TW201343743A - Thermoplastic resin composition for led reflector plates - Google Patents

Abstract

The present invention provides a thermoplastic resin composition for LED reflector plates, which contains 3-100 parts by mass of (B) a white pigment and 5-100 parts by mass of (C) a needle-like or fibrous reinforcing material per 100 parts by mass of (A) a thermoplastic resin, and which satisfies [{the refractive index of the thermoplastic resin (A)} - {the refractive index of the reinforcing material (C)} ≥ 0.02]. This thermoplastic resin composition for LED reflector plates has excellent reinforcing effect of the reinforcing material and scarcely inhibits light reflection/scattering effect of the white pigment such as titanium oxide. Consequently, the thermoplastic resin composition for LED reflector plates is effective for luminance enhancement and durability improvement of an LED.

Description

Thermoplastic resin composition for LED reflector

The present invention relates to a thermoplastic resin composition for an LED reflector which is excellent in surface reflectance, heat discoloration resistance, and the like, and which is effective for increasing the luminance of an LED.

In recent years, LEDs (light-emitting diodes) are characterized by low power consumption, long life, high brightness, and miniaturization, and are used in lighting fixtures, optical components, mobile phones, backlights for liquid crystal displays, automobile dashboards, and signal devices. , display panels, etc., but need further high brightness and durability.

As a method of increasing the brightness of the LED, there is a method of improving the light reflection characteristics of the LED reflector. In order to improve the light reflection characteristics of the LED reflector and to improve dimensional stability or mechanical strength, it has been proposed to contain a white pigment such as titanium oxide and a reinforcing material in a base resin such as polyamine (Patent Documents 1 to 3).

For example, in Patent Document 1, it is disclosed that a dicarboxylic acid unit consisting of 100% by mole of terephthalic acid unit and 2-methyl-1,5-pentamethylenediamine and hexamethylenediamine are separately different. 50 mol% of the copolymerized polyamine contains a potassium silicate fiber or a polyamide resin composition of strontite and titanium oxide. Patent Document 2 discloses a dicarboxylic acid unit consisting of 100% by mole of terephthalic acid unit and a unit of 1,9-nonanediamine: 2-methyl-1,8-octanediamine A polyamine resin composition containing titanium dioxide and aluminum borate whisker or calcium silicate whisker in a copolymerized polyamine having an ear ratio of 80:20. Further, Patent Document 3 discloses a polyamine resin composition containing potassium titanate and titanium oxide in a partially aromatic polyamine.

However, it has been explained that in the resin composition, the reinforcing material blended for improving dimensional stability or mechanical strength absorbs light from the LED light-emitting element or a part of the reflected light from white pigment such as titanium oxide, and thus It hinders the improvement of whiteness or light reflectance, and becomes an obstacle to the manufacture of LEDs with higher brightness.

Prior technical literature

Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-294070

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-75994

Patent Document 3: Japanese Laid-Open Patent Publication No. 2008-182172

An object of the present invention is to provide a thermoplastic resin composition for an LED reflector, which is excellent not only as a reinforcing material but also as a newly discovered problem, which hinders the light reflection and scattering effects of a white pigment such as titanium oxide. It is effective for high brightness and durability improvement of LEDs.

In order to achieve the above object, the inventors of the present invention have completed the present invention by carefully examining the results of the composition of the reinforcing material which does not hinder the reflection characteristics of the white pigment by the white pigment and the reinforcing material.

That is, the present invention has the following configurations (1) to (10).

(1) A thermoplastic resin composition for an LED reflector comprising 3 to 100 parts by mass of a white pigment (B) and a acicular or fibrous reinforcing material with respect to 100 parts by mass of the thermoplastic resin (A). C) 5 to 100 parts by mass, and satisfying the following (i); (i) {refractive index of thermoplastic resin (A)} - {refractive index of reinforcing material (C)} ≧ 0.02.

(2) The thermoplastic resin composition for an LED reflector according to (1), wherein the reinforcing material (C) is a basic magnesium sulfate whisker.

(3) The thermoplastic resin composition for an LED reflector according to (1) or (2), wherein the thermoplastic resin (A) is a semi-aromatic polyamide resin (A1) having a melting point of 290 to 350 °C.

(4) A thermoplastic resin composition for an LED reflector according to (3), wherein the semi-aromatic polyamide resin (A1) contains 50 mol% or more of a diamine having a carbon number of 2 to 12 and a p-benzoic acid a constituent unit obtained by equating a molar amount of formic acid, and satisfying the following (a) and (b); (a) 7.5 carbon atoms in the polyamine resin / number of guanamine bonds in the polyamide resin; (b) The number of carbon atoms in the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin ≦ 0.35.

(5) The thermoplastic resin composition for LED reflectors according to (3) or (4), wherein the semi-aromatic polyamide resin (A1) contains 50 mol% or more of carbon number 2 to 8 a constituent unit obtained by equating a molar amount of an amine with terephthalic acid, and satisfying the following (a') and (b'), and the thermoplastic resin composition satisfies the following (c); (a') 7.5 碳 polyamine resin in the number of carbon atoms / polyamine resin in the number of guanamine bonds ≦ 8.2; (b') the number of carbon atoms in the aromatic ring in the 0.28 Å polyamine resin / the total number of carbon atoms in the polyamide resin ≦ 0.35; (c) The DSC melting peak temperature of the lowest temperature side of the polyamide resin derived from the thermoplastic resin composition is 300 to 340 °C.

(6) The thermoplastic resin composition for LED reflectors according to (4) or (5), wherein the semi-aromatic polyamide resin (A1) is used as a diamine and a para-benzene having 2 to 8 carbon atoms. One or a mixture of one or more of an aminocarboxylic acid having a carbon number of 11 to 18 or a decylamine having a component other than the constituent unit derived from an equivalent amount of the dicarboxylic acid.

(7) The thermoplastic resin composition for an LED reflector according to any one of (3) to (6) wherein the semi-aromatic polyamide resin (A1) is derived from hexamethylenediamine and The constituent unit of the equivalent molar salt of terephthalic acid is 55 to 75 mol% and is composed of 45 to 25 mol% of the constituent unit derived from 11-aminoundecanoic acid or undecanoin.

(8) The thermoplastic resin composition for an LED reflector according to any one of (1) to (7) wherein the white pigment (B) is selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, and tin oxide. , alumina, cerium oxide, magnesium oxide, calcium oxide, cerium oxide, titanium hydroxide, zinc hydroxide, zirconium hydroxide, aluminum hydroxide, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, phosphoric acid At least one of the group consisting of aluminum, calcium phosphate, calcium carbonate, lead carbonate, cesium carbonate, and magnesium carbonate.

(9) The thermoplastic resin composition for an LED reflector according to any one of (1) to (8), wherein the reflow heat resistance temperature is 280 ° C or higher.

(10) A method for producing a thermoplastic resin composition for an LED reflector, comprising: a thermoplastic resin comprising a thermoplastic resin (A), a white pigment (B), and a needle-like or fibrous reinforcing material (C); At the time of the object, the thermoplastic resin (A) and the reinforcing material (C) are selected in such a manner as to satisfy the following (i); (i) {refractive index of thermoplastic resin (A)} - {refractive index of reinforcing material (C)} ≧ 0.02.

Since the thermoplastic resin composition for an LED reflector of the present invention has a refractive index lower than that of the base resin, the refractive index of the reinforcing material can be suppressed by light or white pigment reflected from the LED light-emitting element. The base resin is incident on the reinforcing material. As a result, the thermoplastic resin composition for an LED reflector of the present invention can improve the light extraction efficiency of the LED light-emitting element.

Further, in the case where the base resin is a polyamide resin, the pH of the reinforcing material is alkaline, and thermal discoloration can be suppressed, and an LED reflector having better durability can be provided.

The resin composition for an LED reflector according to the present invention comprises a thermoplastic resin (A), a white pigment (B), and at least one selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material. (C).

The thermoplastic resin used in the present invention may, for example, be polyamine (PA), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aromatic polyamide resin, polyether ether ketone (PEEK), or poly Ether ketone (PEK), polyether quinone imine (PEI), thermoplastic polyimine, polyamidimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether oxime (PES), polyfluorene (PSU), polyarylate (PAR), polyester (PEs), polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethyl Ke Alkene (TPX), polystyrene (PS), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), fluororesin, polyacrylic acid Ester and the like. Among them, polyamines, polyesters, liquid crystal polymers, cyclic polyolefins, and aligned polystyrene have high melting points and are suitable for surface mounting technology, which is preferable. Among them, polyamine and polyester are better, and polyamine is especially preferred.

The polyamine resin used in the present invention is not particularly limited, but in the use of an LED reflector, since it is desirable to have a high melting point and heat resistance as much as possible, a semi-aromatic polyamine or a semi-alicyclic polyamine Or the copolymerized polyamine of the polyamines, and the blend of the polyamines, and the melting point is about 290 to 350 ° C in terms of ease of formation, handleability, energy saving, and the like. More practical.

Examples of the semi-aromatic polyamine (A1) include 6T polyamine (for example, polyamine 6T6I composed of terephthalic acid/isophthalic acid/hexamethylenediamine, and terephthalic acid. Polyamide 6T66 consisting of adipic acid/hexamethylenediamine, polyamine 6T6I66 consisting of terephthalic acid/isophthalic acid/adipic acid/hexamethylenediamine, from terephthalic acid/ Polyamine 6T/M-5T composed of hexamethylenediamine/2-methyl-1,5-pentamethylenediamine, composed of terephthalic acid/hexamethylenediamine/ε-caprolactam Polyamide 6T6, polyamine 6T/4T composed of terephthalic acid/hexamethylenediamine/tetramethylenediamine, 9T polyamine (terephthalic acid/1,9-壬2) Amine/2-methyl-1,8-octanediamine), 10T polyamine (terephthalic acid/1,10-decanediamine), 12T polyamine (terephthalic acid/1,12) - dodecanediamine), polydecylamine composed of azelaic acid/p-xylenediamine, and the like.

Examples of the semialicyclic polyamines include polyamines composed of 1,4-cyclohexanedicarboxylic acid/hexamethylenediamine and 1,4-cyclohexanedicarboxylic acid/1. a polydecylamine composed of 9-nonanediamine/2-methyl-1,8-octanediamine, a polyamine composed of 1,4-cyclohexanedicarboxylic acid/1,10-decanediamine, and the like .

Among the above-mentioned polyamide resins, the above-mentioned semi-aromatic polyamide resin (A1) is preferable in that it can achieve excellent UV resistance in addition to high melting point and low water absorption.

The semi-aromatic polyamide resin (A1) contains 50 mol% or more of a constituent unit obtained from an equivalent amount of a molar amount of a diamine having 2 to 12 carbon atoms and terephthalic acid, and satisfies the following (a). And (b) is ideal.

(a) 7.5 碳 Polyamine resin in the number of carbon atoms / the number of guanamine bonds in the polyamide resin

(b) The number of carbon atoms in the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin ≦ 0.35

Further, the semi-aromatic polyamide resin (A1) contains 50 mol% or more of a constituent unit derived from an equivalent amount of a molar amount of a diamine having 2 to 8 carbon atoms and terephthalic acid, and satisfies the following (a') and (b'), and the thermoplastic resin composition also satisfies the following (c).

(a') Number of carbon atoms in 7.5 ≦ polyamine resin / number of guanamine bonds in polyamide resin ≦ 8.2

(b') The number of carbon atoms in the aromatic ring in the 0.28 ≦polyamine resin / the total number of carbon atoms in the polyamide resin ≦0.35

(c) The DSC melting peak temperature of the lowest temperature side of the polyamidamide resin (A) derived from the thermoplastic resin composition is 300 to 340 ° C

The diamine component having 2 to 12 carbon atoms in the semi-aromatic polyamide resin (A1) may, for example, be 1,2-ethylenediamine, 1,3-trimethylenediamine or 1,4-tetramethylene. Amine, 1,5-pentamethylenediamine, 2-methyl-1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptethylenediamine, 1,8 - octamethyldiamine, 1,9-non-methylenediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1, 12-dodecanediamine, these may be used singly or in combination. When the constituent unit obtained from the equivalent molar amount of the diamine having 2 to 12 carbon atoms and the terephthalic acid is less than 50 mol%, the crystallinity and mechanical properties are lowered, which is not preferable.

However, in the case of a semi-aromatic polyamine which is composed of a constituent unit derived from an equivalent amount of a molar amount of a diamine having a carbon number of 9 or more and terephthalic acid, it may have a melting point at 300 ° C or lower. Therefore, it contains 50 mol% or more of a constituent unit derived from an equivalent amount of a molar amount of a diamine having 2 to 8 carbon atoms and terephthalic acid, and a polyamine resin having a melting point of 300 ° C or higher on the lowest temperature side. More ideal.

In the semi-aromatic polyamide resin (A1), other components may be copolymerized in an amount of 50% by mole or less in the constituent unit. Examples of the copolymerizable diamine component include 1,13-tridecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 2,2,4 (or Is an aliphatic diamine such as 2,4,4)-trimethylhexamethylenediamine, such as diazonium, cyclohexanediamine, bis(3-methyl-4-aminohexyl)methane, An alicyclic diamine such as bis-(4,4'-aminocyclohexyl)methane or isophorone diamine, m-xylylenediamine, p-xylenediamine, p-phenylenediamine, isophthalic acid An aromatic diamine such as an amine or a hydride or the like.

Examples of the copolymerizable acid component include isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-diphenyldicarboxylic acid. An aromatic dicarboxylic acid such as 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, sodium 5-sulfonate isophthalic acid or 5-hydroxyisophthalic acid, Fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14 -tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, An aliphatic or alicyclic dicarboxylic acid such as 4-methyl-1,2-cyclohexanedicarboxylic acid or a dimer acid. Further, examples thereof include decylamine such as ε-caprolactam, 11-aminoundecanoic acid, eleven meglumine, 12-aminododecanoic acid, and 12-laurol decylamine, and the like. Aminocarboxylic acid or the like of the structure after the ring.

Among them, as the copolymerization component, it is preferred to copolymerize one or more of a diamine having a carbon number of 10 to 18, a dicarboxylic acid, an aminocarboxylic acid or an indoleamine. More preferably, it is preferred to copolymerize one or more of an aminocarboxylic acid having a carbon number of 11 to 18 or an indoleamine.

When the copolymerization component is composed of a dicarboxylic acid and a diamine, the melting point becomes less than 300 ° C depending on the combination, which is not preferable. An aminocarboxylic acid or an indoleamine having a carbon number of 11 to 18, which has an effect of adjusting a melting point, raising a temperature of crystallization, and improving formability, reducing water absorption, and improving an accident caused by a change in physical properties or dimensional change upon water absorption, and The effect of fluidity at the time of melting is improved by introducing a flexible skeleton.

The semi-aromatic polyamide resin (A1) of the present invention preferably satisfies 7.5 Å [the number of carbon atoms in the polyamide resin/the number of guanamine bonds in the polyamide resin). (The following is a case where [the number of carbon atoms in the polyamide resin/the number of guanamine bonds in the polyamide resin] is simply referred to as the average number of carbon atoms between the guanamine bonds.)

When [the number of carbon atoms in the polyamine resin/the number of guanamine bonds in the polyamide resin] is less than 7.5, since the water absorbability becomes too high, foaming may occur in the subsequent reflow step. Moreover, it is easy to change color due to heat or light. On the other hand, when the ketone resin or epoxy resin is sealed in the reflector of the LED, the reaction point of the fluorenone resin or the epoxy resin is reduced, and the adhesion is lowered, and the LED package is made. Reliability is greatly reduced, so [carbon atoms in polyamine resin It is more preferable that the number of guanamine bonds in the number/polyamide resin is 8.2 or less.

Further, the semi-aromatic polyamide resin (A1) of the present invention satisfies [the number of carbon atoms in the aromatic ring in the polyamine resin/the total number of carbon atoms in the polyamide resin] ≦ 0.35. (The following is a case where [the number of carbon atoms in the aromatic ring in the polyamine resin/the total number of carbon atoms in the polyamide resin] is simply referred to as the carbon atom ratio on the aromatic ring.)

In the LED reflector for illumination or automotive interior and exterior, not only the light emitted by the LED chip is continuously received, but also ultraviolet rays are received when used outdoors, so the material needs high UV resistance. When [the number of carbon atoms in the aromatic ring in the polyamine resin/the total number of carbon atoms in the polyamine resin] exceeds 0.35, the absorption of light particularly in the ultraviolet region becomes large, and the light-induced aggregation The deterioration of the guanamine resin is remarkable. Further, when an aromatic ring is present, the polyamide resin is likely to form a conjugated structure which is a main cause of discoloration due to deterioration, and exhibits remarkable discoloration. Therefore, the concentration of the aromatic ring in the polyamide resin is preferably low. On the other hand, from the viewpoint of achieving heat resistance or high melting point, it is more preferable that the number of carbon atoms in the aromatic ring/the total number of carbon atoms in the polyamide resin is 0.28 or more in the polyamide resin.

The semi-aromatic polyamide resin (A1) in the present invention is particularly preferably composed of hexamethylenediamine/terephthalic acid/11-aminoundecanoic acid (undeceneamine) or hexamethylenediamine. /terephthalic acid/12-aminododecanoic acid (12-lauryl decylamine), guanidine diamine/terephthalic acid/11-aminoundecanoic acid (undeceneamine), guanidine diamine Polydecylamine composed of terephthalic acid/12-aminododecanoic acid (12-lauryl decylamine). Among them, from the viewpoint of high melting point, a constituent unit derived from an equivalent amount of a molar salt of a diamine having a carbon number of 2 to 8 and terephthalic acid has a derived from hexamethylenediamine and terephthalic acid. In the case of a constituent unit of the same amount of the molar salt, in addition to achieving high heat resistance, fluidity, and low water absorbability, in order to achieve more excellent formability, the constituent unit 55 to 75 mol% and the 11-amino group. A copolymerized polyamine resin having a composition of 45 to 25 mol% of the constituent units of undecanoic acid or eleven indoleamine is preferred.

The semi-aromatic polyamide resin (A1) is characterized in that it is not only greatly improved as a conventional 6T-based polyamine (for example, polyamine composed of terephthalic acid/isophthalic acid/hexamethylenediamine). 6T6I, polyamine 6T66 consisting of terephthalic acid/adipic acid/hexamethylenediamine, from terephthalic acid / Polyamido 6T6I66 composed of isophthalic acid / adipic acid / hexamethylenediamine, composed of terephthalic acid / hexamethylenediamine/2-methyl-1,5-pentamethylenediamine Polyacetamide 6T/M-5T, polyacetamide 6T6 consisting of terephthalic acid / hexamethylenediamine / ε-caprolactam, high water absorption, and also highly meet the needs of LED reflectors Heat resistance or surface reflectance. Further, since it has a long-chain fat skeleton derived from the flexibility of the polyamide 11 component, it is also characterized in that fluidity is easily secured.

Corresponding to a component of 6T polydecylamine obtained by co-condensation polymerization of hexamethylenediamine (6) and terephthalic acid (T) by an equivalent amount of Mo (hereinafter, 6T), specifically, The one shown in the formula (I).

The 6T component is a main component of the semi-aromatic polyamide resin (A1), and has an effect of imparting excellent heat resistance, mechanical properties, and the like to the semi-aromatic polyamide resin (A1). The blending ratio of the 6T component in the semi-aromatic polyamide resin (A1) is preferably 55 to 75 mol%, more preferably 60 to 70 mol%, and particularly preferably 62 to 68 mol%. When the blending ratio of the 6T component is less than the above lower limit, the 6T polyamine which is a crystal component may be inhibited by the crystal due to the copolymerization component, and may have a decrease in formability or high-temperature characteristics. On the other hand, when the above upper limit is exceeded, the melting point may become too high and decomposition may occur during processing, which is not preferable.

The 11-polyamide component (hereinafter referred to as 11NY) obtained by polycondensing 11-aminoundecanoic acid or undecanoin, specifically, is represented by the following formula (II).

The 11NY component is a water-absorbent property and fluidity for improving the disadvantage of the 6T component, and has a function of adjusting the melting point of the semi-aromatic polyamide resin (A1) and raising the temperature of crystallization to improve the formability, and to reduce the water absorption rate. The effect of an accident caused by a change in physical properties or a change in size at the time of water absorption, and an effect of improving the fluidity at the time of melting by introducing a flexible skeleton. The blending ratio of the 11NY component in the semi-aromatic polyamide resin (A1) is preferably 45 to 25 mol%, more preferably 40 to 30 mol%, and particularly preferably 38 to 32 mol%. When the blending ratio of the 11NY component is less than the above lower limit, the melting point of the semi-aromatic polyamide resin (A1) is not sufficiently lowered, and the formability is insufficient, and the effect of reducing the water absorption rate of the obtained resin is insufficient. And when it absorbs water, it may cause instability of physical properties such as a decrease in mechanical properties. When the above upper limit is exceeded, the melting point of the semi-aromatic polyamide resin (A1) may be excessively lowered and the crystallization rate may be slow, and the formability may be deteriorated, and the amount of the 6T component may be small, and mechanical properties or heat resistance may be obtained. The possibility of sexual deficiencies is less than ideal.

The thermoplastic resin composition for an LED reflector of the present invention, wherein the thermoplastic resin (A) is a semi-aromatic polyamide resin (A1), is present in the DSC measurement from the lowest temperature side of the polyamide resin. The DSC melting peak temperature (the melting peak temperature on the low temperature side in the case of double peak), that is, the low temperature side melting point (Tm) is preferably 290 to 350 °C. The Tm is preferably 300 to 340 ° C, and particularly preferably 310 to 340 ° C. When Tm exceeds the above upper limit, the processing temperature required for the injection molding of the thermoplastic resin composition of the present invention is extremely high, so that the thermoplastic resin composition is decomposed during processing, and the purpose is not obtained. Physical condition or appearance. On the other hand, when Tm is less than the above lower limit, the crystallization rate becomes slow, and it may become difficult to form all of them. Further, there is a possibility that the solder heat resistance may be lowered. When the Tm is 310 to 340 ° C, it is suitable for the reflow heat resistance of 280 ° C, and can also be adapted to the gold/tin eutectic soldering step, which is preferable. As a method of measuring the melting point, it was measured at 105 ° C in an aluminum dish (manufactured by TA Instruments, part number 900793.901). 10 mg of the polyamide resin after drying for 15 hours under reduced pressure was sealed with aluminum (manufactured by TA Instruments, part number 900794.901), and a measurement sample was prepared, and then a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) was used. The temperature was raised from room temperature at 20 ° C / min, and after holding at 350 ° C for 3 minutes, the test sample was taken out, immersed in liquid nitrogen, and rapidly cooled. Thereafter, the sample was taken out from liquid nitrogen, and after standing at room temperature for 30 minutes, the differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) was again used, and the temperature was raised from room temperature at 20 ° C /min, and held at 350 ° C for 3 minutes. At this time, the peak temperature of the endotherm caused by the melting is taken as the melting point (Tm).

In the semi-aromatic polyamine resin (A1) of the present invention, a constituent unit derived from an equivalent amount of a molar salt of a diamine having a carbon number of 2 to 8 and terephthalic acid is used as a main component, and a guanamine is simultaneously used. Since the bond concentration and the aromatic ring concentration are set to a specific range, in addition to the high melting point or formability, the balance between low water absorption and fluidity is also good, and the light resistance is also excellent. Therefore, the thermoplastic resin composition for LED reflecting sheets of the present invention obtained from the semi-aromatic polyamide resin (A1) has a high melting point of 300 ° C or higher in the formation of the reflecting plate of the surface mount type LED. In addition to low water absorption, it may also be a thin-walled, high-turn forming.

The semi-aromatic polyamide resin (A1) may also be a constituent unit derived from the same amount of the molar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid, or obtained from the above carbon number 10~ The constituent unit of the aminocarboxylic acid or the indoleamine other than the constituent unit of one or more of the diamine, the dicarboxylic acid, the aminocarboxylic acid or the indoleamine of 18 is copolymerized at a maximum of 20 mol%.

In the production of the semi-aromatic polyamide resin (A1), phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt or an ammonium salt or an ester thereof may be mentioned as a catalyst to be used. Specific examples of the metal of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, rhenium, titanium, ruthenium and the like. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, stearyl ester, decyl ester, stearyl ester, phenyl ester or the like can be added. Further, from the viewpoint of improving the melt retention stability, an alkali compound such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or magnesium oxide is preferably added.

The relative viscosity (RV) of the semi-aromatic polyamide resin (A1) measured at 20 ° C in 96% concentrated sulfuric acid is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.5 to 2.5. Making the relative viscosity of polyamine into A method of adjusting the molecular weight is mentioned as a method of a certain range.

The semi-aromatic polyamide resin (A1) can adjust the terminal group amount and molecular weight of the polyamide by adjusting the molar ratio of the amine group to the molar ratio of the carboxyl group and performing polycondensation or by adding a terminal blocking agent. In the case where the molar ratio of the amine group to the molar ratio of the carboxyl group is polycondensed at a certain ratio, the molar ratio of the total diamine to the total dicarboxylic acid used is adjusted to diamine/dicarboxylic acid = 1.00/1.05 to 1.10. The range of /1.00 is ideal.

The period at which the terminal blocking agent is added may be, for example, when the raw material is added, at the time of starting the polymerization, at the later stage of the polymerization, or at the end of the polymerization. The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amine group or a carboxyl group at the terminal of polyamine, and an acid anhydride such as a monocarboxylic acid, a monoamine or a phthalic anhydride can be used. Monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like. Examples of the terminal blocking agent include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and trimethylacetic acid. Aliphatic monocarboxylic acid such as isobutyric acid, alicyclic monocarboxylic acid such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, benzene An anhydride such as acetic acid or the like, an aromatic acid such as maleic anhydride, phthalic anhydride or hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine or decylamine. An alicyclic monoamine such as stearylamine, dimethylamine, diethylamine, dipropylamine or dibutylamine, an alicyclic monoamine such as cyclohexylamine or dicyclohexylamine; aniline, toluidine, diphenylamine, naphthalene An aromatic monoamine such as an amine.

The acid value and the amine value of the semi-aromatic polyamide resin (A1) are preferably from 0 to 200 eq/ton and from 0 to 100 eq/ton. When the terminal functional group exceeds 200 eq/ton, not only gelation or deterioration is promoted at the time of melt retention, but also problems such as coloring or hydrolysis are caused in the use environment. On the other hand, when a reactive compound such as a glass fiber or a maleic acid-denatured polyolefin is mixed, it is preferred to blend the reactivity and the reactive group to have an acid value and/or an amine price of 5 to 100 eq/ton.

The semi-aromatic polyamide resin (A1) can be produced by a conventionally known method, and can be easily synthesized, for example, by subjecting a raw material monomer to a co-condensation reaction. The order of the co-condensation polymerization reaction is not particularly limited, and all of the raw material monomers may be all reacted together, or a part of the raw material monomers may be reversed. Should, the residual starting monomer is then reacted. Further, the polymerization method is not particularly limited, and the addition of the raw material may be progressed to the production of the polymer in a continuous step, or the oligomer may be first produced, or the polymerization may be carried out by an extruder or the like in another step, or the oligomer may be used. The method of polymerizing a polymer by solid phase polymerization. The ratio of each constituent unit in the synthesized copolymerized polyamine can be controlled by adjusting the addition ratio of the raw material monomers.

The polyester resin used in the present invention may be terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4 as an acid component. Aromatic diprotonic acid such as 4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid or 4,4'-diphenyl ether dicarboxylic acid, succinic acid, fumaric acid, and Malay Acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane Aliphatic or alicyclic diprotonic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylate, such as carboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid, etc. Multi-protonic acid copolymerization of acid, ethylene glycol bis(benzene trimellitic anhydride), glycerol ginseng (benzene trimellitic anhydride), and the like. Among these, in order to obtain a polyester having heat resistance or a melting point of interest, terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid is more desirable.

Further, the diol component is not particularly limited, and ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,2-butanediol may be copolymerized. , 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, dipropylene glycol, 2, 2, 4-Trimethyl-1,5-pentanediol, neopentylhydroxytrimethylacetate, oxyethylene adduct of bisphenol A and oxypropylene adduct, oxyethylene addition of hydrogenated bisphenol A And oxypropylene adduct, 1,9-nonanediol, 2-methyloctanediol, 1,10-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, 1, 4-cyclohexanedimethanol, tricyclodecane dimethanol, polycarbonate diol, glycerin, trimethylolpropane, pentaerythritol, dimethylolbutanoic acid, dimethylolpropionic acid, and the like. Among these, in order to obtain a polyester having heat resistance or a melting point of interest, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, Preferably, 1,4-cyclohexanedimethanol or neopentyl glycol is preferred.

In particular, when it is used as a resin for an LED reflector, it is preferable that the melting point is 290 ° C or more from the viewpoint of reflow heat resistance, and terephthalic acid / 1,4-cyclohexane is preferred as a resin composition. An alcohol, a naphthalene dicarboxylic acid/arbitrary diol, a diphenyldicarboxylic acid/arbitrary diol is preferable as the main component, and terephthalic acid/1,4-cyclohexanedimethanol is more preferable.

The thermoplastic resin (A) is preferably present in the thermoplastic resin composition of the present invention in an amount of from 25 to 90% by mass, more preferably from 40 to 75% by mass. When the proportion of the thermoplastic resin (A) is less than the above lower limit, the mechanical strength becomes low, and when it exceeds the above upper limit, the blending amount of the white pigment (B) or the reinforcing material (C) is insufficient, and it becomes difficult to obtain a desired effect. .

The white pigment (B) is blended to increase the surface reflectance of the reflecting plate, and the white pigment (B) is selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, cerium oxide, and oxidation. Magnesium, calcium oxide, barium oxide, titanium hydroxide, zinc hydroxide, zirconium hydroxide, aluminum hydroxide, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, calcium phosphate, calcium carbonate, At least one of the group consisting of lead carbonate, cesium carbonate, and magnesium carbonate. The white pigment (B) preferably has a refractive index higher than that of the base resin. Among these white pigments, titanium oxide is preferred because it has a high refractive index, is stable, and can be obtained at low cost.

Examples of the titanium oxide include rutile-type and anatase-type titanium oxide (TiO ₂ ), titanium oxide (TiO), and titanated titanium (Ti ₂ O ₃ ) produced by a sulfuric acid method or a chlorine method. It is particularly preferable to use rutile-type titanium oxide (TiO ₂ ). The average particle diameter of the titanium oxide is generally 0.05 to 2.0 μm, preferably 0.15 to 0.5 μm, and one type may be used, or titanium oxide having a different particle diameter may be used in combination. The concentration of the titanium oxide component is 90% or more, preferably 95% or more, and more preferably 97% or more. Further, the titanium oxide may be subjected to surface treatment using a metal oxide such as cerium oxide, aluminum oxide, zinc oxide or zirconium oxide, a coupling agent, an organic acid, an organic polyol, a decane or the like.

The ratio of the white pigment (B) is from 3 to 100 parts by mass, preferably from 10 to 70 parts by mass, per 100 parts by mass of the thermoplastic resin (A). When the ratio of the white pigment (B) is less than the above lower limit, the surface reflectance is lowered, and when it exceeds the above upper limit, there is a possibility that the workability such as a large drop in physical properties or a decrease in fluidity may be lowered.

As a acicular or fibrous reinforcing material (C), as long as it is a thermoplastic resin with a refractive index higher than that of the base resin The refractive index of the resin (A) is not particularly limited as long as it is less than 0.02, and a conventionally known reinforcing material can be used depending on the refractive index of the base resin. {Refractive index of thermoplastic resin (A)} - {Refractive index of reinforcing material (C)} is preferably 0.03 or more.

Examples of the needle-shaped reinforcing material include potassium titanate whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium carbonate whiskers, basic magnesium sulfate whiskers, and apatite. At least one selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material is used. Examples of the fibrous reinforcing material include glass fibers, carbon fibers, boron fibers, ceramic fibers, and metal fibers. As the glass fibers, diced or continuous monofilament fibers having a length of 0.1 mm to 100 mm can be used. For the cross-sectional shape of the glass fiber, a circular cross section and a glass fiber having a non-circular cross section can be used. The diameter of the circular cross section glass fiber is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less. Further, glass fibers having a non-circular cross section are preferred depending on the physical surface or fluidity. The glass fiber having a non-circular cross section also includes a cross section perpendicular to the longitudinal direction of the fiber length, which is slightly elliptical, slightly rounded, and slightly rounded, and preferably has a flatness of 1.5 to 8. Here, the flatness is assumed to be a rectangle having a minimum area perpendicular to the cross section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of the rectangle is taken as the long diameter, and the length of the short side is taken as the long diameter of the short diameter. / Short diameter ratio. The thickness of the glass fiber is not particularly limited, but the short diameter is 1 to 20 μm and the long diameter is about 2 to 100 μm. Further, it is preferable to use a fiber bundle as a fiber bundle and cut into a strand having a fiber length of about 1 to 20 mm.

In general, the refractive index of the thermoplastic resin is about 1.35 to 1.74, and when considering the refractive index of a substance which can be used as a reinforcing material, {the refractive index of the thermoplastic resin (A)}-{the reinforcing material (C) The refractive index} is preferably 0.4 or less. The refractive index of the reinforcing material (C) is preferably 1.70 or less, more preferably 1.65 or less, particularly preferably 1.60 or less, and most preferably 1.54 or less.

When the semi-aromatic polyamide resin or the polyester resin described above is used as the thermoplastic resin (A), the refractive index of the reinforcing member (C) is preferably 1.54 or less in order to satisfy the difference in refractive index.

Among the above-mentioned reinforcing materials, basic magnesium sulfate whiskers have a low refractive index and are easy to obtain a difference in refractive index from the base resin, which is particularly preferable. Among them, at least the surface is alkaline, and it is preferable to suppress the thermal discoloration of the polyamide resin.

The ratio of the acicular or fibrous reinforcing material (C) is 5 to 100 parts by mass, preferably 10 to 60 parts by mass, per 100 parts by mass of the thermoplastic resin (A). When the proportion of the reinforcing material (C) is less than the above lower limit When the mechanical strength of the molded article is lowered, the surface reflectance and the formability tend to decrease when the upper limit is exceeded.

Non-fibrous or non-needle fillers may be included for the purpose thereof without departing from the scope of the effects of the present invention. Examples of the non-fibrous or non-needle-shaped filler include reinforcing fillers, conductive fillers, magnetic fillers, flame-retardant fillers, heat-conductive fillers, and fillers for suppressing thermal yellowing, and specific examples thereof. Glass beads, glass cullet, glass balloon, cerium oxide, talc, kaolin, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotubes, fullerenes, indium oxide, tin oxide, iron oxide, oxidation Magnesium, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, red phosphorus, calcium carbonate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, barium sulfate, and non-acicular bismuth Gray stone, potassium titanate, aluminum borate, magnesium sulfate, zinc oxide, calcium carbonate, and the like. These fillers may be used alone or in combination of two or more. Among these, talc is preferable because the crystallization temperature (Tc1) at the time of temperature rise is lowered and the formability is improved. The amount of the filler to be added may be selected in an optimum amount, but may be added up to 50 parts by mass based on 100 parts by mass of the thermoplastic resin (A), and from 0.1 to 20% from the viewpoint of mechanical strength of the resin composition. Preferably, it is preferably 1 to 10 parts by mass. Further, in order to improve the affinity with the thermoplastic resin, the fibrous reinforcing material or the filler may be used by an organic treatment or a coupling agent, or may be used in combination with a coupling agent during melt synthesis, and may be used as a coupling agent. Any one of a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent, among which an amino decane coupling agent and an epoxy decane coupling agent are particularly preferable.

In the thermoplastic resin composition for an LED reflector of the present invention, various additives of a thermoplastic resin composition for a conventional LED reflector can be used. Examples of the additive include a stabilizer, an impact-improving material, a flame retardant, a mold release agent, a slidability-improving material, a colorant, a plasticizer, a crystal nucleating agent, and a resin different from the thermoplastic resin (A).

Examples of the stabilizer include organic antioxidants such as hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants, and heat stabilizers, hindered amine-based, benzophenone-based, and imidazole-based light stabilizers. Or UV absorbers, metal passivators, etc. As the copper compound for the stabilizer for polyamine, copper (I) chloride, copper (I) bromide, copper (I) iodide, copper (II) chloride, copper (II) bromide, iodide can be used. a copper salt of an organic carboxylic acid such as copper (II), copper (II) phosphate, copper (II) pyrophosphate, copper sulfide, copper nitrate or copper acetate. Further, as a constituent component other than the copper compound, a halogenated alkali metal compound is preferable, and examples of the halogenated alkali metal compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, and sodium bromide. Sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, and the like. These additives may be used alone or in combination of two or more. The amount of the stabilizer to be added may be selected in an optimum amount, but may be added in an amount of up to 5 parts by mass based on 100 parts by mass of the thermoplastic resin (A).

Examples of the impact modifier include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer, and ethylene. Polyolefin resin such as methacrylate copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), ethylene polymer resin such as styrene-isoprene-styrene copolymer (SIS), acrylate copolymer, etc., using polybutylene terephthalate or polybutylene naphthalate as Polyester block copolymer, polyamidamide elastomer, urethane obtained by hard segment and polytetramethylene glycol or polycaprolactone, or polycarbonate diol as soft segment An elastomer, an acrylate elastomer, a ruthenium rubber, a fluorine-based rubber, a polymer particle having a core-shell structure composed of two different polymers, and the like. The amount of the impact modifier to be added may be selected in an optimum amount, but may be added up to 30 parts by mass based on 100 parts by mass of the thermoplastic resin (A).

As the flame retardant, a halogen-based flame retardant and a flame retardant auxiliary agent can be combined, and examples of the halogen-based flame retardant include brominated polystyrene, brominated polyphenylene ether, and brominated bisphenol epoxy polymer. Brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane and brominated crosslink An aromatic polymer or the like is preferable, and examples of the flame retardant auxiliary agent include layered niobate such as antimony trioxide, antimony pentoxide, sodium antimonate, zinc stannate, zinc borate, and montmorillonite, and fluorine polymerization. Things, fluorenone and the like. Among them, from the viewpoint of thermal stability, dibromopolystyrene as a halogen-based flame retardant is preferably combined with any of antimony trioxide, sodium citrate, and zinc stannate as a flame retardant auxiliary. Further, examples of the non-halogen flame retardant include melamine cyanurate, red phosphorus, a metal salt of phosphinic acid, and a nitrogen-containing phosphate-based compound. In particular, a combination of a metal phosphinate and a nitrogen-containing phosphate compound is preferred, and as a nitrogen-containing phosphate compound, A reactive organism of melamine, or a melamine condensate such as melam, a trimeric dicyandiamide, and a polyphosphoric acid or a mixture thereof. When a flame retardant or a flame retardant auxiliary agent is used, it is preferable to add a hydrotalcite-based compound or an alkali compound to prevent metal corrosion such as a mold. The amount of the flame retardant to be added is not particularly limited, and may be added in an amount of up to 50 parts by mass based on 100 parts by mass of the thermoplastic resin (A).

The release agent may, for example, be a long-chain fatty acid or an ester thereof, or a metal salt, a guanamine-based compound, a polyethylene wax, an anthrone or a polyoxyethylene. The long-chain fatty acid is preferably a carbon number of 12 or more, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and octadecanoic acid, and some or all of the carboxylic acid may be used alone. The diol or polyglycol is esterified or a metal salt can also be formed. Examples of the guanamine-based compound include ethyl bis-p-xylyleneamine and methylenebisstearylamine. These release agents may be used singly or as a mixture. The amount of the release agent to be added may be selected in an optimum amount, but may be added in an amount of up to 5 parts by mass based on 100 parts by mass of the thermoplastic resin (A).

The thermoplastic resin composition for an LED reflector of the present invention can be produced by blending each of the above-described constituent components by a conventionally known method. For example, a component may be added during the polycondensation reaction of the thermoplastic resin (A), or the thermoplastic resin (A) may be dry-blended with other components, or a twin-screw type extrusion machine may be used. A method in which each component is melted and kneaded.

Example

The present invention will be further specifically described below based on examples, but the present invention is not limited to the examples. Further, the measured values described in the examples were measured by the following methods.

(1) Refractive index

The refractive index of the thermoplastic resin is based on the A method of JIS K-7142, and the sodium D line (wavelength: 589 nm) is used as a light source, and an Abbe refractometer type 4 (manufactured by Atago Co., Ltd.) is used for the unstretched film. Determination. At this time, the contact liquid was measured using 1-bromonaphthalene under the conditions of a temperature of 23 ° C and a relative humidity of 65%.

The refractive index of the reinforcing material was measured in accordance with the B method (Becker method) of JIS K-7142, using a sodium D line (wavelength: 589 nm) as a light source, and measuring at a temperature of 23 ° C and a relative humidity of 65%. also, Those who have literature values and who have difficulty in measuring are based on literature values.

(2) Diffusion reflectivity and its retention rate

Toshiba mechanical injection molding machine EC-100 was used, the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a flat plate having a longitudinal direction of 100 mm, a width of 100 mm, and a thickness of 2 mm was injection-molded, and a test piece for evaluation was produced. Using the test piece, an integrating sphere made by the company was placed in an automatic recording spectrophotometer "U3500" manufactured by Hitachi, Ltd., and the reflectance at a wavelength of 350 nm to 800 nm was measured. In the comparison of the reflectances, the diffuse reflectances at wavelengths of 460 nm and 600 nm were obtained. Further, in the evaluation of the heat-resistant discoloration property, the diffusion reflectance of the sample after being treated at 170 ° C for 2 hours in an oven was measured. In addition, the ratio of the diffuse reflectance of the test piece containing the evaluation of each reinforcing material to the diffuse reflectance of the test piece for evaluation in the case where the reinforcing material is not contained is described as the retention ratio (%).

(3) Bending characteristics, heat distortion temperature

The pellets of the examples and the comparative examples were subjected to injection molding test pieces according to ISO 294-1, and physical properties were evaluated. The method of physical property evaluation is as follows.

Bending properties...ISO 178

Heat distortion temperature (load 1.8MPa)...ISO 75-1

(4) Solder heat resistance

Toshiba mechanical injection molding machine EC-100 was used, the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a test piece for UL combustion test having a molding length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mm was injected. Make a test piece. The test piece was placed in a gas atmosphere at 85 ° C and 85% RH (relative humidity) for 72 hours. The test piece was heated in an air reflow furnace (AIS-20-82C manufactured by Eightech) from room temperature to 150 ° C for 60 seconds, and after preliminary heating, preheating was carried out at a temperature increase rate of 0.5 ° C /min to 190 ° C. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C/min, and after cooling at a predetermined temperature for 10 seconds, it was cooled. The set temperature was increased from 240 ° C at a pitch of 5 ° C, and the highest set temperature at which no expansion or deformation of the surface was generated was used as the reflow heat resistance temperature, and was used as an index of solder heat resistance.

◎: Reflow heat resistance temperature is 280 ° C or higher

○: Reflow heat resistance temperature is 260 ° C or more and less than 280 ° C

×: Reflow heat resistance temperature is less than 260 ° C

<Synthesis Example of Polyamine Resin 1>

7.54 kg of 1,6-hexamethylenediamine, 10.79 kg of terephthalic acid, 7.04 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphite as a catalyst, 40 g of acetic acid as a terminal regulator, and ion exchange 17.52 kg of water was placed in a 50-liter autoclave, pressurized with N ₂ from normal pressure to 0.05 MPa, and discharged to a normal pressure. This operation was carried out three times, and after N ₂ substitution, it was uniformly dissolved at 135 ° C and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feeding pump, and the mixture was heated to 240 ° C in a heating pipe and heated for 1 hour. Next, the reaction mixture was supplied to the pressurized reaction tank, and the mixture was heated to 290 ° C to maintain the internal pressure of the tank at 3 MPa, and one part of the water was distilled off to obtain a lower condensate. After that, the lower condensate was supplied to the biaxial extruder (screw diameter: 37 mm, L/D = 60), and the resin temperature was 330 ° C. The water was discharged from the three holes while melting. Polycondensation was carried out to obtain a polyamine resin 1.

The obtained polyamide resin 1 had a 6T/11=65/35 (mole ratio), a relative viscosity of 2.1, an average carbon number of 8.0 between the guanamine bonds, and a carbon atom ratio of 0.281 on the aromatic ring. At 314 ° C, the refractive index is 1.56.

<Synthesis Example of Polyamine Resin 2>

15.51 kg of 1,10-decanediamine, 14.95 kg of terephthalic acid, 2.01 kg of 11-aminoundecanoic acid, 9 g of sodium diphosphite as a catalyst, 40 g of acetic acid as a terminal regulator, and ion exchange water of 17.52 The kg is added to a 50-liter autoclave, and the polyamide resin 2 is synthesized in the same manner as the polyamide resin 1.

The obtained polyamide resin 2 has a 10T/11 = 90/10 (mole ratio), a relative viscosity of 2.0, an average carbon number of 9.1 between the guanamine bonds, and a carbon atom ratio of 0.312 on the aromatic ring. The refractive index was 1.57 at 304 °C.

<Synthesis Example of Polyester Resin 1>

Polycyclohexane terephthalic acid dimethylene methyl ester (PCT resin) can be obtained according to the method described in the specification of U.S. Patent No. 2,901,466. The PCT resin had a melting point of 290 ° C and a refractive index of 1.57.

With respect to 100 parts by mass of the thermoplastic resin of the examples and the comparative examples and the reference examples and the synthesis examples, the content of the titanium oxide is 55 parts by mass, the content of each of the following reinforcing materials is 30 parts by mass, and the release agent is stabilized. The content of the agent was changed to 0.6 parts by mass, and a biaxial extruder STS-35 manufactured by Coperion Co., Ltd. was used. The polyamide resin 1 and the polyamide resin 2 were melt-kneaded at 330 ° C, and the polyester resin 1 was used. The thermoplastic resin composition of the examples and the comparative examples was obtained by melt-kneading at 310 °C. Further, a composition having only a point where the reinforcing material was not blended was obtained as a reference example. The evaluation results are shown in Tables 1 to 3.

White pigment (B)

Titanium oxide: TIPAQUE CR-60, rutile TiO ₂ , average particle size 0.2 μm

Reinforced material (C)

Basic magnesium sulfate whisker (abbreviation: MS): manufactured by Ube Material, MOS HIGEA-1, pH 9.5, refractive index 1.53, average fiber diameter 0.7 μm, average fiber length 28 μm, aspect ratio 28

Glass fiber (abbreviation: GF): Japan Electric Glass Co., Ltd., T-275H

Acicular apatite (abbreviation: WN): NYCO (share) system, NYGLOS8

Calcium carbonate whisker (abbreviation: CC): white stone calcium, WHISCAL

Aluminum borate whisker (abbreviation: AB): Four countries, ALBOREX

Release agent: magnesium stearate

Stabilizer: 肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester (manufactured by Ciba Specialty Chemicals, Irganox 1010)

【Table 1】

【table 3】

In the white LED, in order to further improve the luminous efficiency, it is important to increase the reflectance of the blue LED (luminous peak 440 to 460 nm) and the yellow phosphor (luminous peak 550 to 650 nm). It is known from Tables 1 to 3 that alkaline magnesium sulfate whiskers having characteristics of {refractive index of thermoplastic resin (A)}-{refractive index of reinforcing material (C)} ≧ 0.02 are compared with others. The reinforced material has a high reflectance at the beginning of 460 nm and 600 nm.

Further, even after heat treatment at 170 ° C for 2 hours, high reflectance can be maintained. Further, the basic magnesium sulfate whisker exhibits high heat resistance in the reflow heat resistance test because a sufficient reinforcing effect is obtained.

According to the above, it is confirmed that the combination of the characteristics satisfying the {refractive index of the thermoplastic resin (A)}-{the refractive index of the reinforcing material (C)} ≧ 0.02 is maintained for the initial reflectance and the long-term reflectance required for the LED reflector. Has a special effect.

Industrial use

The thermoplastic resin composition for an LED reflector of the present invention has excellent light reflection characteristics, improves light extraction efficiency of the LED light-emitting element, and suppresses thermal discoloration, thereby contributing to high luminance and durability of the LED. Sexual improvement.

Claims (10)

A thermoplastic resin composition for an LED reflector comprising 3 to 100 parts by mass of a white pigment (B) and a acicular or fibrous reinforcing material (C) 5 to 100 parts by mass of the thermoplastic resin (A). 100 parts by mass of the thermoplastic resin composition, and satisfying the following (i); (i) {refractive index of the thermoplastic resin (A)} - {refractive index of the reinforcing material (C)} ≧ 0.02. The thermoplastic resin composition for an LED reflector according to the first aspect of the invention, wherein the reinforcing material (C) is a basic magnesium sulfate whisker. The thermoplastic resin composition for LED reflectors according to claim 1 or 2, wherein the thermoplastic resin (A) is a semi-aromatic polyamide resin (A1) having a melting point of 290 to 350 °C. The thermoplastic resin composition for LED reflectors of claim 3, wherein the semi-aromatic polyamide resin (A1) contains 50 mol% or more of diamine and p-benzoic acid having 2 to 12 carbon atoms. a constituent unit obtained by equating a molar amount of formic acid, and satisfying the following (a) and (b); (a) 7.5 碳 a number of carbon atoms in the polyamide resin / a number of guanamine bonds in the polyamide resin; And (b) the number of carbon atoms in the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin ≦ 0.35. The thermoplastic resin composition for LED reflectors according to claim 3, wherein the semi-aromatic polyamide resin (A1) contains 50 mol% or more of a diamine having 2 to 8 carbon atoms. A constituent unit obtained by equating a molar amount of terephthalic acid, and satisfying the following (a') and (b'), and the thermoplastic resin composition satisfies the following (c); (a') 7.5 ≦ The number of carbon atoms in the amine resin / the number of guanamine bonds in the polyamide resin ≦ 8.2; (b') 0.28 碳 The number of carbon atoms in the aromatic ring in the polyamide resin / the total carbon atoms in the polyamide resin The number of ≦0.35; (c) the DSC melting peak temperature of the lowest temperature side of the polyamide resin derived from the thermoplastic resin composition is 300 to 340 °C. The thermoplastic resin composition for LED reflectors of claim 4 or 5, wherein the semi-aromatic polyamide resin (A1) is used as a diamine and terephthalic acid having 2 to 8 carbon atoms. The component other than the constituent unit obtained by the same amount of the molar component is obtained by copolymerizing one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or an indoleamine. The thermoplastic resin composition for LED reflectors according to any one of claims 3 to 6, wherein the semi-aromatic polyamide resin (A1) is derived from hexamethylenediamine and para-benzoic acid. Dimethyl The constituent unit of the acid equivalent amount of the molar salt is 55 to 75 mol% and is composed of 45 to 25 mol% of the constituent unit derived from 11-aminoundecanoic acid or undecanoin. The thermoplastic resin composition for LED reflectors according to any one of claims 1 to 7, wherein the white pigment (B) is selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, and oxidation. Aluminum, cerium oxide, magnesium oxide, calcium oxide, cerium oxide, titanium hydroxide, zinc hydroxide, zirconium hydroxide, aluminum hydroxide, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, At least one of the group consisting of calcium phosphate, calcium carbonate, lead carbonate, cesium carbonate, and magnesium carbonate. The thermoplastic resin composition for LED reflectors according to any one of claims 1 to 8, wherein the reflow heat resistance temperature is 280 ° C or higher. A method for producing a thermoplastic resin composition for an LED reflector, in the production of a thermoplastic resin composition comprising a thermoplastic resin (A), a white pigment (B), and a needle-like or fibrous reinforcing material (C) The thermoplastic resin (A) and the reinforcing material (C) are selected in the following manner (i); (i) {refractive index of the thermoplastic resin (A)} - {refractive index of the reinforcing material (C) ≧ 0.02.