Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/10—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• • 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
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the present invention relates to a reflecting plate for a light emitting device such as a light emitting diode element (hereinafter referred to as “LED”) and a resin composition for a reflecting plate that can be suitably used as the reflecting plate.
• a light emitting device such as a light emitting diode element (hereinafter referred to as “LED”)
• resin composition for a reflecting plate that can be suitably used as the reflecting plate.
• the LED light-emitting device is small and lightweight, easy to incorporate into various devices, strong against vibrations and repeated ON / OFF, has a very long life, has a vivid color, and has excellent visibility, plus power consumption comparison It has various desirable characteristics such as low and high. Above all, with the practical use of white LED light emitting devices that combine blue LEDs and phosphors, they can be used as backlights for liquid crystal display screens of mobile phones, computers, televisions, etc., as light sources for automobile headlights, instrument panels, lighting equipment, etc. Has attracted a lot of attention.
• the LED light emitting device is mainly composed of an LED as a light emitting part, a reflector (reflector) also serving as a housing, a transparent sealing material for sealing and protecting the LED, and a lead wire.
• a silicone resin is usually used because of its high light resistance and heat resistance. In order to increase the reliability of the apparatus, high adhesion between the silicone resin constituting the sealing material and the reflector is required.
• thermoplastic resin is used for the reflective plate from the viewpoint of mass productivity.
• the thermoplastic resin changes color due to heat in the manufacturing process such as injection molding and soldering, heat and light during use, and the like. It is a problem that the degree decreases.
• the polyamide resin that is widely used as a heat resistant resin has a problem that it is easily discolored by heat and light.
• the reflector of the LED light emitting device is required to have whiteness and discoloration resistance as well as high adhesion to the silicone resin.
• Patent Document 1 proposes an LED light emitting device comprising a package containing potassium titanate fibers and / or wollastonite, titanium oxide, and semi-aromatic polyamide. Since this package uses potassium titanate fiber and / or wollastonite instead of the conventional glass fiber, smoothness of the package surface is ensured, and adhesion between the silicone resin as a sealing material and the package (It corresponds to the comparative example 1 of this specification). However, the adhesion of this package is not always satisfactory. Further, this package tends to discolor due to continuous exposure to heat and light, and the whiteness tends to be greatly reduced.
• substrate is plasma-processed and then it uses a primer composition (silane coupling agent etc.). It has been proposed that after the primer treatment, the LED is sealed with a sealing material, thereby improving the adhesion between the substrate and the sealing material and improving the reliability of the device.
• the plasma treatment has a problem that the resin composition constituting the substrate may be deteriorated, and the production cost increases due to an increase in the number of steps.
• An object of the present invention is to provide a light-emitting device reflector (hereinafter referred to as “a light-emitting device”) having high whiteness, excellent discoloration resistance to heat and light, and high adhesion (adhesion) with a silicone resin. And a resin composition for a reflecting plate which is a raw material of the reflecting plate.
• the present inventors have found that a reflector obtained by molding a resin composition containing a polyamide resin, titanium oxide, inorganic fibers, and a silanol condensate has high whiteness.
• the present inventors have found that excellent discoloration resistance to heat and light and high adhesion with a silicone resin can be exhibited. Based on this knowledge, the present invention was completed by further research.
• the present invention provides the following resin composition for a reflector and a reflector obtained by molding the resin composition.
• a resin composition for a reflector comprising a polyamide resin, titanium oxide, inorganic fibers, and a silanol condensate.
• Item 2 The resin composition for a reflector according to Item 1, wherein the silanol condensate is a hydrolysis condensate of a silane coupling agent and / or a silicone compound.
• the resin composition for a reflector according to Item 2 obtained by mixing and heating a mixture containing the polyamide resin, titanium oxide, inorganic fibers, and a silane coupling agent and / or a silicone compound.
• Item 4 0.1 to 10 wt% of the silane coupling agent and / or silicone compound in 100 wt% of the mixture containing the polyamide resin, titanium oxide, inorganic fibers, and the silane coupling agent and / or silicone compound Item 4.
• the silanol condensate is represented by the general formula (1) R 1 n Si (OR 2 ) 4-n (1)
• n represents an arbitrary integer selected from 1 to 3
• R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group, and these groups have a substituent.
• R 2 represents an alkyl group having 1 to 4 carbon atoms, and when a plurality of R 2 are present May be the same or different from each other.
• Item 3 The resin composition for a reflector according to Item 1 or 2, which is a hydrolysis-condensation product of the compound represented by:
• Item 6 The resin composition for a reflector according to any one of Items 1 to 5, wherein the polyamide resin has a melting point of 280 ° C or higher.
• Item 7 The resin composition for a reflector according to any one of Items 1 to 6, wherein the polyamide resin is a semi-aromatic polyamide resin in which the ratio of aromatic monomers in all monomer components is 20 mol% or more. .
• Item 8 The reflector resin composition according to any one of Items 1 to 7, wherein the polyamide resin is a semi-aromatic polyamide resin containing an aromatic dicarboxylic acid and an aliphatic alkylenediamine as monomer components.
• Item 9 A reflector obtained by molding the resin composition according to any one of Items 1 to 8.
• Item 10 The reflector according to Item 9, wherein the reflector is for LED.
• a reflector (reflector) obtained from the resin composition for a reflector of the present invention has a high whiteness, excellent discoloration resistance to heat and light, and a silicone resin constituting a sealing material. High adhesion (adhesion). It also has excellent mechanical strength as a reflector. Therefore, it can be suitably used as a reflector for light emitting devices (particularly for LEDs).
• the resin composition for a reflector of the present invention is characterized by containing a polyamide resin, titanium oxide, inorganic fibers, and a silanol condensate.
• the silanol condensate is dispersed in a polyamide resin which is a matrix of the reflector resin composition.
• the silanol condensate comprises a hydrolysis condensate of a silane coupling agent and / or a silicone compound, and when these compounds have a reactive functional group capable of reacting with a polyamide resin, the resin composition for a reflector
• the product includes those in which the silanol condensate and polyamide resin or the like are partially reacted to form a covalent bond.
• polyamide resin As the polyamide resin used in the present invention, various aliphatic monomers and aromatic monomers can be used as the monomer component, and any polyamide resin can be used without any particular limitation.
• the polyamide resin used in the present invention preferably has a melting point of 280 ° C. or higher in order to suppress deformation, discoloration, etc. of the reflector during reflow soldering.
• the melting point is preferably 350 ° C. or lower, and more preferably 330 ° C. or lower.
• the melting point can be measured according to JIS-K7121.
• the polyamide resin used in the present invention is preferably a semi-aromatic polyamide resin in order to suppress deformation and deterioration of physical properties due to moisture absorption.
• the semi-aromatic polyamide resin means a polyamide resin containing an aromatic monomer as a monomer component of the polyamide resin.
• the aromatic monomer in the monomer component constituting the polyamide resin is usually 20 mol% or more, preferably 25 mol% or more, more preferably 25 to 60 mol%.
• the molar fraction of the aromatic monomer in the semi-aromatic polyamide resin means the molar fraction of the aromatic monomer in all the monomers used for the polymerization raw material.
• aromatic monomer examples include aromatic diamine, aromatic dicarboxylic acid, aromatic aminocarboxylic acid and the like.
• aromatic diamines include p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, paraxylenediamine, and metaxylenediamine.
• aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and phthalic acid. 2-methyl terephthalic acid, naphthalene dicarboxylic acid and the like, and examples of the aromatic amino carboxylic acid include p-aminobenzoic acid and the like. Of these, aromatic dicarboxylic acids are preferred.
• Aromatic monomers can be used alone or in combination of two or more.
• monomer components other than aromatic monomers include aliphatic dicarboxylic acids, aliphatic alkylene diamines, alicyclic alkylene diamines, and aliphatic amino carboxylic acids.
• aliphatic dicarboxylic acid examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and the like. Among these, adipic acid is preferable. Aliphatic dicarboxylic acid can be used individually by 1 type, or can use 2 or more types together.
• the aliphatic alkylene diamine may be linear or branched. Specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, Examples thereof include 2-methylpentamethylenediamine and 2-ethyltetramethylenediamine. Of these, hexamethylenediamine, 2-methylpentamethylenediamine and the like are preferable.
• An aliphatic alkylenediamine can be used individually by 1 type, or can use 2 or more types together.
• Examples of the alicyclic alkylenediamine include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, bis (aminomethyl) cyclohexane, and bis (4-aminocyclohexyl) methane. 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, isophoronediamine, piperazine and the like.
• An alicyclic alkylenediamine can be used individually by 1 type, or can use 2 or more types together.
• aliphatic aminocarboxylic acids examples include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminodokecanic acid, and the like, and corresponding lactams may be used.
• Aliphatic aminocarboxylic acids can be used alone or in combination of two or more.
• aliphatic dicarboxylic acid aliphatic alkylene diamine and the like are preferable.
• These monomer components can be used alone or in combination of two or more.
• dicarboxylic acid is preferably terephthalic acid, a mixture of terephthalic acid and adipic acid, a mixture of terephthalic acid and isophthalic acid, or a mixture of terephthalic acid, isophthalic acid and adipic acid.
• those having a terephthalic acid ratio of 25 mol% or more are particularly preferable.
• semiaromatic polyamide resins those in which the aliphatic alkylenediamine is hexamethylenediamine or a mixture of hexamethylenediamine and 2-methylpentamethylenediamine are particularly preferable.
• the semi-aromatic polyamide resins particularly preferable examples include terephthalic acid 25 to 30 mol% (especially about 27.5 mol%), adipic acid 20 to 25 mol% (particularly about 22.5 mol%). And hexamethylenediamine 45-55 mol% (especially about 50 mol%), terephthalic acid 30-35 mol% (especially about 32 mol%), adipic acid 15-20 mol% (especially about 18 mol%) and 45 to 55 mol% (especially about 50 mol%) of hexamethylene diamine, 45 to 55 mol% (especially about 50 mol%) terephthalic acid, 20 to 30 mol of hexamethylene diamine % (Particularly about 25 mol%) and 2-methylpentamethylenediamine 20 to 30 mol% (particularly about 25 mol%).
• the melting point and the like can be appropriately adjusted by appropriately selecting the composition ratio and type of the aromatic monomer and other monomer components constituting the semi-aromatic polyamide resin.
• Titanium oxide used in the present invention can be used without particular limitation as long as it is a titanium oxide capable of improving the whiteness as a reflector. If necessary, it may be treated with a known surface treating agent such as alumina, silica, silane coupling agent, titanium coupling agent and the like.
• titanium oxide used in the present invention various crystal forms such as anatase type, rutile type, monoclinic type and the like can be used, but a rutile type having a high refractive index and good light stability is preferable.
• powders of various shapes such as particles, fibers, and plates (including flakes, scales, mica, etc.) can be used, and preferably particles are used. Is good.
• the size of the titanium oxide used in the present invention is not particularly limited, but from the viewpoint of increasing whiteness, the average particle size is preferably 0.05 to 0.5 ⁇ m, more preferably 0.1 to 0.00. 3 ⁇ m.
• the average particle diameter of titanium oxide can be measured by a laser diffraction method.
• titanium oxide used in the present invention one or more of the above-mentioned titanium oxides can be used.
• inorganic fibers used in the present invention include glass fiber, glass milled fiber, zinc oxide fiber, sodium titanate fiber, potassium titanate fiber, aluminum borate fiber, magnesium borate fiber, magnesium oxide fiber, and silicic acid.
• Aluminum fiber, silicon nitride fiber, wollastonite, etc. are mentioned. 1 type (s) or 2 or more types selected from the group which consists of the above-mentioned inorganic fiber can be used, and the mechanical strength, dimensional stability, and heat resistance of the resin composition obtained can be improved.
• the inorganic fiber used in the present invention uses one or more selected from the group consisting of wollastonite and potassium titanate fibers from the viewpoint of increasing the hiding power, and from the viewpoint of planar smoothness and microreinforcing properties. It is preferable to do this.
• Wollastonite is an inorganic fiber made of calcium metasilicate.
• the dimensions of wollastonite are not particularly limited, but usually the average fiber diameter is 0.1 to 15 ⁇ m, preferably 2.0 to 7.0 ⁇ m, the average fiber length is 3 to 180 ⁇ m, preferably 20 to 100 ⁇ m, and the average aspect The ratio is 3 or more, preferably 3 to 50, more preferably 5 to 30. Commercially available products can also be used in the present invention.
• Vistal W (trade name: manufactured by Otsuka Chemical Co., Ltd., average fiber length: 25 ⁇ m, average fiber diameter: 3 ⁇ m), Nyglos I-10013 (trade name: manufactured by Nyco, average fiber length) : 65 ⁇ m, average fiber diameter: 5 ⁇ m) and the like can be used.
• the potassium titanate fiber is not particularly limited and conventionally known ones can be widely used.
• potassium titanate fiber, potassium titanate fiber, potassium potassium titanate fiber, and the like can be used.
• the dimensions of the potassium titanate fiber are not particularly limited, but usually the average fiber diameter is 0.01 to 1 ⁇ m, preferably 0.1 to 0.5 ⁇ m, the average fiber length is 1 to 50 ⁇ m, preferably 3 to 30 ⁇ m, and the average The aspect ratio is 10 or more, preferably 15 to 35.
• commercially available products can also be used.
• TISMO D102 (trade name: manufactured by Otsuka Chemical Co., Ltd., average fiber length: 15 ⁇ m, average fiber diameter: 0.5 ⁇ m) can be used.
• the average fiber length and average fiber diameter of the wollastonite and potassium titanate fibers can be measured by observation with an optical microscope or a scanning electron microscope.
• the inorganic fiber used in the present invention may be subjected to a surface treatment.
• the surface treatment may be performed using a silane coupling agent, a titanium coupling agent or the like according to a known method.
• a silane coupling agent is preferable and aminosilane is particularly preferable.
• silanol condensate used in the present invention is an oligomer or polymer having a siloxane bond as a main skeleton and an organic group.
• the silanol condensate is preferably a hydrolysis condensate of a silane coupling agent or a silicone compound.
• a resin composition for a reflector is obtained by mixing and heating (particularly, melt-kneading) a silane coupling agent and / or a silicone compound together with a polyamide resin, titanium oxide, and inorganic fibers.
• a silane coupling agent when used, it reacts (hydrolyzes) with water molecules present in the polyamide resin and moisture in the air during mixing to form silanol, which is condensed by heat treatment to form a silanol condensate. give.
• a silicone type compound itself can become a silanol condensate.
• Examples of the silanol condensate used in the present invention include, for example, the general formula (1) R 1 n Si (OR 2 ) 4-n (1) (In the formula, n represents an arbitrary integer selected from 1 to 3, R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group, and these groups have a substituent.
• R 1 s when there are a plurality of R 1 s , they may be the same or different from each other, R 2 represents an alkyl group having 1 to 4 carbon atoms, and when a plurality of R 2 are present May be the same or different from each other.
• the hydrolysis-condensation product of the compound (silane coupling agent) represented by these is mentioned.
• the silanol condensate may be produced from one or a mixture of two or more compounds represented by the general formula (1) through hydrolysis and condensation.
• Examples of the alkyl group represented by R 1 include a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group , Nonyl group, decyl group and the like.
• An alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 2 to 4 carbon atoms is more preferable.
• the alkyl group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at any position.
• Examples of the cycloalkyl group represented by R 1 usually include a cycloalkyl group having 3 to 10 carbon atoms. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. A cycloalkyl group having 5 to 8 carbon atoms is preferred. The cycloalkyl group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at any position.
• Examples of the alkenyl group represented by R 1 include linear or branched alkenyl groups having 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Specific examples include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl, 2-butenyl group, pentenyl group, hexenyl, heptenyl group and the like. An alkenyl group having 2 to 4 carbon atoms is preferred.
• the alkenyl group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at any position.
• Examples of the cycloalkenyl group represented by R 1 usually include a cycloalkenyl group having 3 to 10 carbon atoms. Specific examples include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like. A cycloalkyl group having 5 to 8 carbon atoms is preferred.
• the cycloalkenyl group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at any position.
• the aryl group represented by R 1 usually includes an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms. Specifically, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group etc. are mentioned, for example. An aryl group having 6 to 9 carbon atoms is preferred.
• the aryl group may have 1 to 4 substituents (preferably 1 to 3, more preferably 1) described later at any position.
• Each of the groups represented by R 1 may have a substituent.
• substituents include an amino group and an epoxy group which may be substituted with an aryl group (for example, a phenyl group) or an amino lower (for example, having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms) alkyl group.
• a reactive functional group capable of reacting with the amide group, amino group or carboxyl group of the polyamide resin is preferable from the viewpoint of affinity with the polyamide resin which is the matrix of the resin composition.
• an amino lower group for example, 3 to 6 carbon atoms, preferably 2 to 4 carbon atoms
• an alkyl group for example, an epoxy group, a glycidoxy group, a carboxyl group, an epoxycycloalkyl group (for example, 3, 4-epoxycyclohexyl group, etc.), hydroxyl group, isocyanate group and the like are preferable.
• an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxy cyclohexyl which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms, are preferable.
• an amino group, an epoxy group, a glycidoxy group, a carboxyl group, an isocyanate group, and an epoxycyclohexyl group that may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms are more preferable.
• R 1 particularly preferably, an alkyl substituted with one group selected from the group consisting of an amino group, a phenylamino group, an aminoethylamino group, an epoxy group, a glycidoxy group, and an epoxycyclohexyl group Groups.
• R 1 Preferable specific examples of the group represented by R 1 include groups represented by the following general formulas (1a) to (1g).
• a to g may be the same or different and each represents an integer of 2 to 6) a to g are preferably 2 or 3, more preferably a is 2 and b to g are 3.
• Examples of the alkyl group having 1 to 4 carbon atoms represented by R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Preferred are a methyl group, an ethyl group, and an isopropyl group, and more preferred is a methyl group or an ethyl group.
• the compound represented by the general formula (1) include, for example, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltri Methoxysilane, 3-iso
• the compound represented by the general formula (1) used in the present invention (that is, the silane coupling agent) is mixed and heated with the polyamide resin, so that a part or all of the alkoxy group (—OR 2 ) is a polyamide resin. It reacts with moisture contained in it or moisture in the air to produce silanol groups (hydrolysis), and it becomes a silanol condensate by condensation reaction between silanol groups.
• the silanol condensate is generated by the heat of melt kneading, and the silanol condensate can be dispersed in the polyamide resin by the shearing force of melt kneading. Furthermore, when the silanol condensate has a reactive functional group, it is considered that it forms a bond by reacting with the polyamide resin, so that the dispersion state of the silanol condensate in the polyamide resin can be maintained (held), As a result, bleeding out of the silanol condensate can be suppressed.
• the compound represented by the general formula (1) is added to the polyamide resin and mixed (for example, while stirring the polyamide resin, the general formula (1) By dropping, spraying, or the like.
• a mixer such as a super mixer or a Henschel mixer can be used.
• the compound represented by the general formula (1) may be used as it is, or may be used as a solution by dissolving in a solvent that promotes hydrolysis (for example, water, alcohol, or a mixed solvent thereof).
• the compound represented by the general formula (1) and the polyamide resin are melt-kneaded, whereby the produced silanol condensate is present or dispersed in the matrix polyamide resin. It is characterized by being.
• the resin composition for a reflector according to the present invention is greatly improved in adhesion, whiteness and discoloration resistance with a silicone resin (encapsulant) because a silanol condensate having a siloxane bond as a main skeleton in a polyamide resin. It is thought that is formed. In this respect, the same effect is exhibited when a resin composition is prepared using a silicone compound having a polysiloxane bond as a main skeleton described below (typically, a compound represented by the general formula (2)). Can be easily understood.
• the resulting resin composition has a resistance to discoloration, particularly discoloration due to light. An excellent effect that can be further suppressed.
• the mechanism of action is unknown, it is assumed that a part or all of the reactive functional group forms a chemical bond such as a covalent bond or a hydrogen bond with the amide group, amino group or carboxyl of the polyamide resin.
• a silanol condensate obtained by condensing the compound represented by the general formula (1) in advance can also be used as a raw material.
• the said silicone type compound is a silanol condensate obtained by hydrolyzing and condensing 1 type, or 2 or more types of the compound shown by General formula (1).
• silicone compound examples include, for example, dimethyl silicone oil, methylphenyl silicone oil, amino modified silicone oil, epoxy modified silicone oil, carbinol modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, methyl hydrogen silicone oil.
• Silicone oils such as mercapto modified silicone oil, methacrylic modified silicone oil, polyether modified silicone oil, aralkyl modified silicone oil, fluoroalkyl modified silicone oil, long chain alkyl modified silicone oil, higher fatty acid ester modified silicone oil, phenyl modified silicone oil ; Silicone rubber with a structure in which linear dimethylpolysiloxane is crosslinked; Siloxane bond (CH 3 SiO 3/2) polymethylsilsesquioxane having a crosslinked structure in a three-dimensional network, represented by n oxane; 3 silicone resin or the like of a three-dimensional network structure mainly composed of functional siloxane units can be mentioned .
• These silicone-based compounds include both known compounds that are commercially available and compounds that can be
• R 3 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group, and these groups may have a substituent, and R 3 may be the same as each other. And may be different, l and m represent any integer of 1 or more, and the order of bonding of each repeating unit structure in parentheses is not particularly limited.) The compound represented by these is mentioned.
• an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxy cyclohexyl which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms are preferable.
• an amino group, an epoxy group, a glycidoxy group, a carboxyl group, an isocyanate group, and an epoxycyclohexyl group that may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms are more preferable.
• an alkyl substituted with one group selected from the group consisting of an amino group, a phenylamino group, an aminoethylamino group, an epoxy group, a glycidoxy group, and an epoxycyclohexyl group is particularly preferable.
• R 3 Preferable specific examples of the group represented by R 3 include groups represented by the above general formulas (1a) to (1g).
• L is preferably an integer of 1 to 20,000, more preferably an integer of 1 to 10,000
• m is preferably an integer of 1 to 20,000, more preferably an integer of 1 to 10,000.
• a preferable one is the general formula (3).
• R 3A is selected from the group consisting of an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxycyclohexyl group, which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms.
• R 3A is selected from the group consisting of an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxycyclohexyl group, which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms.
• It is an alkyl group substituted with 1 to 3 groups selected, and l and m are the same as above, and the order of bonding of each repeating unit structure in parentheses is not particularly limited.
• the compound represented by these is mentioned.
• R 3A is preferably a group preferably exemplified as the above R 3 , particularly a group represented by the general formulas (1a) to (1g), more preferably the general formulas (1b), (1c ) And (1d).
• R 3B is selected from the group consisting of an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxycyclohexyl group, which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms.
• R 3B is selected from the group consisting of an amino group, an epoxy group, a glycidoxy group, a carboxyl group, a hydroxyl group, an isocyanate group, and an epoxycyclohexyl group, which may be substituted with a phenyl group or an alkyl group having 2 to 4 amino carbon atoms.
• It is an alkyl group substituted with 1 to 3 groups selected, and l and m are the same as above, and the order of bonding of each repeating unit structure in parentheses is not particularly limited.
• the compound represented by these is mentioned.
• R 3B is preferably a group preferably exemplified as the above R 3 , particularly a group represented by the general formulas (1a) to (1g), more preferably the general formulas (1b), (1c ) And (1d).
• the viscosity (25 ° C.) is usually 10 to 2,000 mm 2 / s, preferably 10 to 1,000 mm 2 / s. s. When the viscosity is within this range, the difference in viscosity from the polyamide resin can be reduced during melt mixing, so that uniform dispersion is facilitated. The viscosity can be measured with a kinematic viscosity measuring device.
• the silicone compound represented by the general formula (2) is solid (for example, silicone rubber, polymethylsilsesquioxane, silicone resin, etc.), the powder form is preferable, and the average particle size is usually 0.1. It is ⁇ 20 ⁇ m, preferably 0.5 to 10 ⁇ m. When the average particle size is in this range, it becomes easier to disperse in the resin composition during melt mixing.
• the average particle diameter can be measured by a laser diffraction method.
• the polyamide resin composition of the present invention contains a silanol condensate having a siloxane bond as the main skeleton in the polyamide resin, thereby improving adhesion with the silicone resin, whiteness, and discoloration resistance. Further, when the silanol condensate has a reactive functional group capable of reacting with an amide group, amino group or carboxyl group in the molecule, an excellent effect can be obtained in that discoloration due to light can be further suppressed. Although the detailed mechanism of action is unknown, it is because part or all of the reactive functional group forms a chemical bond such as a covalent bond or a hydrogen bond with the amide group, amino group or carboxyl of the polyamide resin. Guessed.
• an inorganic filler an antioxidant, a heat stabilizer, a flame retardant, a plasticizer, a nucleating agent, a dye, a pigment, as long as the preferable physical properties are not impaired.
• examples of the inorganic filler include talc, silica, zinc oxide (including tetrapots).
• antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
• phenolic antioxidants include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethylester, N, N'-hexamethylenebis (3,5-di- tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl 2,4,6-tris (3
• pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4- Hydroxy-hydrocinnamamide) is preferred.
• phosphorus antioxidants include, for example, tris (2,4-di-tert-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) Dibenzo [d, f] [1.3.2] dioxaphosphin-6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1dimethyl) Ethyl) dibenzo [d, f] [1.3.2] dioxaphosphobin-6-yl] oxy] -ethyl] ethanamine, bis (2,6-di-tert-butyl-4-methylphenyl) penta Examples include erythritol diphosphite.
• sulfur-based antioxidant examples include, for example, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- ( Dodecylthio) propionate] methane and the like.
• the resin composition of the present invention comprises a polyamide resin, inorganic fibers, titanium oxide, a silane coupling agent and / or a silicone compound in various blending ratios, and further if necessary.
• a mixture containing other additives can be produced by mixing and heating (particularly melt-kneading).
• melt kneading for example, a known melt kneading apparatus such as a twin screw extruder can be used.
• the polyamide resin used in the present invention is preferably blended so as to be 30 to 80% by weight in 100% by weight of the total amount of the above mixture.
• the upper limit value of the polyamide resin used in the present invention is preferably 70% by weight, and more preferably 65% by weight.
• the lower limit of the polyamide resin used in the present invention is preferably 40% by weight, more preferably 45% by weight.
• the titanium oxide used in the present invention is preferably blended so as to be 5 to 50% by weight in the total amount of 100% by weight of the above mixture.
• the upper limit of titanium oxide used in the present invention is preferably 40% by weight, more preferably 30% by weight.
• the lower limit of titanium oxide used in the present invention is preferably 10% by weight, more preferably 15% by weight.
• the inorganic fibers used in the present invention are preferably blended so that the proportion is 5 to 60% by weight in the total amount of 100% by weight of the above mixture.
• the upper limit value of the inorganic fibers used in the present invention is preferably 40% by weight, more preferably 30% by weight.
• the lower limit of the inorganic fibers used in the present invention is preferably 10% by weight, more preferably 15% by weight.
• the silane coupling agent and / or silicone compound used in the present invention is preferably blended so as to be a ratio of 0.1 to 10% by weight in the total amount of 100% by weight of the above mixture.
• the upper limit of the silanol condensate used in the present invention is preferably 7% by weight, more preferably 5% by weight.
• the lower limit of the silane coupling agent and / or silicone compound used in the present invention is preferably 0.3% by weight, and more preferably 0.5% by weight.
• the amount of additives other than the essential components that may be used in the present invention is not particularly limited as long as the preferable physical properties of the resin composition of the present invention are not impaired. Usually, it is 9.9% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less in the total amount of 100% by weight of the above mixture.
• the heating temperature in the melt kneading is not particularly limited as long as the polyamide resin can be melted, and is usually higher than the melting point of the polyamide resin and lower than the decomposition start temperature. Usually, the temperature in the cylinder of the melt kneader used for melt kneading is adjusted to this temperature range.
• silanol condensate and / or silicone compound obtained from the compound represented by the general formula (1) is mixed and dispersed in the polyamide resin by melt kneading treatment.
• silane coupling agent silane coupling agent
• a reactive functional group is present in the molecule of the silanol condensate and / or silicone compound, a part or all of the functional group reacts with the amide group, amino group or carboxyl group of the polyamide resin. To do.
• the resin composition of the present invention is a known resin molding method such as injection molding, insert molding, compression molding, extrusion molding, blow molding, inflation molding, etc., depending on the type, application, shape, etc. of the target molded product.
• Various molded products can be obtained.
• a molding method combining the above molding methods can also be employed.
• the reflecting plate obtained by molding the resin composition of the present invention can be suitably used as an LED reflecting plate because of its excellent adhesion with a silicone resin as a sealing material, and also has whiteness and discoloration resistance. Since the properties are also excellent, it can be used as an LED reflector without plating the light reflecting surface.
• the reflector of the present invention means a reflector for a light emitting device (reflector) as described above.
• the shape will not be specifically limited, It is not limited to a planar shape of a "plate” shape. For example, three-dimensional shapes such as a box shape, a conical shape, and a parabona shape are also included.
• the reflector of the present invention can be applied not only to LED light emitting devices but also to other uses that reflect light.
• various electrical and electronic parts automotive keyless entry systems, refrigerator interior lighting, liquid crystal display backlights, automotive front panel lighting devices, lighting stands, bed lights, household appliance indicators, optical communications equipment such as infrared communications And reflectors such as ceiling lighting devices.
• the polyamide resin, titanium oxide, inorganic fiber, silane coupling agent, and silanol condensate used in the examples and comparative examples are specifically as follows.
• the melting point of the polyamide resin is the endothermic peak obtained by heating at 25 ° C. to 10 ° C./min under a nitrogen stream using a differential scanning calorimeter (trade name: DSC6200, manufactured by Seiko Instruments Inc.). did.
• ⁇ Polyamide resin> A semi-aromatic polyamide resin obtained by polymerizing hexamethylenediamine, terephthalic acid, and adipic acid at a ratio of 50 mol%, 27.5 mol%, and 22.5 mol%, respectively (trade name: Zytel HTN502HF, manufactured by DuPont, melting point 310 ° C)
• Examples 1 to 17 and Comparative Examples 1 to 3 At the blending ratio shown in Table 1, the polyamide resin and the silanol condensate or the silane coupling agent are melted and kneaded from the main hopper of the twin screw extruder, and the inorganic fibers and titanium oxide are added from the side feeder. Manufactured. The cylinder temperature of the twin screw extruder was 320 ° C.
• the obtained pellets were molded into a JIS test piece and a flat plate having a length of 30 mm ⁇ width of 30 mm ⁇ thickness of 3 mm using an injection molding machine, and used as an evaluation sample.
• the cylinder temperature of the injection molding machine was 330 ° C.
• the mold temperature was 130 ° C.

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