristics of the white pigment are deteriorated, and the light reflectance of the obtained light reflection plate may be lowered.
These white pigments must be surface-treated with a surface treatment agent such as a normal polymer, silicone, zirconium coupling agent, titanate coupling agent, aluminate coupling agent, and silicone coupling agent. Is preferred. By being treated with the surface treatment agent, the dispersibility in the polymerizable composition of the present invention and the affinity with the cycloolefin monomer are improved. The amount of these surface treatment agents used is usually 5 parts by weight or less with respect to 100 parts by weight of the white pigment.

  The amount of the white pigment in the white paint is preferably 25 to 400 parts by weight, more preferably 50 to 300 parts by weight, and still more preferably 60 to 260 parts by weight with respect to 100 parts by weight of the binder resin. It is. In addition, when mix | blending a reactive monomer with the white coating material used for this invention, let the compounding quantity of a white pigment be the quantity with respect to a total of 100 weight part of binder resin and reactive monomer mentioned above. If the amount of the white pigment is too small, the light reflectance of the resulting light reflector may be lowered. On the other hand, if the amount is too large, the dispersibility of the white pigment in the white paint will decrease, resulting in There is a possibility that the light reflectivity of the light reflecting plate to be lowered.

Moreover, when using epoxy resin, epoxy acrylate, polyester acrylate, urethane acrylate, and unsaturated polyester as binder resin, it is preferable to mix | blend a hardening | curing agent with white paint.
The curing agent for the epoxy resin may be any one such as a room temperature curing type or a heat curing type, and is not particularly limited. For example, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6- [2′-methylimidazolyl -(1 ')]-E -S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-4'- Methylimidazolyl- (1 ′)]-ethyl-S-triazine, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-dodecyl-2- Imidazole derivatives such as methyl-3-benzoylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride; Dicyandiamide or a derivative thereof; Organic acid dihydrazide such as sebacic acid dihydrazide; 3- (3,4-dichlorophenyl)- Urea derivatives such as 1,1-dimethylurea; polyamidoamines, modified polyamines, Amines such as boron fluoride-monoethylamine complexes; phenolic curing agents; phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, anhydrous Examples thereof include acid anhydrides such as nadic acid, glutaric anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Among these acid anhydride curing agents, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferably used. Among these, those with relatively little coloring are preferable. These may be used alone or in combination of two or more.
As a curing agent for curing epoxy acrylate, polyester acrylate, urethane acrylate, or unsaturated polyester, an organic peroxide is preferable. Bis (4-t-butylcyclohexyl) peroxydicarbonate, lauroyl peroxide, t-amylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. It is done.

When an epoxy resin is used as the binder resin, the mixing ratio of the epoxy resin and the curing agent in the white paint is an active group that can react with the epoxy group in the curing agent with respect to 1 equivalent of the epoxy group in the epoxy resin ( The ratio is such that the acid anhydride group or hydroxyl group is 0.5 to 1.5 equivalents, and more preferably 0.7 to 1.2 equivalents. When the active group is less than 0.5 equivalent, the curing rate of the epoxy resin is slowed and the glass transition temperature of the resulting white coating film may be lowered. , Moisture resistance may be reduced.
When using epoxy acrylate, polyester acrylate, urethane acrylate, or unsaturated polyester as the binder resin, the ratio of the curing agent in the white paint is 100 parts by weight of epoxy acrylate, polyester acrylate, urethane acrylate, or unsaturated polyester. Usually, it is 0.1 to 15 parts by weight. In addition, when mix | blending a reactive monomer with the white coating material used for this invention, the compounding quantity of a hardening | curing agent is with respect to a total of 100 weight part of an epoxy acrylate, polyester acrylate, urethane acrylate, or unsaturated polyester, and a reactive monomer. Amount. If the blending amount of the curing agent is too small, curing may be insufficient, and the light reflectance of the resulting light reflecting plate may be lowered. On the other hand, if the amount is too large, it may be hard and brittle or discolored.

  In addition, the white paint used in the present invention includes a known solvent, a curing accelerator, a polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, a coupling agent, and a flame retardant as necessary. Etc. may be blended.

The method for applying the white paint to the obtained polymer molded product is not particularly limited, and examples thereof include a screen printing method, a curtain coating method, a spray coating method, and a roll coating method. After applying the white paint, heat treatment may be performed as necessary. When performing the heat treatment, the heat treatment temperature is usually 50 to 300 ° C, preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and the heat treatment time is usually 1 to 240 minutes, preferably 5 to 120 minutes, More preferably, it is 10 to 80 minutes. Moreover, when obtaining a light reflection board by the method of said (b), you may perform application | coating of the white coating material to a superposition | polymerization molded object by the in-mold coating method. That is, a white paint is applied in advance in the mold, and at the same time as forming the polymer, a white paint film is prepared on the surface of the polymer molded body, or the polymer is cured, and then the white paint is formed in the mold. The paint is injected to produce a white paint film on the surface of the polymer molded body. Specific examples of the in-mold coating method include the method described in JP-A-2001-71345.
Although the thickness of the coating film formed using a white coating material is not specifically limited, Usually, it is 1-150 micrometers, Preferably it is 5-100 micrometers, More preferably, it is 10-50 micrometers.

  The light reflecting plate of the present invention is obtained by applying a white paint on the surface of a polymer molded body obtained by bulk polymerization of the above-described polymerizable composition for a light reflecting plate of the present invention. In addition, the light reflectance is high, the heat stability is excellent, the water absorption is low, and the solder reflow resistance is also excellent. In particular, the light reflecting plate of the present invention has a high reflectance of 80% or more, preferably 85% or more, more preferably 87% or more at a wavelength of 450 nm. For example, even after the light reflection plate of the present invention is subjected to a deterioration acceleration test such as heating at 180 ° C. for 6 hours, no substantial change is seen when compared with the conventional product. Excellent heat stability. In addition, the light reflector of the present invention uses a cycloolefin monomer having a relatively low viscosity as a monomer for forming the resin component. Therefore, the inorganic filler, which is a component that exhibits thermal conductivity, is compared. Can be contained in a large amount. As the light reflecting plate of the present invention, those having a high thermal conductivity of usually 0.5 W / m · K or more, preferably 0.8 W / m · K or more, more preferably 1 W / m · K or more are suitable. It is. The upper limit of the thermal conductivity is not particularly limited, but is usually about 50 W / m · K. A light reflector having such a thermal conductivity is excellent in heat dissipation characteristics. A light reflector having such desired characteristics can be efficiently produced using, for example, the polymerizable composition of the present invention prepared according to the formulation described herein.

In addition, the light reflecting plate of the present invention is produced by applying a white paint on the surface of a polymer molded body obtained by bulk polymerization of the above-described polymerizable composition for a light reflecting plate of the present invention. Therefore, it can be produced with excellent production efficiency. That is, the curing temperature in the bulk polymerization is 200 ° C. or less, preferably 180 ° C. or less, more preferably 160 ° C. or less, and the curing time is 30 minutes or less, preferably 10 minutes or less, more preferably 5 Bulk polymerization can be carried out in a relatively short time of less than a minute, and the obtained polymer can have a high conversion (polymerization conversion rate). Specifically, the residual monomer content of the polymer obtained (heat loss when heated from 40 ° C. to 260 ° C.) is preferably 2% by weight, more preferably 1.5% by weight or less, still more preferably 1 It can be kept as low as less than wt%. Thus, the resulting polymer can have a high conversion, and by reducing the residual monomer content of the resulting polymer, it is possible to prevent blistering during solder reflow, When the light reflecting plate of the present invention is used in a light emitting element mounting substrate and a light emitting device, which will be described later, the adhesive interface with the sealant can be made favorable. The lower limit of the curing temperature is usually about 50 ° C., and the lower limit of the curing time is usually about 10 seconds.
In particular, in the present invention, the size of the light reflector is usually 2.5 cm or less (for example, thickness 0.5 cm × length), where the total length of thickness, length, and width (hereinafter referred to as total length). 1 cm long × 1 cm wide light reflector), preferably 2 cm or less in total length (for example, a light reflector having a thickness of 0.3 cm × length 0.8 cm × width 0.8 cm), more preferably a total length of 1 Even in the case of a very small size of 0.5 cm or less (for example, a light reflector having a thickness of 0.1 cm, a length of 0.6 cm, and a width of 0.6 cm), the curing temperature and the curing time Since the polymerizable composition can be bulk polymerized and the resulting polymer can have a high conversion (polymerization conversion rate), it is possible to appropriately cope with downsizing of the light emitting device. Thus, it is considered that it is a property peculiar to the polymerizable composition of the present invention that high conversion is obtained by performing bulk polymerization on a very small scale under the above-mentioned conditions. This is an unexpected property.

(Light-emitting element mounting substrate, light-emitting device)
The light emitting element mounting substrate of the present invention comprises the above-described light reflecting plate of the present invention on a base material having wiring for mounting the light emitting elements. The said base material is an insulating base material which can comprise a printed wiring board. The material is not particularly limited, and examples thereof include glass epoxy, bismaleimide-triazine resin, cyanate, liquid crystal polymer, polyphenylene oxide, polyimide, and polycycloolefin.
In the light emitting element mounting substrate of the present invention, in order to efficiently reflect the light emitted from the light emitting element, it is preferable that the light reflecting plate is disposed so as to surround a region for mounting the light emitting element. The substrate for mounting a light emitting element of the present invention is formed by forming a metal wiring on a base material by a method such as punching or etching from a metal foil and surrounding a region for mounting the light emitting element on the metal wiring. Thus, it can manufacture by forming a 1 or several light reflection board. In addition, as a method of forming a light reflection plate on a metal wiring, for example, a light reflection plate is formed so that a metal wiring on a base material surrounds a mold having a desired shape (a region for mounting a light emitting element). In a mold having a shape that can be formed, and the mold is filled with the above-described polymerizable composition for a light reflecting plate of the present invention, and this is subjected to bulk polymerization. For example, a method of applying a white paint to the surface of the shape is mentioned.

  In addition, the light emitting device of the present invention has a light emitting element mounted on a substrate, the light reflecting plate of the present invention is disposed so as to surround the mounted light emitting element, and the mounted light emitting element is sealed with a sealant. It is formed by sealing with. The light emitting device of the present invention can be manufactured, for example, by mounting a light emitting element on the above-described light emitting element mounting substrate and then sealing the mounted light emitting element with a sealant.

Although it does not specifically limit as a light emitting element, The thing using various semiconductors, such as ZnSe and GaN, is mentioned. Among them, preference is given to those short wavelength that can efficiently excite the fluorescent material is used capable of emitting nitride semiconductor _{(In X Al Y Ga 1-} X-Y N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) . Further, this nitride semiconductor may optionally contain boron or phosphorus.

Moreover, it does not specifically limit as a sealing agent, The resin composition containing various resin materials can be used. Such resin materials usually include silicone, epoxy resin, acrylic resin, polyimide resin, polycarbonate resin, and cycloolefin resin. Of these, epoxy resins and silicones are particularly preferable from the viewpoints of heat resistance, weather resistance, low shrinkage, and discoloration resistance. Moreover, these components can be used individually by 1 type or in combination of 2 or more types. Further, the sealing agent may contain a fluorescent substance, a reaction inhibitor, an antioxidant, a light stabilizer, a discoloration preventing agent, and the like.
In particular, the epoxy resin is preferably an alicyclic epoxy having no aromatic ring. Silicone may be either rubber or resin. The resin composition may be any of an addition reaction curable type, a condensation reaction curable type, and a UV curable type, but an addition reaction curable resin composition is preferable in that it can be quickly cured. However, room temperature curable or heat curable compositions are preferred. The addition reaction curable resin composition is preferably a composition in which silicone, a curing agent that cures the silicone, and a curing catalyst, if necessary, are blended. This composition usually comprises a silicone having a functional group such as a vinyl group and a polymer having a Si-H bond in the molecule (for example, LPS-5547, KJR-9022, LPS-3419A, and LPS-3419B, These are compositions composed of Shin-Etsu Chemical Co., Ltd.) and a curing catalyst (platinum-based catalyst, palladium-based catalyst, etc .; for example, C-5547 and C-9022, both manufactured by Shin-Etsu Chemical Co., Ltd.).

  The light-emitting element mounting substrate and the light-emitting device of the present invention use the light-reflecting plate of the present invention, which has a high light reflectance, excellent heat stability, low water absorption, and excellent solder reflow resistance. Therefore, the luminance is high and the stability when used for a long time is excellent. Therefore, the light-emitting element mounting substrate and the light-emitting device of the present invention can be suitably used for a light-emitting module configured by arranging a plurality of light-emitting devices and a lighting device including such a light-emitting module.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice.
Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.

(1) Light reflectance The light reflectance at a wavelength of 450 nm was measured for the light reflector plate sample using a color difference meter (Spectrophotometer SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

(2) Heat-resistant stability of light reflectance After the light reflector plate sample was placed in an oven at 180 ° C. for 6 hours and heated, the light reflectance at a wavelength of 450 nm [light reflectance (180 ° C., 6 hours) according to (1) above. After heating)] was measured and compared with the light reflectance before heating [light reflectance (initial)]. The smaller the change in light reflectance (after heating at 180 ° C. for 6 hours) with respect to the light reflectance (initial), the better the heat stability of the light reflectance.

(3) Loss on heating Using a differential thermal balance (TG-DTA, EXSTER TG / DTA7200, manufactured by SII Nanotechnology), the loss on heating when the light reflector plate was heated from 40 ° C. to 260 ° C. was determined. It was. The weight loss on heating was determined according to the following formula.
Loss on heating (%) = {(weight of sample before heating−weight of sample after heating) / weight of sample before heating} × 100

(4) Solder reflow test A solder reflow test is performed by repeating the operation of placing the light reflector plate sample in a solder reflow device (HAS-6116H, manufactured by Nippon Antom Co., Ltd.) three times at 260 ° C. for 10 seconds. It was. And the solder reflow resistance was evaluated on the following reference | standard by observing the light reflecting plate after performing a solder reflow test visually.
○: No swelling occurred.
X: Swelling occurred.

(5) Thermal conductivity The thermal conductivity (unit: W / m · K) was measured with a rapid thermal conductivity meter (QTM-500, manufactured by Kyoto Electronics Industry Co., Ltd.) using the light reflector plate sample. . The thermal conductivity was measured by the unsteady hot wire comparison method.

(6) Water Absorption Rate A test piece was obtained by processing the light reflecting plate sample into a size of 1 mm thickness × 5 cm length × 5 cm width. And the obtained test piece was put into a constant temperature and humidity chamber of 85 ° C. and 85% RH for 240 hours, and the water absorption rate was determined according to the following formula from the weight change rate of the test piece before and after being put in the constant temperature and humidity chamber. .
Water absorption rate (%) = {(weight of test piece after being placed in constant temperature and humidity chamber−weight of test piece before being placed in constant temperature and humidity chamber) / weight of test piece before being placed in constant temperature and humidity chamber} × 100

Example 1
In a glass flask, 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine are dissolved in 952 parts of toluene. A catalyst solution was prepared.

  Separately from the above, 1000 parts of alumina (Al-47-1, Showa Denko Co., Ltd.) having an average particle size of 1.06 μm was placed in a Henschel mixer, and the mixture was stirred as a silane coupling agent. By spraying 10 parts of bornyltriethoxysilane (LS-5080, manufactured by Shin-Etsu Chemical Co., Ltd.) and then stirring at 120 ° C. for 15 minutes, alumina (surface-treated alumina) surface-treated with a silane coupling agent is obtained. Obtained.

  Further, separately from the above, in a reaction vessel, 100 parts of cycloolefin monomer [dicyclopentadiene: dicyclopentadiene trimer = 90: 10 (weight ratio)] and 300 parts of the surface-treated alumina obtained above. Add 0.5 part of an aluminate coupling agent [Plenact (registered trademark) AL-M, manufactured by Ajinomoto Fine-Techno Co., Ltd.] as a dispersant, and stir with a homogenizer at 9000 rpm for 15 minutes. As a result, a monomer solution was obtained.

  Then, the catalyst solution obtained above is added to the monomer solution obtained above at a rate of 0.12 mL per 100 g of the monomer solution and stirred to obtain a polymerizable composition for a light reflector. It was. In addition, the volume fraction of alumina in the obtained polymerizable composition for a light reflecting plate was 43% by volume. The volume fraction was determined from the specific gravity and quantity ratio of each component.

  The obtained polymerizable composition for a light reflecting plate was prepared by using a mold for flat plate molding having a thickness of 1 mm, a length of 100 mm, and a width of 100 mm (a metal formed by sandwiching a U-shaped spacer between a pair of chrome-plated iron plates with a heater). Was cast for 5 minutes under the conditions of a product surface temperature of 160 ° C. and a back surface temperature of 160 ° C. as a mold temperature, to obtain a flat polymer molded body.

  And the epoxy-type white coating material was apply | coated to the surface of the obtained flat polymer molded object, and the light-reflection board sample was obtained by drying on 150 degreeC on the conditions for 1 hour. The epoxy-based white paint includes 100 parts of an alicyclic epoxy resin [Deconal (registered trademark) EX-252, manufactured by Nagase Chemtech], a curing agent (2,4-diamino-6- [2′-methylimidazolyl). -(1 ')]-Ethyl-s-triazine; 2 parts of 2MZ-A, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and chlorinated rutile titanium oxide (average particle size 0.25 μm, titanium oxide content 90%; Typaque (registered trademark) CR-90, manufactured by Ishihara Sangyo Co., Ltd.] was used by kneading 100 parts with three rolls.

  And each evaluation was performed according to said (1)-(6) using the obtained light-reflection board sample. The results are shown in Table 1.

Example 2
In the same manner as in Example 1 except that the blending amount of the surface-treated alumina as the inorganic filler in preparing the monomer liquid was changed from 300 parts to 700 parts, the polymerizable composition for light reflector and light A reflector sample was prepared and evaluated. The results are shown in Table 1. In addition, the volume fraction of alumina in the obtained polymerizable composition for a light reflector was 64% by volume.

Example 3
Example except that alumina (AS-10, Showa Denko KK) having an average particle diameter of 35 μm was used instead of alumina (Al-47-1, Showa Denko KK) having an average particle diameter of 1.06 μm 1 except that the surface-treated alumina as the inorganic filler was obtained and the amount of the surface-treated alumina as the inorganic filler was changed from 300 parts to 600 parts when preparing the monomer liquid. In the same manner as in Example 1, a polymerizable composition for a light reflecting plate and a light reflecting plate sample were prepared and evaluated. The results are shown in Table 1. In addition, the volume fraction of alumina in the obtained polymerizable composition for a light reflector was 60% by volume.

Example 4
A light-reflective plate polymerizable composition and a light-reflective plate sample were prepared in the same manner as in Example 1 except that an epoxy acrylate-based white paint was used in place of the epoxy-based white paint as the white paint. Went. The results are shown in Table 1. In addition, as an epoxy acrylate type white paint, epoxy acrylate oligomer (DA-250, manufactured by Nagase Chemtech) 50 parts, epoxy acrylate (A-722, Nagase Chemtech) 20 parts, trimethylolpropane trimethacrylate 30 parts, chlorine 100 parts of rutile type titanium oxide (Taipaque CR-90, manufactured by Ishihara Sangyo Co., Ltd.), 1 part of dibutyl phthalate, and Percadox® 16 [di- (4-tert-butylcyclohexyl) peroxydicarbonate and A mixture of 4- (1,1-dimethylethyl) cyclohexanol; manufactured by Kayaku Akzo Co., Ltd.] was used.

Example 5
A light reflector as in Example 1 except that 20 parts of expanded graphite (EC-500, average particle size 30 μm, manufactured by Ito Graphite Co., Ltd.) was used as the inorganic filler instead of 300 parts of the surface-treated alumina. A polymerizable composition and a light reflector sample were prepared and evaluated. The results are shown in Table 1. In addition, the volume fraction of the expanded graphite in the obtained polymerizable composition for light reflector was 8% by volume.

Comparative Example 1
A light reflector plate sample was prepared and evaluated in the same manner as in Example 1 except that the white paint was not applied to the surface of the flat polymer molded body obtained by heat molding. The results are shown in Table 1.

Comparative Example 2
As an inorganic filler, in the same manner as in Example 1, except that trimethoxyepoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of norbornylsilane as the silane coupling agent. A surface-treated alumina was obtained.
Next, in a reaction vessel, 100 parts of bisphenol epoxy resin [Epicoat (registered trademark) 827, manufactured by Japan Epoxy Resin Co., Ltd.], 300 parts of the surface-treated alumina obtained above, hexahydrophthalic anhydride (sum) 140 parts by Kojun Pharmaceutical Co., Ltd.) and 0.4 parts of tetra-n-butylphosphonium-o, o-diethylphosphorodithioate (PX-4ET, Nippon Chemical Industry Co., Ltd.) as a curing accelerator The mixture was kneaded with three rolls to obtain an epoxy resin composition.
Then, the obtained epoxy resin composition was heat-molded under the same conditions as in Example 1 using the same mold as in Example 1, while on the surface of the plate-shaped polymer molded body after heat-molding, A light reflecting plate sample was prepared in the same manner as in Example 1 except that no white paint was applied, and each evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
A light reflector sample was prepared in the same manner as in Comparative Example 2 except that the heat forming time at the time of heat forming was changed from 5 minutes to 120 minutes, and each evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4
Terephthalic acid 3272.9 g (19.70 mol), 1,9-nonanediamine 2849.2 g (18.0 mol), 2-methyl-1,8-octanediamine 316.58 g (2.0 mol), benzoic acid 73 .27 g (0.60 mol), 6.5 g of sodium hypophosphite monohydrate (0.1% with respect to the raw material) and 6 liters of distilled water were placed in an autoclave having an internal volume of 20 liters and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. The reaction was continued for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 2.16 MPa (22 kgf / cm ² ). Next, the pressure was reduced to 0.98 MPa (10 kgf / cm ² ) over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.24 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. under 0.13 × 10 ⁻⁴ MPa (0.1 mmHg) for 10 hours. The melting point was 306 ° C., the intrinsic viscosity [η] was 1.30 dl / g, and the end was sealed. A white polyamide having a rate of 87% was obtained.

  Further, as the silane coupling agent, trimethoxyepoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) is used instead of norbornylsilane, and glass is used instead of alumina having an average particle diameter of 1.06 μm. Surface-treated glass fibers were obtained in the same manner as in Example 1 except that fibers (MF06JB1-20, long axis length: 100 μm, manufactured by Asahi Glast Fiber Co., Ltd.) were used.

  Then, the polyamide obtained above was dried at 120 ° C. for 24 hours, and 30 parts of the surface-treated glass fiber obtained above and chlorinated rutile titanium oxide (type CR -90, Ishihara Sangyo Co., Ltd. (15 parts) was blended and pelletized by melt kneading (cylinder temperature 350 ° C., mold temperature 150 ° C.) with a twin screw extruder. The obtained pelletized resin was injection molded into a mold at a cylinder temperature of 350 ° C. and a mold temperature of 150 ° C. After injecting the resin into the mold, it takes 1 minute from mold release to produce a 1 mm thick light reflector plate sample (without applying white paint). Each evaluation was performed. The results are shown in Table 1.

Comparative Example 5
As an inorganic filler, in the same manner as in Example 1, except that trimethoxyepoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of norbornylsilane as the silane coupling agent. A surface-treated alumina was obtained.
Then, the polyamide obtained in the same manner as in Comparative Example 4 was dried at 120 ° C. for 24 hours, and 100 parts of the dried polyamide was blended with 50 parts of the surface-treated alumina obtained above. Then, it was pelletized by melt kneading (cylinder temperature 350 ° C., mold temperature 150 ° C.). Using the obtained pellets, a flat polymer molded body having a thickness of 1 mm was prepared in the same manner as in Comparative Example 4, and each evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6
The polyamide obtained in the same manner as in Comparative Example 4 was dried at 120 ° C. for 24 hours, and 300 parts of the surface-treated alumina obtained in the same manner as in Example 1 and 100 parts of the chlorine method rutile with respect to 100 parts of the dried polyamide. Pelletization was attempted by blending 15 parts of type titanium oxide (Taipeke CR-90, manufactured by Ishihara Sangyo Co., Ltd.) and melt-kneading (cylinder temperature 350 ° C., mold temperature 150 ° C.) with a twin screw extruder. However, in Comparative Example 6, the viscosity increased greatly during the production, and could not be pelletized. Therefore, a test piece could not be produced.

  From Table 1, it can be seen that the light reflecting plate samples obtained in Examples 1 to 5 all have high light reflectance, good heat stability, and low water absorption. In addition, the light reflecting plate samples obtained in Examples 1 to 5 have low heating loss even when the molding conditions (bulk polymerization conditions) are set to 160 ° C. for 5 minutes, that is, a high weight loss is suppressed. Conversion and excellent solder reflow resistance.

On the other hand, in Comparative Example 1 in which no white paint was applied, the light reflectance was inferior. Moreover, in the comparative examples 2 and 3 which used the bisphenol resin instead of the cycloolefin monomer, it became a result inferior to a light reflectance and a water absorption. In particular, in the case of using a bisphenol resin, when the molding time was set to 5 minutes as in Examples 1 to 5, the loss on heating was high, resulting in poor solder reflow properties.
Furthermore, in Comparative Examples 4 and 5 using polyamide instead of cycloolefin monomer, the results were inferior in thermal conductivity and water absorption. Further, in Comparative Example 6 in which 300 parts of surface-treated alumina having thermal conductivity was blended with 100 parts of polyamide, the thickening became too large during the production, and could not be molded.

Claims (5)

  A polymerizable composition for a light reflector, comprising a cycloolefin monomer, a metathesis polymerization catalyst, and an inorganic filler.   A white paint is applied to the surface of a polymer molded body obtained by bulk polymerization of the polymerizable composition for a light reflector according to claim 1, and the light reflectance at a wavelength of 450 nm is 80% or more. Light reflector.   The light reflecting plate according to claim 2, wherein the thermal conductivity is 0.5 W / m · K or more.   A substrate for mounting a light-emitting element, comprising the light reflecting plate according to claim 2 on a base material including wiring for mounting the light-emitting element.   A substrate, a light emitting element mounted on the substrate, a light reflecting plate surrounding the light emitting element, and a sealing agent for sealing the light emitting element, wherein the light reflecting plate is defined in claim 2 or 3. The light-emitting device which is a light reflection plate of description.