KR101910698B1

KR101910698B1 - Thermoplastic resin composition for led reflector plates

Info

Publication number: KR101910698B1
Application number: KR1020147021564A
Authority: KR
Inventors: 준이치 나카오; 마코토 다마츠시마; 다츠야 오이
Original assignee: 도요보 가부시키가이샤
Priority date: 2012-02-28
Filing date: 2013-02-20
Publication date: 2018-10-22
Also published as: JP6015652B2; WO2013129201A1; TWI570173B; CN104145347A; KR20140130677A; CN104145347B; TW201343743A; JPWO2013129201A1

Abstract

The present invention relates to a thermoplastic resin composition containing 3 to 100 parts by mass of a white pigment (B) and 5 to 100 parts by mass of a needle-like or fibrous reinforcing material (C) relative to 100 parts by mass of a thermoplastic resin (A) (The refractive index of the reinforcing material (C)} 0.02], the thermoplastic resin composition for an LED reflector is excellent in reinforcing effect as a reinforcing material, and the light reflection and scattering effect of a white pigment such as titanium oxide And is effective for improving the brightness and durability of the LED, and a thermoplastic resin composition for an LED reflector is provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a 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 and heat discoloration resistance and is effective for increasing the brightness of an LED.

In recent years, LED (light emitting diode) has been applied to lighting devices, optical devices, cellular phones, backlights for liquid crystal displays, automobile console panels, signaling devices, and display panels by utilizing features such as low power consumption, long life, However, higher brightness and durability are required.

As one means of increasing the brightness of the LED, there is a method of improving the light reflection characteristic of the LED reflector. It has been proposed to incorporate a white pigment such as titanium oxide and a reinforcement into a base resin such as polyamide in order to improve the light reflection characteristic of the LED reflector and to improve dimensional stability and mechanical strength (Patent Documents 1 to 3) .

For example, Patent Document 1 discloses that a copolymerized polyamide containing 50 mol% of dicarboxylic acid units consisting of 100 mol% of terephthalic acid units and 2 mol% of 2-methyl-1,5-pentamethylenediamine and hexamethylenediamine, Discloses a polyamide resin composition containing potassium fiber, wollastonite, and titanium oxide. Patent Document 2 discloses a process for producing a polyurethane resin containing a diamine unit comprising a dicarboxylic acid unit comprising 100 mol% of terephthalic acid unit and a 80: 20 molar ratio of 1,9-nonanediamine unit: 2-methyl- A polyamide resin composition containing titanium dioxide, an aluminum borate whisker and a calcium silicate whisker in a copolymerized polyamide is disclosed. Patent Document 3 discloses a polyamide resin composition containing potassium titanate and titanium oxide in a partially aromatic polyamide.

However, in these resin compositions, the reinforcing material blended for the improvement of dimensional stability and mechanical strength absorbs part of the light reflected from the LED light-emitting element or the white pigment such as titanium oxide, The effect is hindered and it has been newly proved that it becomes an obstacle when it is desired to produce LED of higher luminance.

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-294070 Patent Document 2: Japanese Patent Application Laid-Open No. 2004-75994 Patent Document 3: JP-A-2008-182172

The object of the present invention is not only to provide a reinforcement effect as a reinforcing material but also to a newly found problem that there is almost no problem of inhibiting the light reflection and scattering effect of a white pigment such as titanium oxide, And to provide an effective thermoplastic resin composition for an LED reflector.

In order to achieve the above objects, the present inventors have intensively studied the composition of a reinforcing material which does not inhibit the reflection characteristic of a white pigment in a system of a white pigment and a reinforcing material, and as a result, the present invention has been completed.

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

(1) A thermoplastic resin composition comprising 3 to 100 parts by mass of a white pigment (B) and 5 to 100 parts by mass of a needle-like or fibrous reinforcing material (C) based on 100 parts by mass of the thermoplastic resin (A) A) satisfies the following expression (1).

(A) (refractive index of thermoplastic resin (A)) - {refractive index of reinforcing material (C)} 0.02

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

(3) The thermoplastic resin composition for LED reflector according to (1) or (2), wherein the thermoplastic resin (A) is a semiaromatic polyamide resin (A1) having a melting point of 290 to 350 캜.

(4) The thermoplastic resin composition according to any one of (1) to (4), wherein the semiaromatic polyamide resin (A1) comprises 50 mol% or more of constitutional units obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, The thermoplastic resin composition for an LED reflector according to item 3).

(a) 7.5? number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin

(b) the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin < = 0.35

(5) The thermoplastic resin composition according to the above item (1), wherein the semiaromatic polyamide resin (A1) contains 50 mol% or more of constitutional units obtained from an equimolar molar salt of a diamine having 2 to 8 carbon atoms with terephthalic acid, (3) or (4), wherein the thermoplastic resin composition satisfies the following (c).

(a ') 7.5? number of carbon atoms in polyamide resin / amide bond number in polyamide resin? 8.2

(b ') 0.28? number of carbon atoms on the aromatic ring in the polyamide resin / total number of carbon atoms in the polyamide resin?? 0.35

(c) the DSC melting peak temperature at the lowest temperature side due to the polyamide resin of the thermoplastic resin composition is 300 ° C to 340 ° C

(6) The thermosetting resin composition according to the above item (1), wherein the semi-aromatic polyamide resin (A1) is a component other than the constitutional unit obtained from the equivalent molar salt of diamine and terephthalic acid having 2 to 8 carbon atoms, The thermoplastic resin composition for LED reflector according to any one of (4) to (5), wherein the thermoplastic resin composition is obtained by copolymerizing two or more kinds of thermoplastic resins.

(7) The thermosetting resin composition according to the above item (1), wherein the semiaromatic polyamide resin (A1) comprises 55 to 75 mol% of constitutional units obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, % By weight based on the total weight of the thermoplastic resin composition for LED reflector. (3) The thermoplastic resin composition for LED reflector according to any one of (3) to (6).

(8) The white pigment according to any one of (1) to (5), wherein the white pigment (B) is at least one selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, (1) to (7), which is at least one selected from the group consisting of magnesium, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, calcium phosphate, calcium carbonate, lead carbonate, barium carbonate and magnesium carbonate, The thermoplastic resin composition for an LED reflector according to one of claims 1 to 3.

(9) The thermoplastic resin composition for LED reflector according to any one of (1) to (8), wherein the solder reflow endothermic temperature is 280 占 폚 or higher.

(10) A method for producing a thermoplastic resin composition containing a thermoplastic resin (A), a white pigment (B) and a needle-like or fibrous reinforcing material (C) And the reinforcing material (C) are selected. The method for producing a thermoplastic resin composition for an LED reflector according to claim 1,

Since the refractive index of the reinforcement material is lower than that of the base resin, the thermoplastic resin composition for an LED reflector of the present invention can suppress the incidence of light from the LED light emitting element or light reflected from the white pigment into the reinforcement material from the base resin have. As a result, the thermoplastic resin composition for an LED reflector of the present invention can enhance the light extraction efficiency of the LED light emitting device.

Further, when the base resin is a polyamide resin, the pH of the reinforcing material is alkaline, whereby heat discoloration can be suppressed, and it is possible to provide an LED reflector with excellent durability.

The resin composition for LED reflector of the present invention contains at least one kind of reinforcing material (C) selected from the group consisting of a thermoplastic resin (A), a white pigment (B), a fiber reinforcing material and a needle type reinforcing material.

The thermoplastic resin to be used in the present invention may be at least one selected from the group consisting of polyamide (PA), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate , Polyesters (PEs), polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS), polymethylmethacrylate Styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), fluororesin, polyacrylate, and the like. Among them, polyamide, polyester, liquid crystal polymer, cyclopolyolefin, syndiotactic polystyrene are preferable because they have a high melting point and can adapt to the surface mounting technique. Of these, polyamide and polyester are more preferable, and polyamide is particularly preferable.

The polyamide resin to be used in the present invention is not particularly limited, but in the use of an LED reflector, it is desirable that the heat resistance is as high as possible with a high melting point. Polyamides, and blends of these polyamides are preferable. A melting point of about 290 to 350 캜 is practical in terms of ease of molding, handling, and energy saving.

Examples of the semi-aromatic polyamide (A1) include 6T polyamide (e.g., polyamide 6T6I comprising terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T66 comprising terephthalic acid / adipic acid / hexamethylenediamine, terephthalic acid / isophthalic acid / Polyamide 6T6I66 composed of adipic acid / hexamethylenediamine, polyamide 6T / M-5T composed of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexamethylenediamine / epsilon -caprolactam Polyamide 6T6 composed of terephthalic acid / hexamethylenediamine / tetramethylenediamine), 9T polyamide (terephthalic acid / 1,9-nonanediamine / 2-methyl-1,8-octanediamine) 10T system polyamide (terephthalic acid / 1,10-decanediamine), 12T system polyamide (terephthalic acid / 1,12-dodecanediamine), sebacic acid / Eojineun there may be mentioned polyamides or the like.

Examples of the ring-modified polyamide include polyamides composed of 1,4-cyclohexanedicarboxylic acid / hexamethylenediamine, 1,4-cyclohexanedicarboxylic acid / 1,9-nonanediamine / 2-methyl- , Polyamides composed of 8-octanediamine, and polyamides composed of 1,4-cyclohexanedicarboxylic acid / 1,10-decanediamine.

Among these polyamide resins, the following semi-aromatic polyamide resin (A1) is preferable in view of being able to realize excellent UV resistance in addition to high melting point and low water absorption.

The semiaromatic polyamide resin (A1) preferably contains 50 mol% or more of the constitutional unit obtained from the equivalent molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, and preferably satisfies the following conditions (a) and (b) .

The semiaromatic polyamide resin (A1) contains 50 mol% or more of the constitutional unit obtained from the equivalent molar salt of a diamine having 2 to 8 carbon atoms with terephthalic acid and satisfies the following conditions (a ') and (b') , And it is more preferable that the thermoplastic resin composition satisfies the following (c).

(c) a DSC melting peak temperature at the lowest temperature side attributable to the polyamide resin (A) of the polyamide resin composition is 300 ° C to 340 ° C

Examples of the diamine component having 2 to 12 carbon atoms in the semiaromatic polyamide resin (A1) include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, Hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1, Octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine. These may be used singly or in combination. If the amount of the constituent unit derived from the equivalent molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid is less than 50 mol%, crystallinity and mechanical properties deteriorate, which is not preferable.

However, in the case of a semiaromatic polyamide composed of a constituent unit derived from an equivalent molar salt of a diamine having 9 or more carbon atoms and terephthalic acid, a melting point may be 300 占 폚 or lower, so that an equivalent molar salt of a diamine having 2 to 8 carbon atoms with terephthalic acid And a melting point on the lowermost side of 300 占 폚 or higher is preferable.

In the semiaromatic polyamide resin (A1), other components can be copolymerized in 50 mol% or less of the constitutional units. Examples of the copolymerizable diamine component include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylene Aliphatic diamines such as diamine, alicyclic diamines such as piperazine, cyclohexane diamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'- aminocyclohexyl) Aromatic diamines such as xylylenediamine, p-xylylenediamine, paraphenylenediamine, and metaphenylenediamine, and hydrogenated products thereof.

Examples of the copolymerizable acid component include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-di Aromatic dicarboxylic acids such as phenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid and 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-cyclohexanedicar Alicyclic or alicyclic dicarboxylic acids such as benzoic acid, 3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4-methyl-1,2-cyclohexane dicarboxylic acid, And the like. Examples thereof include lactams such as? -Caprolactam, 11-amino undecanoic acid, undecanolactam, 12-aminododecanoic acid and 12-lauryllactam, and aminocarboxylic acids having a ring-opened structure.

Among them, as the copolymerization component, it is preferable to copolymerize one or more kinds of diamines, dicarboxylic acids, aminocarboxylic acids or lactams having 10 to 18 carbon atoms. More preferably, it is preferable that one or more kinds of aminocarboxylic acids or lactams having 11 to 18 carbon atoms are copolymerized.

When the copolymerization component is composed of a dicarboxylic acid and a diamine, depending on the combination, the melting point is less than 300 ° C, which is not preferable. The aminocarboxylic acid or lactam having a carbon number of 11 to 18 has a role of improving the moldability by adjusting the melting point and the temperature-rise crystallization temperature, the role of reducing the water absorption rate and improving the trouble due to the change in physical properties and dimensional changes upon absorption, And has a role of improving fluidity at the time of melting by introducing one skeleton.

The semiaromatic polyamide resin (A1)

7.5? [Number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin]

Is satisfied. (Hereinafter, [the number of carbon atoms in the polyamide resin / the number of amide bonds in the polyamide resin] may be simply referred to as the average number of carbon atoms between the amide bonds)

When the number of carbon atoms in the polyamide resin / number of amide bonds in the polyamide resin is less than 7.5, foaming may occur in the following reflow soldering process because the water absorbability is too high. In addition, . On the other hand, when sealing the silicone resin or the epoxy resin to the reflector in the packaging of the LED, the active sites of reaction with the silicone resin or the epoxy resin are reduced, the adhesiveness is lowered, and the reliability of the LED package is significantly lowered , And [number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin] is more preferably 8.2 or less.

In addition, the semiaromatic polyamide resin (A1)

[The number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin]? 0.35

Is satisfied. (Hereinafter, [the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin] may simply be abbreviated to the carbon atomic ratio on the aromatic ring)

In the LED reflector for lighting and automotive interior and exterior, not only receives light from the LED chip continuously but also receives ultraviolet rays when used outdoors, high UV resistance is required for the material. When [the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin] exceeds 0.35, the absorption of light particularly in the ultraviolet region becomes large, and the deterioration of the polyamide resin becomes remarkable. In addition, when aromatic rings are present, the polyamide resin tends to form a conjugated structure that is a factor of discoloration due to deterioration, and exhibits remarkable discoloration. Therefore, the aromatic ring concentration in the polyamide resin is preferably low. On the other hand, for the purpose of achieving heat resistance and a high melting point, [number of carbon atoms on the aromatic ring in the polyamide resin / total number of carbon atoms in the polyamide resin] is more preferably 0.28 or more.

As the semiaromatic polyamide resin (A1) in the present invention, hexamethylenediamine / terephthalic acid / 11-amino undecanoic acid (undecalactam), hexamethylenediamine / terephthalic acid / 12-aminododecanoic acid (12- , Decamethylenediamine / terephthalic acid / 11-aminoundecanoic acid (undecalactam), and decamethylenediamine / terephthalic acid / 12-aminododecanoic acid (12-lauryllactam). Among them, in the case of having a constitutional unit derived from an equimolar molar salt of hexamethylenediamine and terephthalic acid as a constitutional unit obtained from an isomorphous salt of a diamine having 2 to 8 carbon atoms with terephthalic acid in view of a high melting point, It is preferable that the copolymer is a copolymerized polyamide resin comprising 55 to 75 mol% of the constituent unit and 45 to 25 mol% of a constituent unit derived from 11-amino undecanoic acid or undecane lactam in order to realize excellent moldability in addition to low water absorption .

The semiaromatic polyamide resin (A1) can be obtained by a conventional 6T polyamide (for example, polyamide 6T6I comprising terephthalic acid / isophthalic acid / hexamethylene diamine, polyamide 6T66 comprising terephthalic acid / adipic acid / hexamethylene diamine, Polyamide 6T6I66 composed of isophthalic acid / adipic acid / adipic acid / hexamethylenediamine, polyamide 6T / M-5T composed of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, terephthalic acid / hexamethylenediamine / polyamide 6T6 made of? -caprolactam), which is a drawback of the polyamide 6T6, is remarkably improved, and also the heat resistance and surface reflectance required for the LED reflector are highly satisfactory. Further, it has a feature of being easy to secure fluidity in that it has a flexible long-chain fat skeleton derived from the polyamide 11 component.

The component (hereinafter referred to as 6T) corresponding to 6T polyamide obtained by co-polycondensation of hexamethylenediamine (6) and terephthalic acid (T) in an equimolar amount is specifically represented by the following formula (I).

The 6T component is a main component of the semiaromatic polyamide resin (A1) and has a role of imparting excellent heat resistance and mechanical properties to the semiaromatic polyamide resin (A1). The mixing 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 still more preferably 62 to 68 mol%. When the compounding ratio of the 6T component is less than the lower limit described above, the 6T polyamide as a crystal component may be inhibited from being crystallized by the copolymerization component, resulting in deterioration of moldability and high temperature characteristics. On the other hand, when the upper limit is exceeded, the melting point is excessively high and there is a risk of decomposition at the time of processing, which is not preferable.

The 11 polyamide component (hereinafter referred to as 11NY) obtained by polycondensation of 11-amino undecanoic acid or undecane lactam is specifically represented by the following formula (II).

The 11NY component is intended to improve the absorbency and fluidity which are defects of the 6T component. It serves to improve moldability by adjusting the melting point and temperature-rise crystallization temperature of the semiaromatic polyamide resin (A1) Has a role of improving troubles due to changes and dimensional changes, and improving fluidity at the time of melting by introducing a flexible skeleton. The mixing 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 still more preferably 38 to 32 mol%. When the mixing ratio of the 11NY component is less than the lower limit described above, the melting point of the semiaromatic polyamide resin (A1) is not sufficiently lowered, which may result in insufficient moldability and insufficient effect of reducing the absorptivity of the obtained resin, There is a fear that the mechanical properties are deteriorated and instability of the physical properties is caused. When the upper limit is exceeded, the melting point of the semi-aromatic polyamide resin (A1) is excessively lowered, the crystallization rate is slowed, and the moldability is deteriorated. On the other hand, the amount of the 6T component is decreased and mechanical properties and heat resistance There is a possibility of insufficient, which is not preferable.

When the thermoplastic resin (A) is a semiaromatic polyamide resin (A1), the thermoplastic resin composition for an LED reflector of the present invention has a DSC melting peak temperature (The melting peak temperature on the low-temperature side in the case of double peaks), that is, the low-temperature side melting point (Tm) is preferably 290 to 350 ° C. The Tm is more preferably 300 to 340 占 폚, and still more preferably 310 to 340 占 폚. When the Tm exceeds the upper limit, since the processing temperature required for injection molding of the thermoplastic resin composition of the present invention becomes extremely high, the thermoplastic resin composition is decomposed at the time of processing and the desired physical properties and appearance are not obtained . Conversely, when the Tm is less than the lower limit, the crystallization speed is slowed, and molding may become difficult in some cases, and the solder heat resistance may be lowered. A Tm of 310 to 340 占 폚 is preferable because it satisfies the reflow soldering heat resistance at 280 占 폚 and is adaptable to the gold / tin process (eutectic soldering) process. As a method for measuring the melting point, 10 mg of a polyamide resin dried under reduced pressure at 105 占 폚 for 15 hours was weighed in an aluminum pan (manufactured by TA Instruments, part number 900793.901) and sealed with aluminum cover (manufactured by TA Instruments, 900794.901) After the sample was prepared, the temperature was raised from room temperature to 20 DEG C / min using a differential scanning calorimeter DSCQ100 (manufactured by TA Instruments), and the sample pan was held at 350 DEG C for 3 minutes. Then, the measurement sample pan was immersed in liquid nitrogen , And quenched. Thereafter, the sample was taken out from the liquid nitrogen, allowed to stand at room temperature for 30 minutes, then elevated from room temperature to 20 DEG C / min using a differential scanning calorimeter DSCQ100 (manufactured by TA Instruments) and held at 350 DEG C for 3 minutes. At this time, the peak temperature of endothermic melting is defined as the melting point (Tm).

The semiaromatic polyamide resin (A1) of the present invention contains a constituent unit derived from an isomeric molar salt of a diamine having 2 to 8 carbon atoms with terephthalic acid as a main component, and also has an amide bond concentration and an aromatic ring concentration set in a specific range It has excellent balance of low absorptivity and fluidity in addition to high melting point and moldability, and is excellent in light resistance. Therefore, the thermoplastic resin composition for an LED reflector of the present invention obtained from such a semiaromatic polyamide resin (A1) has a high melting point and a low absorption of 300 DEG C or more in the formation of a reflector of a surface mount type LED, High-cycle molding is possible.

The semiaromatic polyamide resin (A1) is a structural unit derived from an equivalent molar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid, or a structural unit derived from a diamine, dicarboxylic acid, aminocarboxylic acid or lactam having 1 to 18 carbon atoms A structural unit derived from an aminocarboxylic acid or a lactam other than the structural or plural structural units may be copolymerized at a maximum of 20 mol%.

Examples of the catalyst to be used in the production of the semi-aromatic polyamide resin (A1) include phosphoric acid, phosphorous acid, hypophosphoric acid, metal salts thereof, ammonium salts and esters. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium and antimony. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added. From the viewpoint of improving the melt stability, it is preferable to add an alkali compound such as sodium hydroxide, potassium hydroxide, magnesium hydroxide or magnesium oxide.

The relative viscosity (RV) measured in 96% concentrated sulfuric acid of the semi-aromatic polyamide resin (A1) at 20 캜 is preferably 0.4 to 4.0, more preferably 1.0 to 3.0, and still more preferably 1.5 to 2.5. As a method of setting the relative viscosity of the polyamide within a certain range, a means for adjusting the molecular weight may be mentioned.

The terminal group content and the molecular weight of the polyamide can be adjusted by a method of polycondensation by adjusting the amount of amino group and a molar ratio of carboxyl group, or a method of adding a terminal sealing agent to the semi-aromatic polyamide resin (A1). When the amount of the amino group and the molar ratio of the carboxyl group are polycondensed at a certain ratio, the molar ratio of the total diamine to the total dicarboxylic acid to be used is preferably adjusted to the range of diamine / dicarboxylic acid = 1.00 / 1.05 to 1.10 / 1.00 .

The time of adding the end sealant may be at the time of injecting the raw material, at the beginning of the polymerization, at the end of the polymerization, or at the end of the polymerization. The terminal sealing agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the terminal of the polyamide. An acid anhydride such as monocarboxylic acid or monoamine or phthalic anhydride, a monoisocyanate, Mono-esters, mono-alcohols, and the like. Examples of the terminal sealing agent include aliphatic alcohols such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid Alicyclic monocarboxylic acids such as monocarboxylic acids and cyclohexanecarboxylic acids, aromatic mono-carboxylic acids such as benzoic acid, toluic acid, -naphthalenecarboxylic acid, -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid Examples thereof include acid anhydrides such as carboxylic acid, maleic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and organic anhydrides such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, Aliphatic monoamines such as amine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; And aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

The acid value and the amine value of the semi-aromatic polyamide resin (A1) are preferably 0 to 200 eq / ton and 0 to 100 eq / ton, respectively. When the terminal functional group is more than 200 eq / ton, gelation or deterioration is promoted at the time of melt retention, and problems such as coloring and hydrolysis are caused even under the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid-modified polyolefin is compounded, the acid value and / or the amine value is preferably 5 to 100 eq / ton in accordance with the reactivity and the reactor.

The semiaromatic polyamide resin (A1) can be produced by a conventionally known method, and can be easily synthesized, for example, by carrying out a cocondensation reaction of raw material monomers. The order of the co-polymerization is not particularly limited, and all raw material monomers may be reacted at once, or some raw material monomers may be reacted first, followed by reacting the remaining raw material monomers. The polymerization method is not particularly limited, but the polymerization may be carried out continuously from the injection of the raw material to the production of the polymer. Alternatively, the oligomer may be produced once and then the polymerization may be carried out by an extruder or the like, Or the like may be used. By adjusting the injection ratio of the raw material monomer, the proportion of each constituent unit in the copolymerized polyamide to be synthesized can be controlled.

The polyester resin used in the present invention is preferably an acid component selected from the group consisting of terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'- Diphenyl dicarboxylic acid, and 4,4'-diphenyl ether dicarboxylic acid; aromatic dibasic acids such as succinic acid, fumaric acid, maleic acid, adipic acid, azelaic acid, sebacic acid, Dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid (Anhydrotrimellitate) such as aliphatic or alicyclic dibasic acid such as trimellitic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, ethylene glycol bis (anhydrotrimellitate) and glycerol tris Polybasic acid can be copolymerized.

Among them, in order to obtain a polyester having heat resistance and a desired melting point, there can be mentioned terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, orthophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid Is more preferable.

Examples of the glycol component include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, Butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, dipropylene glycol, 2,2,4-trimethyl- Ethylene oxide adducts and propylene oxide adducts of bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, 1,9-nonanediol, 2-methyloctanediol, 1, Cyclohexanedimethanol, tricyclodecane dimethanol, polycarbonate glycol, glycerin, trimethylol propane, pentaerythritol, dimethyl (2-ethylhexyl) Ortho-carbonic acid, dimethylol propanoic acid and the like can be copolymerized.

Among them, in order to obtain a polyester having heat resistance and a desired melting point, it is preferable to use a polyester such as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol , Neopentyl glycol is preferably used.

Particularly, when used as a resin for an LED reflector, the melting point is preferably 290 DEG C or higher from the viewpoint of heat resistance of solder reflow, and the resin composition includes terephthalic acid / 1,4-cyclohexanedimethanol, naphthalenedicarboxylic acid / Glycol, diphenyldicarboxylic acid / optional glycol as the main component, and terephthalic acid / 1,4-cyclohexanedimethanol is particularly preferable.

The thermoplastic resin (A) is preferably present in a proportion of from 25 to 90 mass%, more preferably from 40 to 75 mass%, in the thermoplastic resin composition of the present invention. If the ratio of the thermoplastic resin (A) is less than the lower limit, the mechanical strength is lowered. If the ratio exceeds the upper limit, the blending amount of the white pigment (B) and the reinforcement (C) is insufficient.

The white pigment (B) is blended to increase the surface reflectance of the reflector. Examples of the white pigment (B) include titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, A group consisting of antimony, titanium hydroxide, zinc hydroxide, zirconium hydroxide, aluminum hydroxide, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, calcium phosphate, calcium carbonate, lead carbonate, barium 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 preferable because it has a high refractive index and is stable and inexpensive to obtain.

Examples of the titanium oxide include rutile and anatase titanium dioxide (TiO ₂ ), titanium monoxide (TiO ₂ ) and titanium trioxide (Ti ₂ O ₃ ) produced by a sulfuric acid method or a chlorine method, the titanium dioxide (TiO ₂₎ is preferably used. The average particle size of titanium oxide is generally in the range of 0.05 to 2.0 占 퐉, preferably 0.15 to 0.5 占 퐉, and may be used as one kind or titanium dioxide having different particle sizes may be used in combination. The titanium oxide component concentration is 90% or more, preferably 95% or more, and more preferably 97% or more. The titanium oxide may be a titanium oxide treated with a metal oxide such as silica, alumina, zinc oxide or zirconia, a coupling agent, an organic acid, an organic polyhydric alcohol or a siloxane.

The proportion of the white pigment (B) is 3 to 100 parts by mass, preferably 10 to 70 parts by mass, per 100 parts by mass of the thermoplastic resin (A). If the ratio of the white pigment (B) is less than the lower limit, the surface reflectance is lowered. If the upper limit is exceeded, there is a fear that the molding property is lowered, such as a drastic decrease in physical properties or lowered fluidity.

The needle-like or fibrous reinforcing material (C) is not particularly limited as long as it has a refractive index lower by 0.02 or more than the refractive index of the thermoplastic resin (A) of the base resin, and conventionally known reinforcement materials can be used according to the refractive index of the base resin . {The refractive index of the thermoplastic resin (A)} - {the refractive index of the reinforcement (C)} is preferably 0.03 or more.

Examples of the needle-like reinforcement material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium carbonate whisker, basic magnesium sulfate whisker, wollastonite, and the like. At least one selected from a fibrous reinforcement material and an needle-like reinforcement material is used. Examples of the fiber-reinforced material include glass fiber, carbon fiber, boron fiber, ceramic fiber and metal fiber. As the glass fiber, it is possible to use? Strand or continuous filament fiber having a length of 0.1 mm to 100 mm It is possible. As the cross-sectional shape of the glass fiber, glass fibers having a circular cross section and a non-circular cross section can be used. The diameter of the circular cross-section glass fiber is 20 占 퐉 or less, preferably 15 占 퐉 or less, more preferably 10 占 퐉 or less. In addition, glass fibers having a non-circular cross section are preferable from the viewpoint of physical properties and fluidity. The glass fiber having a non-circular cross-section includes a substantially elliptical shape, a substantially circular shape, and a substantially cogged shape in cross section perpendicular to the longitudinal direction of the fiber length, and preferably has a flatness of 1.5 to 8. Here, the flatness means a rectangular shape having a minimum area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, assuming that the length of the long side of the rectangle is a long diameter and the length of the short side is a short diameter, / Is the ratio of the diameter to the diameter. The thickness of the glass fiber is not particularly limited, but the diameter of the glass fiber is 1 to 20 mu m and the long diameter is 2 to 100 mu m or so. Further, the glass fiber may be a fiber strand type fiber bundle which has been cut to a fiber length of about 1 to 20 mm.

Generally, the refractive index of the thermoplastic resin is about 1.35 to 1.74, and the refractive index (the refractive index of the thermoplastic resin (A)) - (the refractive index of the reinforcement (C)) is 0.4 or less desirable. The refractive index of the reinforcing material (C) is preferably 1.70 or less, more preferably 1.65 or less, still more preferably 1.60 or less, and particularly preferably 1.54 or less.

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

Among the above reinforcing materials, the basic magnesium sulfate whisker is particularly preferable because it has a relatively low refractive index and is easy to take a difference in refractive index from the base resin. Among them, it is preferable that at least the surface has a basicity because it tends to suppress thermal discoloration of the polyamide resin.

The ratio of the needle-like 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). If the ratio of the reinforcing material (C) is less than the above lower limit, the mechanical strength of the molded article is lowered, and if it exceeds the upper limit, the surface reflectance and molding processability tend to be lowered.

A non-fibrous or non-needle-like filler may be added according to the purpose without impairing the effects of the present invention. As the non-fiber type or non-needle type filler, for example, a reinforcing filler, a conductive filler, a magnetic filler, a flame retardant filler, a heat conduction filler and a heat yellowing inhibiting filler may be cited. Specific examples thereof include glass beads, glass flakes, A metal oxide such as silica, talc, kaolin, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotube, fullerene, indium oxide, tin oxide, iron oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, Barium titanate, aluminum nitride, boron nitride, zinc borate, barium sulfate, and non-needle type wollastonite, potassium titanate, aluminum borate, magnesium sulfate, zinc oxide and calcium carbonate. These fillers may be used alone or in combination of several kinds. Among these, talc is preferable because it lowers the crystallization temperature (Tc1) at the time of elevating the temperature and improves the moldability. The amount of the filler to be added may be selected in an optimum amount. From the viewpoint of the mechanical strength of the resin composition, the amount is preferably 0.1 to 20 parts by mass, more preferably 50 to 50 parts by mass, Preferably 1 to 10 parts by mass. In order to improve the affinity with the thermoplastic resin, the fibrous reinforcement material and the filler are preferably treated with an organic treatment or a coupling agent, or used in combination with a coupling agent at the time of the melting compound. As the coupling agent, Any of a coupling agent, a titanate-based coupling agent and an aluminum-based coupling agent may be used, and among these, an aminosilane coupling agent and an epoxy silane coupling agent are particularly preferable.

In the thermoplastic resin composition for LED reflector of the present invention, various additives of conventional thermoplastic resin composition for LED reflector can be used. Examples of additives include stabilizers, impact modifiers, flame retardants, mold release agents, slip improvers, colorants, plasticizers, nucleating agents and resins different from the thermoplastic resins (A).

Examples of the stabilizer include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants and phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones and imidazoles, ultraviolet absorbers, metal deactivators, etc. . Examples of the copper compound which is a stabilizer for polyamide include cuprous chloride, cuprous bromide, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Examples of the halogenated alkali metal compounds include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, 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 several kinds. The amount of the stabilizer to be added may be selected in an optimum amount, and it is possible to add up to 5 parts by mass to 100 parts by mass of the thermoplastic resin (A).

Examples of the impact modifier include an ethylene-propylene rubber (EPM), an ethylene-propylene-diene rubber (EPDM), an ethylene-acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid copolymer, Styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS) , Acrylic ester copolymers, etc., polyester block copolymers having polybutylene terephthalate or polybutylene naphthalate as hard segment and polytetramethylene glycol or polycaprolactone or polycarbonate diol as soft segment , Polyamide elastomer, urethane elastomer, acrylic elastomer, silicone rubber, Subtotal may be a rubber, such as polymer particles having a core shell structure consisting of polymers of different kinds. The amount of the impact modifier to be added may be selected in an optimum amount, and it is possible to add up to 30 parts by mass to 100 parts by mass of the thermoplastic resin (A).

As the flame retardant, a combination of a halogen-based flame retardant and a flame retardant auxiliary is preferable. Examples of the halogen-based flame retardant include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, styrene bromo styrene a maleic anhydride polymer, brominated epoxy resin, , Decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, and brominated crosslinked aromatic polymer. As the flame retardant auxiliary, antimony trioxide, antimony pentoxide, sodium antimonate, zinc stearate, zinc borate , Montmorillonite and the like, fluorine-based polymers, silicon and the like. Among them, as the halogen-based flame retardant, dibromo-polystyrene and the flame-retardant auxiliary are preferably combined with any of antimony trioxide, sodium antimonate and zinc stannate in terms of thermal stability. Examples of the non-halogen flame retardant include melamine cyanurate, lignin, metal salts of phosphinic acid, and compounds of nitrogen-phosphorous acid-based compounds. Particularly, a combination of a phosphinic acid metal salt and a nitrogen-phosphorus-based compound is preferable, and the nitrogen-phosphorus-based compound includes a melamine or a condensate of melamine such as melam or melon, and a reaction product of polyphosphoric acid or a mixture thereof . As other flame retarding agents and flame retarding auxiliary agents, when these flame retarding agents are used, the addition of a hydrotalcite compound or an alkaline compound is preferable as a metal corrosion prevention of a mold or the like. The amount of the flame retardant to be added may be selected in an optimum amount, and it is possible to add up to 50 parts by mass to 100 parts by mass of the thermoplastic resin (A).

Examples of the release agent include long-chain fatty acids or esters or metal salts thereof, amide compounds, polyethylene waxes, silicones, and polyethylene oxides. Examples of the long-chain fatty acid are preferably 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, and the like. Partial or total carboxylic acid is esterified with monoglycol or polyglycol Or a metal salt may be formed. Examples of the amide compound include ethylenebisterephthalamide and methylenebisstearylamide. These release agents may be used alone or as a mixture. The amount of the releasing agent to be added may be selected in an optimum amount, and it is possible to add up to 5 parts by mass to 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 compounding the respective components described above by a conventionally known method. For example, it is possible to add each component during the polycondensation reaction of the thermoplastic resin (A), dry blend the thermoplastic resin (A) and other components, or melt-knead each constituent component using a twin screw extruder .

Example

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. The measurement values described in the examples were measured by the following methods.

(1) Refractive index

The refractive index of the thermoplastic resin was measured using an Abbe's refractometer type 4 (manufactured by Atago Co., Ltd.) using a sodium D line (wavelength: 589 nm) as a light source and an undrawn film in accordance with Method A of JIS K-7142 did. At this time, 1-bromonaphthalene was used as a contact liquid and measurement was carried out under conditions of a temperature of 23 DEG C and a relative humidity of 65%.

The refractive index of the reinforcing material was measured under the conditions of a temperature of 23 캜 and a relative humidity of 65% using a sodium D line (wavelength: 589 nm) as a light source in accordance with Method B (Bake line method) of JIS K-7142. In addition, it is based on the literature value that the literature value and the measurement are difficult.

(2) Diffuse Reflectance and Retention Rate

A flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm was injection-molded by setting an injection temperature of EC-100, manufactured by Toshiba Machine Co., Ltd., at a cylinder temperature of +20 캜 and a mold temperature of 140 캜, A test piece for evaluation was prepared. Using this test piece, an integrating sphere manufactured by the company was installed in a magnetic spectrophotometer " U3500 " manufactured by Hitachi, Ltd., and the reflectance at a wavelength of from 800 nm to 800 nm was measured. For the reflectance comparison, the diffuse reflectance at a wavelength of 460 nm and 600 nm was determined. For evaluation of heat discoloration resistance, the diffuse reflectance of a sample treated in an oven at 170 DEG C for 2 hours was measured.

The ratio of the diffuse reflectance of each test piece for evaluation of the reinforcing material content to the diffuse reflectance of the test piece for evaluation in the case of not containing the reinforcement material is expressed as the retention ratio (%).

(3) Bending characteristics, heat distortion temperature

The pellets of Examples and Comparative Examples were subjected to injection molding of a test piece according to ISO 294-1, and physical properties were evaluated. The method of evaluation of physical properties is as follows.

Bending properties · · · ISO 178

Heat deformation temperature (load 1.8 MPa) · · · ISO 75-1

(4) Solder heat resistance

A test piece for UL combustion test having a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mm was set at a cylinder temperature of 20 ° C. and a mold temperature of 140 ° C. by using an injection molding machine EC-100 manufactured by Toshiba Machine Co., And injection molding was carried out to prepare a test piece. The test piece was allowed to stand in an atmosphere at 85 캜 and 85% RH (relative humidity) for 72 hours. The test piece was preheated by raising the temperature from room temperature to 150 ° C over a period of 60 seconds in an air reflow furnace (AIS-20-82C manufactured by Aitec Corporation), and then preheated to 190 ° C at a heating rate of 0.5 ° C / . Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C / minute, held at a predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 deg. C to 5 deg. C intervals, and the highest set temperature at which no surface expansion or deformation occurred was used as the reflow heat resisting temperature and used as an index of soldering heat resistance.

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

O: Reflow heat resistance temperature is 260 占 폚 or more and less than 280 占 폚

X: Reflow heat resistance temperature is less than 260 占

&Lt; Synthesis Example of Polyamide 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 diaphosphate as a catalyst, 40 g of acetic acid as a terminal modifier and 17.52 kg of ion-exchanged water were charged into a 50 liter autoclave , Pressurized from normal pressure to 0.05 MPa with N ₂ , depressurized, and returned to normal pressure. This operation was carried out three times, followed by N ₂ substitution, and then uniformly dissolved at 135 ° C and 0.3 MPa under stirring. Thereafter, the solution was continuously fed by a feed pump, heated to 240 캜 by a heating pipe, and heated for 1 hour. Thereafter, a reaction mixture was supplied to the pressurized reaction can, heated to 290 DEG C, and a portion of the water was distilled off so as to maintain the can internal pressure at 3 MPa to obtain a lower condensate. Thereafter, the lower condensate was fed directly to a twin-screw extruder (screw diameter 37 mm, L / D = 60) while maintaining the molten state, the resin temperature was 330 ° C, water was withdrawn from the three vents The polycondensation proceeded under melting to obtain polyamide resin 1.

The resulting polyamide resin 1 had 6T / 11 = 65/35 (molar ratio), relative viscosity 2.1, average number of carbon atoms between amide bonds: 8.0, ratio of carbon atoms on aromatic ring: 0.281, melting point: 314 占 폚, and refractive index: 1.56.

&Lt; Synthesis Example of Polyamide Resin 2 >

15.51 kg of 1,10-decamethylene diamine, 14.95 kg of terephthalic acid, 2.01 kg of 11-aminoundecanoic acid, 9 g of sodium diaphosphate as a catalyst, 40 g of acetic acid as a terminal modifier and 17.52 kg of ion-exchanged water were charged into a 50 liter autoclave And a polyamide resin 2 was synthesized by the same method as that of the polyamide resin 1.

The resulting polyamide resin 2 had 10T / 11 = 90/10 (molar ratio), a relative viscosity of 2.0, an average number of carbon atoms between amide bonds of 9.1 and an aromatic ring carbon atom ratio of 0.312, a melting point of 304 占 폚 and a refractive index of 1.57.

&Lt; Synthesis Example of Polyester Resin 1 >

Polycyclohexanedimethylene terephthalate (PCT resin) was obtained by the method described in U.S. Patent No. 2901466. This PCT resin had a melting point of 290 占 폚 and a refractive index of 1.57.

Examples, Comparative Examples and Reference Examples

The content of the releasing agent and the stabilizer was set to 0.6 parts by mass so that the content of titanium oxide was 55 parts by mass and the content of each reinforcing material was 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin of the synthetic example. Kneaded at 330 DEG C for polyamide resin 1 and polyamide resin 2 and at 310 DEG C for polyester resin 1 using a twin-screw extruder STS-35 manufactured by Tosoh Corporation to obtain thermoplastic resin compositions of Examples and Comparative Examples . In addition, as a reference example, different compositions were also obtained except that no reinforcing material was added. The evaluation results are shown in Tables 1 to 3.

White pigment (B)

Titanium oxide: Tiefer CR-60 manufactured by Ishihara Industries Co., Ltd., rutile type TiO ₂ , average particle diameter 0.2 μm

Reinforced material (C)

Basic pH: 9.5, refractive index: 1.53, average fiber diameter: 0.7 mu m, average fiber length: 28 mu m, aspect ratio: 28 (MS: manufactured by Ube Materials,

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

Needle-shaped wollastonite (abbreviation: WN): manufactured by NYCO, NYGLOS8

Calcium carbonate whisker (abbreviation: CC): Shiraishi calcium manufacturing, wiscar

Aluminum borate whisker (abbreviation: AB): manufactured by Shikoku Kasei, Alborex

Release agent: Magnesium stearate

Stabilizer: pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Irganox 1010)

In the white LED, it is important to increase the reflectance of the blue LED (emission peak: 440 to 460 nm) and the yellow phosphor (emission peak: 550 to 650 nm) in order to further improve the luminous efficiency. It can be seen from Tables 1 to 3 that by using a basic magnesium sulfate whisker having the characteristics of {the refractive index of the thermoplastic resin (A)} - {the refractive index of the reinforcement (C)} 0.02, The initial reflectance is high.

In addition, a high reflectance is maintained even after the heat treatment at 170 DEG C for 2 hours. Further, in the basic magnesium sulfate whisker, a sufficient reinforcing effect was obtained, and therefore, the heat resistance was high even in the reflow heat resistance test.

From the above, the combination of satisfying the characteristics of {the refractive index of the thermoplastic resin (A)} - {the refractive index of the reinforcement (C)}? 0.02 has confirmed the remarkable effect of maintaining the initial reflectance and long-term reflectance required for the LED reflector.

Industrial availability

INDUSTRIAL APPLICABILITY The thermoplastic resin composition for an LED reflector of the present invention is excellent in reflection characteristics of light and can enhance extraction efficiency of light of an LED light emitting element and can suppress thermal discoloration, You can contribute.

Claims

A thermoplastic resin composition comprising 3 to 100 parts by mass of a white pigment (B) and 5 to 100 parts by mass of a needle-like or fibrous reinforcing material (C) based on 100 parts by mass of the thermoplastic resin (A) ) Is a semiaromatic polyamide resin (A1) or polycyclohexanedimethylene terephthalate (PCT) resin having a melting point of 290 to 350 ° C and satisfies the following (A):
(A) (refractive index of thermoplastic resin (A)) - {refractive index of reinforcement (C)} 0.02.

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

The thermoplastic resin composition for LED reflector according to claim 2, wherein the thermoplastic resin (A) is a semiaromatic polyamide resin (A1) having a melting point of 290 to 350 캜.

The polyimide resin composition according to claim 3, wherein the semiaromatic polyamide resin (A1) contains at least 50 mol% of constitutional units obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms with terephthalic acid, A thermoplastic resin composition for an LED reflector which satisfies:
(a) 7.5? number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin
(b) the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin < / = 0.35.

The polyimide resin composition according to claim 3, wherein the semiaromatic polyamide resin (A1) contains at least 50 mol% of constitutional units obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms with terephthalic acid, ), And the thermoplastic resin composition satisfies the following (c):
(a ') 7.5? number of carbon atoms in polyamide resin / amide bond number in polyamide resin? 8.2
(b ') 0.28? number of carbon atoms on the aromatic ring in the polyamide resin / total number of carbon atoms in the polyamide resin?? 0.35
(c) the DSC melting peak temperature at the lowest temperature side due to the polyamide resin of the thermoplastic resin composition is 300 to 340 占 폚.

6. The antifouling paint composition according to claim 5, wherein the semiaromatic polyamide resin (A1) is at least one member selected from the group consisting of aminocarboxylic acids having 11 to 18 carbon atoms or 1 A thermoplastic resin composition for an LED reflector, and a thermoplastic resin composition for an LED reflector.

The polyimide resin composition according to any one of claims 3 to 6, wherein the semiaromatic polyamide resin (A1) comprises 55 to 75 mol% of constitutional units obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, And 45 to 25 mol% of constitutional units derived from undecanactam.

6. The white pigment according to claim 4 or 5, wherein the white pigment (B) is at least one selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, Wherein at least one LED reflector is at least one selected from the group consisting of zirconium hydroxide, aluminum hydroxide, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, calcium phosphate, calcium carbonate, lead carbonate, barium carbonate, And a thermoplastic resin composition.

The white pigment according to claim 7, wherein the white pigment (B) is at least one selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, antimony oxide, titanium hydroxide, zinc hydroxide, There is provided a thermoplastic resin composition for an LED reflector which is at least one selected from the group consisting of aluminum, magnesium hydroxide, lead hydroxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum phosphate, calcium phosphate, calcium carbonate, lead carbonate, barium carbonate and magnesium carbonate .

The thermoplastic resin composition for LED reflector according to claim 4 or 5, wherein the solder reflow endothermic temperature is 280 占 폚 or higher.

The thermoplastic resin composition for an LED reflector according to claim 7, wherein the solder reflow endothermic temperature is 280 占 폚 or higher.

A thermoplastic resin composition comprising a thermoplastic resin (A), a white pigment (B) and a needle-like or fibrous reinforcing material (C) Wherein the thermoplastic resin (A) is selected from the group consisting of a thermoplastic resin (A) of a semi-aromatic polyamide resin (A1) or a polycyclohexanedimethylene terephthalate (PCT) resin having a melting point of 290 to 350 ° C, &Lt; / RTI >
(A) (refractive index of thermoplastic resin (A)) - {refractive index of reinforcement (C)} 0.02.