KR20120075348A - Polyamide resin composition having improved surface reflectance and heat resistance - Google Patents

Abstract

The polyamide resin composition according to the present invention is (A) 10 to 70% by weight of the crystalline polyamide resin, (B) 10 to 70% by weight of the amorphous polyamide resin having a glass transition temperature of 110 to 200 ℃, (C) inorganic filler 10 To 60% by weight, (D) 10 to 50% by weight of the white pigment, and 100% by weight of the total amount of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D) It contains 0.05-2 weight part of (E) light stabilizers with respect to a part, and is excellent in surface reflectance, heat resistance, mechanical strength, workability, light resistance, and discoloration resistance.

Description

Polyamide resin composition having improved surface reflectance and heat resistance

The present invention relates to a polyamide resin composition, and more particularly, to a polyamide resin composition having excellent surface reflectance and heat resistance.

Reflectors are used in many fields for the efficient use of light. In recent years, semiconductors of light sources, i.e., switching to semiconductor lasers and light emitting diodes (hereinafter referred to as "LEDs") for miniaturization of devices and miniaturization of light sources have been advanced. In the reflecting plate of LED and the resin composition for its manufacture, physical properties, such as high light reflectivity, high whiteness, favorable workability, high dimensional stability, high mechanical strength, and high heat resistance, are calculated | required.

In other words, not only the mechanical strength but also the reflecting plate used for the LED is required for heat resistance according to the surface mounting on the printed wiring board and the like, and the excellent moldability is required as the device is downsized. In addition, the reflector is required to have a high reflectance as an inherent function, and particularly to suppress a decrease in reflectance due to heating in the assembly and reflow soldering process of the LED. Moreover, in order to obtain the reflecting plate of high reflectance, special insert molding is also performed, and the resin composition which can be used for such a use is calculated | required.

Conventionally, LCP (liquid crystal polymer) or heat-resistant polyamide resin has been used as a material which can endure reflow soldering at the temperature of 260 degreeC using a lead-free solder. LCP has excellent heat resistance, light resistance and fluidity during molding, but has a problem in that adhesiveness with sealing resin such as epoxy resin used when sealing the resin after installing the light emitting diode on the reflecting plate is lowered. Since it is low, it has a problem that it is difficult to exhibit sufficient high reflectance as a reflecting plate. In addition, although polyamide resins that are widely used in the past are aliphatic polyamides (PA6, PA66, PA11, PA12) having excellent strength characteristics and injection moldability, they are not sufficiently resistant to heat and low absorption to withstand the temperatures of the reflow soldering process. However, there is a problem that the reflectance is lowered by discoloration when heated.

Japanese Laid-Open Patent Publication No. 2000-204244 discloses specific average particle diameters for polycarboxylic acids produced from dicarboxylic acid units containing 60 to 100 mol% of terephthalic acid units and aliphatic alkylenediamine units having 6 to 18 carbon atoms. Eggplant is disclosed a polyamide composition incorporating an inorganic filler. This composition is excellent in heat resistance at the time of moisture absorption, dimensional stability, surface smoothness and excellent surface appearance, but has a problem that it cannot fully prevent the fall of the light reflectivity by discoloration.

International Patent Publications No. 2003-085029 and Japanese Patent Application Laid-open No. Hei 7-228776 disclose a resin composition for reflecting plates made by mixing an inorganic filler with a polyamide resin composed of 1,9-diaminononane. However, this resin composition has the problem that adhesiveness with sealing resin is bad. In addition, Japanese Laid-Open Patent Publication No. 2002-294070 discloses a polyamide resin containing potassium titanate fibers and / or wollastonite. However, this resin cannot obtain sufficient rigidity in molding and has a problem in use in insert molding. Japanese Laid-Open Patent Publication No. 2004-75994 discloses a useful polyamide composition which is a high whiteness, high surface reflectivity molded article and lamp reflector material. This polyamide composition has a disadvantage in that heat resistance is high compared with a resin composition using a conventional heat resistant polyamide such as PA6T or PA46, but does not completely solve discoloration by heating.

It is an object of the present invention to provide a polyamide resin composition having excellent surface reflectance.

Another object of the present invention is to provide a polyamide resin composition having excellent heat resistance.

Still another object of the present invention is to provide a polyamide resin composition having excellent mechanical strength and processability.

Another object of the present invention is to provide a polyamide resin composition having excellent light resistance.

Another object of the present invention is to provide a polyamide resin composition having excellent discoloration resistance.

Still another object of the present invention is to provide a molded article prepared from the polyamide resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

The polyamide resin composition according to the present invention is (A) 10 to 70% by weight of the crystalline polyamide resin, (B) 10 to 70% by weight of the amorphous polyamide resin having a glass transition temperature of 110 to 200 ℃, (C) inorganic filler 10 To 60% by weight, (D) 10 to 50% by weight of the white pigment, and 100% by weight of the total amount of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D) (E) 0.05 to 2 parts by weight of the light stabilizer.

In one embodiment of the present invention, the polyamide resin composition is based on 100 parts by weight of the total content of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D) (F) 0.05 to 3 parts by weight of inorganic fine particles are further included.

In one embodiment of the present invention, the crystalline polyamide resin (A) has a melting point of 260 ~ 350 ℃, the crystallization temperature of 260 ~ 320 ℃, the glass transition temperature is less than 100 ℃.

In one embodiment of the invention, the crystalline polyamide resin (A) consists of a unit derived from (a-1) dicarboxylic acid and a unit derived from (a-2) diamine; Unit (a-1) derived from the said dicarboxylic acid is 30-100 mol% of units derived from terephthalic acid, 0-70 mol% of units derived from aromatic dicarboxylic acids other than terephthalic acid, and 4-4 carbon atoms 0 to 70 mol% of units derived from 20 aliphatic aliphatic dicarboxylic acids or 0 to 70 mole% of units derived from aromatic dicarboxylic acids other than terephthalic acid and the above-mentioned aliphatic dicarboxylic acids having 4 to 20 carbon atoms. 70 mole%; Unit (a-2) derived from the said diamine is a unit derived from the linear or branched aliphatic diamine which has 4-20 carbon atoms.

In one embodiment of the present invention, the amorphous polyamide resin (B) has a glass transition temperature of 120 ~ 160 ℃.

In one embodiment of the invention, the amorphous polyamide resin (B) is a polyamide prepared from terephthalic acid, 2,2,4-trimethyl hexamethylene diamine and 2,4,4-trimethyl hexamethylene diamine; Polyamides prepared from isophthalic acid and 1,6-hexamethylene diamine; Polyamides prepared from terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine; Copolyamides prepared from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam; Polyamides prepared from 1,12-dodecanoic acid and 4,4'-diaminodicyclohexylmethane; Copolyamides prepared from terephthalic acid, isophthalic acid, 3,3-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam and mixtures thereof.

In one embodiment of the present invention, the inorganic filler (C) comprises a glass fiber having an average length of 0.1 to 20mm, an aspect ratio of 10 to 2,000.

In one embodiment of the present invention, the white pigment (D) is selected from the group consisting of titanium oxide, zinc sulfide, lead white, zinc sulfate, alumina oxide and mixtures thereof.

In one embodiment of the present invention, the light stabilizer (E) is a hindered amine compound.

In one embodiment of the present invention, the inorganic fine particles (F) is calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, barium sulfate, zinc emulsion, alkaline carbonate, mica titanium, antimony oxide, magnesium oxide, calcium phosphate, silica, Alumina, mica, talc, kaolin and mixtures thereof.

In one embodiment of the present invention, the polyamide resin composition is an additive selected from the group consisting of antioxidants, heat stabilizers, flame retardants, fluorescent brighteners, plasticizers, thickeners, antistatic agents, mold release agents, pigments, nucleating agents and mixtures thereof It includes more.

The molded article according to the present invention is prepared using the polyamide resin composition.

In one embodiment of the present invention, the molded article has a reflectance of 440 nm light having a wavelength of 80 to 90%, measured after irradiating an LED light source having a wavelength of 460 nm for 200 hours.

In one embodiment of the present invention, the molded article has a yellowness of 1 to 5, measured after irradiation with an LED light source having a wavelength of 460 nm for 200 hours.

The polyamide resin composition according to the present invention is excellent in surface reflectance, heat resistance, mechanical strength, processability, light resistance and discoloration resistance.

Hereinafter, the content of the present invention will be described in more detail.

The polyamide resin composition according to the present invention is (A) 10 to 70% by weight of the crystalline polyamide resin, (B) 10 to 70% by weight of the amorphous polyamide resin having a glass transition temperature of 110 to 200 ℃, (C) inorganic filler 10 To 60% by weight, (D) 10 to 50% by weight of the white pigment, and 100% by weight of the total amount of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D) (E) 0.05 to 2 parts by weight of the light stabilizer.

(A) Crystalline Polyamide Resin

The said crystalline polyamide resin (A) consists of the unit derived from (a-1) dicarboxylic acid, and the unit derived from (a-2) diamine.

(a-1) Unit derived from dicarboxylic acid

The unit derived from the dicarboxylic acid means a residue from which hydroxyl groups at both ends are removed from the dicarboxylic acid, and examples of the dicarboxylic acid include aromatic dicarboxylic acid or aliphatic dicarboxylic acid.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and the like, which may be used alone or in a mixture.

The number of carbon atoms of the aliphatic dicarboxylic acid is not particularly limited and is 4 to 20, preferably 6 to 12. Examples of the aliphatic dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, undecanoic acid, dodecanoic acid, and the like, which may be used alone or in a mixture. Of these, adipic acid is preferred.

In one embodiment of the present invention, the unit derived from dicarboxylic acid, 30 to 100 mol% of units derived from terephthalic acid, preferably 40 to 100, relative to 100 mol% of units derived from dicarboxylic acid Mole%, more preferably 40 to 80 mole%,

In one embodiment of the present invention, the unit derived from the dicarboxylic acid, 0 to 70 units derived from aromatic dicarboxylic acids other than the terephthalic acid relative to 100 mol% of units derived from the dicarboxylic acid Mol%, preferably 0 to 60 mol%, more preferably 20 to 60 mol%.

In one embodiment of the present invention, the unit derived from the dicarboxylic acid has 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms, based on 100 mol% of the unit derived from the dicarboxylic acid. And 0 to 70 mol%, preferably 0 to 60 mol%, more preferably 20 to 60 mol% of units derived from an acid.

In one embodiment of the present invention, the unit derived from dicarboxylic acid is 30 to 100 mol% of units derived from terephthalic acid, and aromatic dica other than terephthalic acid with respect to 100 mol% of units derived from dicarboxylic acid. 0 to 70 mol% of units derived from a leric acid, 0 to 70 mol% of units derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, or a unit derived from an aromatic dicarboxylic acid other than the terephthalic acid. 0 to 70 mol% of units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

In one embodiment of the present invention, the unit (a-1) derived from the dicarboxylic acid may include a small amount, for example, 10 mol% or less of a unit derived from a polybasic acid having three or more carboxyl groups. . Examples of the polybasic acid having three or more carboxyl groups include trimellitic acid and pyromellitic acid.

(a-2) units derived from diamines

The unit derived from the diamine means a residue from which hydrogen at both ends is removed from the diamine, and as the diamine, a linear or branched aliphatic diamine having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms is preferable.

Examples of the linear aliphatic diamines include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1, 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like, which can be used alone or in mixture.

In one embodiment of the present invention, the unit derived from the diamine comprises 50 to 100 mol% of units derived from 1,6-diaminohexane.

Examples of the branched aliphatic diamines include 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1, 8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 2-methyl-1,11-diaminoundecane and the like, which are alone Or in mixtures. Among them, 2-methyl-1,5-diaminopentane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane and 2-methyl-1,9-diaminono It is preferable to use eggs.

The said crystalline polyamide resin (A) can be manufactured by a well-known method, and can be manufactured through polycondensation of a dicarboxylic acid component and a diamine component. For example, as disclosed in WO 2003-085029, the dicarboxylic acid component and the diamine component are heated in the presence of a catalyst to obtain a prepolymer, and by applying a shear stress to the melt of the prepolymer, polycondensation is performed. Crystalline polyamide resins can be prepared.

In one embodiment of the present invention, the crystalline polyamide resin (A) has an intrinsic viscosity [η] of 0.3 to 0.9 dl / g, preferably 0.5 to 0.9 dl / g, measured in a temperature of 25 ° C. and 96.5% sulfuric acid, more Preferably 0.6 to 0.9 dl / g. When the intrinsic viscosity of the crystalline polyamide resin is within the above range, the fluidity during molding can be maintained excellent.

In one embodiment of the present invention, the crystalline polyamide resin (A) has a melting point measured by a differential scanning calorimeter (DSC) of 260 ~ 350 ℃, preferably 290 ~ 335 ℃. In one embodiment of the present invention, the crystalline polyamide resin (A) has a crystallization temperature of 260 ~ 320 ℃, preferably 280 ~ 300 ℃ measured by DSC. In one embodiment of the present invention, the crystalline polyamide resin (A) has a glass transition temperature of less than 100 ℃ measured by DSC. When the melting point, crystallization temperature and glass transition temperature of the crystalline polyamide resin are within the above range, the heat resistance can be maintained excellent. As the crystalline polyamide resin having the above characteristics, C3200 of Mitsui Chemical Co., Ltd. (Japan) and A4002 of Solvay (Belgium) are typical.

In one embodiment of the invention, the crystalline polyamide resin (A) consists of a unit derived from (a-1) dicarboxylic acid and a unit derived from (a-2) diamine; Unit (a-1) derived from the said dicarboxylic acid is 30-100 mol% of units derived from terephthalic acid, 0-70 mol% of units derived from aromatic dicarboxylic acids other than terephthalic acid, and 4-4 carbon atoms 0 to 70 mol% of units derived from 20 aliphatic aliphatic dicarboxylic acids or 0 to 70 mole% of units derived from aromatic dicarboxylic acids other than terephthalic acid and the above-mentioned aliphatic dicarboxylic acids having 4 to 20 carbon atoms. 70 mole%; Unit (a-2) derived from the said diamine is a unit derived from the linear or branched aliphatic diamine which has 4-20 carbon atoms.

The crystalline polyamide resin (A) is 10 to 70% by weight based on 100% by weight of the total content of crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D). %, Preferably 10 to 50% by weight.

(B) amorphous polyamide resin

The amorphous polyamide resin (B) having a glass transition temperature of 110 to 200 ° C according to the present invention is prepared from the following monomers.

Linear or branched aliphatic dicarboxylic acids having 6 to 22 carbon atoms, for example adipic acid, 2,2,4-trimethyl adipic acid, 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, 1 , 12-dodecanoic acid and the like can be used.

Cyclic aliphatic dicarboxylic acids having 6 to 22 carbon atoms, for example cyclohexane-1,4-dicarboxylic acid, 4,4'-dicarboxydicyclohexylpropane, 1,4-bis-carboxymethyl- Cyclohexane and the like can be used.

Aromatic dicarboxylic acids having 8 to 22 carbon atoms, for example 4,4'-diphenylmethanedicarboxylic acid, isophthalic acid, tributyl isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 1 , 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid and the like can be used.

Linear or branched aliphatic diamines having 6 to 14 carbon atoms, for example 1,6-hexamethylene diamine, 2-methyl-1,5-diaminopentane, 2,2,4-trimethyl hexamethylene diamine, 2, 4,4-trimethyl hexamethylene diamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,12-dodecamethylene diamine and the like can be used.

Cyclic aliphatic diamines having 6 to 22 carbon atoms, for example 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'- Diaminodicyclopropane, 1-4-diaminocyclohexane, 1,4-bisaminomethylcyclohexane, 2,6-bisaminomethylnorbornene, 3-aminomethyl-3,5,5-trimethylcyclohexylamine And the like can be used.

Aromatic diamines having 8 to 22 carbon atoms, for example m-xylene diamine, p-xylene diamine, bis-4-aminophenylpropane and the like can be used.

Lactams having 6 to 12 carbon atoms, such as ε-caprolactam or laurotaxam, ω-aminodicarboxylic acid, ε-aminocaproic acid, ω-aminododecanoic acid and the like can be used.

In one embodiment of the invention, the amorphous polyamide resin (B) is a polyamide prepared from terephthalic acid, 2,2,4-trimethyl hexamethylene diamine and 2,4,4-trimethyl hexamethylene diamine; Polyamides prepared from isophthalic acid and 1,6-hexamethylene diamine; Polyamides prepared from terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine; Copolyamides prepared from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam; Polyamides prepared from 1,12-dodecanoic acid and 4,4'-diaminodicyclohexylmethane; Copolyamides prepared from terephthalic acid, isophthalic acid, 3,3-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam and mixtures thereof.

In one embodiment of the present invention, the amorphous polyamide resin (B) has a glass transition temperature of 110 ~ 200 ℃, preferably 120 ~ 160 ℃ measured by DSC. Amorphous polyamide resin having the above characteristics is typical of CX7323 and ARKEMA G350 of Evonik Corporation.

The amorphous polyamide resin (B) is 10 to 70% by weight based on 100% by weight of the total content of the crystalline polyamide resin (A), the amorphous polyamide resin (B), the inorganic filler (C) and the white pigment (D). %, Preferably 10 to 50% by weight.

(C) inorganic filler

The said inorganic filler (C) can be added to the mixture of a crystalline polyamide resin (A) and an amorphous polyamide resin (B), and can improve the strength of resin. Specifically, various inorganic fillers having a shape such as fibrous, powdery, granular, plate, needle, cloth or mat can be used. In more detail, inorganic fibers such as glass fibers, metal-coated glass fibers, ceramic fibers, carbon fibers, metal carbide fibers, metal cured fibers, asbestos fibers and boron fibers may be used as the inorganic filler.

As such a fibrous filler, glass fibers are particularly preferred. By using the glass fiber, the moldability of the composition is improved, and mechanical properties such as tensile strength, bending strength, flexural modulus, and heat resistance such as heat deformation temperature of the molded article formed from the resin composition are improved.

In one embodiment of the invention, the glass fiber has an average length of 0.1 to 20mm, preferably 0.3 to 6mm, the aspect ratio (L (average length of the fiber) / D (average outer diameter of the fiber)) is 10 To 2,000, preferably 30 to 600. In the present invention, it is preferable to use glass fibers having an average length and aspect ratio within the above range.

The inorganic filler (C) is 10 to 60% by weight, based on 100% by weight of the total content of crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D), Preferably 10 to 40% by weight, more preferably 10 to 30% by weight.

(D) white pigment

Examples of the white pigment (D) include titanium oxide, zinc sulfide, lead white, zinc sulfate, alumina oxide, and the like, which may be used alone or in a mixture. As the white pigment, a white pigment treated with a silane coupling agent, a titanium coupling agent, or the like can be used. For example, the white pigment surface-treated with silane type compounds, such as vinyl triethoxysilane, 2-aminopropyl triethoxysilane, and 2-glycidoxy propyl triethoxysilane, can be used. Titanium oxide is preferable as the white pigment, and optical properties such as reflectance and concealability are improved by using the titanium oxide. In addition, the titanium oxide is preferably a rutin type. Further, the particle diameter of the titanium oxide is 0.05 to 2.0 µm, preferably 0.05 to 0.7 µm.

The white pigment (D) is 10 to 50% by weight, based on 100% by weight of the total content of the crystalline polyamide resin (A), the amorphous polyamide resin (B), the inorganic filler (C) and the white pigment (D). , Preferably 10 to 40% by weight, more preferably 10 to 35% by weight.

(E) light stabilizer

The polyamide resin composition of the present invention may further include a light stabilizer in order to prevent discoloration and to suppress a decrease in light reflectance. Examples of the light stabilizer include ultraviolet absorption such as benzophenone compound, salicylate compound, benzotriazole compound, acrylonitrile compound, and other resonance compound. Effective compounds; A compound having a radical trapping ability such as a hindered amine compound, a hindered phenol compound, or a mixture of two or more thereof.

In particular, a compound having an amide bond in the molecule is preferable because it has high solubility in the mixture of the crystalline polyamide resin (A) and the amorphous polyamide resin (B) and excellent in heat resistance. In addition, when a compound having an ultraviolet absorbing effect and a compound having a radical trapping ability are used in combination, a higher effect can be obtained.

The light stabilizer (E) is a crystalline polyamide resin (A), an amorphous polyamide resin (B), an inorganic filler (C), in view of the effect of preventing discoloration of the polyamide resin composition and suppressing a decrease in light reflectance. With respect to 100 parts by weight of the total amount of the white pigment (D), it may be included in 0.05 to 2 parts by weight, preferably 0.1 to 2 parts by weight.

(F) inorganic fine particles

The polyamide resin composition of the present invention may further contain inorganic fine particles in order to suppress a decrease in light reflectance. Examples of the inorganic fine particles include calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, barium sulfate, zinc emulsion, alkaline carbonate, mica titanium, antimony oxide, magnesium oxide, calcium phosphate, silica, alumina, mica, talc, kaolin, and the like. These may be used alone or in mixtures.

The inorganic fine particles (F) is 0.05 to 3 parts by weight, based on 100 parts by weight of the total content of the crystalline polyamide resin (A), the amorphous polyamide resin (B), the inorganic filler (C) and the white pigment (D), Preferably from 0.05 to 2 parts by weight may be included.

(G) additive

The polyamide resin composition of the present invention includes additives such as antioxidants, heat stabilizers, flame retardants, fluorescent brighteners, plasticizers, thickeners, antistatic agents, mold release agents, pigments, nucleating agents, etc., depending on the use within the scope of not impairing the object of the present invention. can do. Examples of the antioxidant include phenols, amines, sulfur, humans, and the like. Examples of the heat stabilizer include lactone compounds, hydroquinones, halogenated copper, and iodine compounds. Examples of the flame retardant include bromine, chlorine, and phosphorus. , Antimony and inorganic systems.

Moreover, the polyamide resin composition of this invention is an ethylene-methylacrylate copolymer, ethylene-ethylacrylate copolymer, ethylene-propylene copolymer, ethylene-1-butene depending on a use within the range which does not impair the objective of this invention. Olefin copolymers such as copolymers, propylene-1-butene copolymers or modified olefin copolymers, polystyrenes, fluorine resins, silicone resins, liquid crystal polymers (LCP), and the like.

The polyamide resin composition of the present invention is a known method, for example, a method of mixing the above components with Henschel mixer, V blender, ribbon blender, tumbler blender, or the like, or after mixing, a single screw extruder, a multi screw extruder, a kneader, a Banbury mixer, or the like. After further melt kneading, it can be produced through the method of granulation or grinding.

The polyamide resin composition according to the present invention not only has excellent light reflectance, heat resistance, adhesion to sealing resins such as epoxy resins, but also can be suitably used as a reflecting plate by suppressing a decrease in reflectance when used as a reflecting plate of an LED drive element.

The present invention provides a molded article prepared from the polyamide resin composition. More specifically, the polyamide resin composition according to the present invention is produced as a reflecting plate for LED devices by heating molding such as injection molding (insert molding of metal such as hoop molding), melt molding, extrusion molding, inflation molding, blow molding, and the like. Can be. In addition, the LED reflector produced from the polyamide resin composition according to the present invention is sealed, bonded or bonded together with a sealing resin together with a general LED element and other components.

The polyamide resin composition and the molded article produced therefrom according to the present invention can be applied not only to LED applications, but also to applications that reflect other rays. For example, the reflecting plate manufactured from the polyamide resin composition which concerns on this invention can be used as a reflecting plate for light emitting devices, such as various electrical and electronic components, room lighting, ceiling lighting, outdoor lighting, automobile lighting, display equipment, a headlight, and the like. The reflecting plate can be produced by heating and melting the polyamide resin composition according to the present invention, followed by molding into a desired mold and cooling. For example, it can shape | mold in a reflecting plate using well-known methods, such as an injection molding method, a compression molding method, and an extrusion molding method.

In one embodiment of the present invention, the molded article prepared from the polyamide resin composition, the reflectance of the wavelength of 440nm light, measured after irradiating an LED light source having a wavelength of 460nm for 200 hours, 70 to 100%, preferably 80 to 90 %, More preferably 85 to 90%.

In one embodiment of the present invention, the yellowness is 1 to 10, preferably 1 to 5, more preferably measured after irradiating an LED light source having a wavelength of 460nm to the molded article prepared from the polyamide resin composition for 200 hours. 1 to 4.5.

Example

The specification of each component used by the following Example and the comparative example is as follows.

(A) Crystalline Polyamide Resin

The melting point measured by DSC was 320 ° C, the crystallization temperature measured by DSC was 288 ° C, and the glass transition temperature measured by DSC was 85 ° C.

(B) amorphous polyamide resin

The glass transition temperature measured by DSC was 142 ° C., and CX7323 manufactured by Eovnik Co., Ltd., which showed no crystallization temperature when measured by DSC, was used.

(C) inorganic filler

CS 910 from OCV reinforcements (USA) was used.

(D) white pigment

Tiron 2233 from KRONOS Corporation (USA) was used.

(E) light stabilizer

CHIMASSORB944 from BASF (GERMANY) was used.

Example  1 to 4 and Comparative Example  1-4

Each component, antioxidant, heat stabilizer and mold release agent were added to a conventional mixer, mixed, extruded using a twin screw extruder heated to 250 to 350 ° C. having L / D = 35 and Φ = 45 mm, and then the extrudate was extruded. After preparing in pellet form, a plate-shaped specimen (length 90 mm, width 49 mm, thickness 2.5 mm) was prepared using a 10 oz injection machine at an injection temperature of 320 to 340 ° C. After leaving the specimen at 48 ° C. for 48 hours at 23 ° C. and 50% relative humidity, the physical properties were measured in the following manner, and the results are shown in Table 1 below.

How to measure property

[Melting point]

Using PerkinElemer DSC7, the temperature was first maintained at 330 ° C for 5 minutes, then lowered to 23 ° C at a rate of 10 ° C / min, and then raised to 10 ° C / min. The endothermic peak at the time of melting was determined as melting point.

[Crystallization temperature]

Using PerkinElemer's DSC7, the highest point of the phase transition temperature generated when first held at 330 ° C. for 5 minutes and then cooled to 23 ° C. at a rate of 10 ° C./min was determined as the crystallization temperature.

[Glass Transition Temperature]

Using PerkinElemer DSC7, the temperature was first maintained at 330 ° C for 5 minutes, then lowered to 23 ° C at a rate of 10 ° C / min, and then raised to 10 ° C / min. The endothermic peak before the melting point was determined by the glass transition temperature.

[reflectivity]

The reflectance at the wavelength of 440 nm was measured using the plate-shaped specimen. Initial reflectance was measured, and reflectance was measured after 200 hours of irradiation with an LED light source having a wavelength of 460 nm in a constant temperature and humidity oven at 85 ° C. and 85% relative humidity. The CM3500d of Minolta Co., Ltd. (KONICA MINOLTA HOLDINGS, INC.) Was used as a reflectance measuring instrument.

[Evaluation evaluation]

Peelability evaluation was performed in order to judge the presence or absence of peeling phenomenon by release defect or mixing of different resin at the time of injection molding of polyamide resin composition. Cup-shaped molded articles having a length of 3 mm, a width of 2.5 mm, and a height of 2 mm were hoop-molded, and aqueous ink was flown into the contact portion between the hoop material and the cup-shaped molded article, and the presence or absence of infiltration into the contact surface between the cup-shaped molded article and the hoop material by the capillary phenomenon. Was evaluated visually. Initial peelability was evaluated and the peelability after leaving for 3 hours in a 170 degreeC thermostat oven was evaluated.

○: does not seep, △: seeps less, ×: seeps through

[Yellow Index]

According to ASTM D1925, Minolta 3600D CIE Lab. The yellowness of the 2.5 mm thick specimen was measured using a color difference meter. The yellowness was measured after the initial yellowness was measured for 200 hours with an LED light source having a wavelength of 460 nm in a constant temperature and humidity oven at 85 ° C. and a relative humidity of 85%.

As shown in Table 1, Examples 1 to 4 it can be seen that even after irradiating an LED light source having a wavelength of 460nm for 200 hours in a constant temperature and humidity oven at 85 ℃ and 85% relative humidity maintains a reflectance of more than 85%. However, when crystalline polyamide resin or amorphous polyamide resin was used alone (Comparative Examples 1 or 2), and when inorganic filler was used outside the content range of the present invention (Comparative Example 3), 85 ° C and relative After irradiating an LED light source having a wavelength of 460 nm for 200 hours in a constant temperature and humidity oven with a humidity of 85%, it can be seen that the reflectance decreases rapidly.

In addition, when the light stabilizer was used outside the content range of the present invention (Comparative Example 4), the LED light source having a wavelength of 460 nm in a constant temperature and humidity oven at an initial yellowness of 85 ° C. and a relative humidity of 85% for 200 hours was used. It can be seen that the yellowness after the irradiation increases rapidly.

In addition, when the amorphous polyamide resin was used alone (Comparative Example 2), the yellowness after irradiating an LED light source having a wavelength of 460 nm for 200 hours in a constant temperature and humidity oven at 85 ° C. and a relative humidity of 85% was excellent. It can be seen that the degree increases rapidly. When the yellowness is increased, when light generated from the LED light source enters the LED reflector, the degree of absorption of the incident light by the reflector increases, resulting in a decrease in the efficiency of the LED light source.

In addition, when polyamide resin alone was used (Comparative Example 1) and when the inorganic filler was used outside the content range of the present invention (Comparative Example 3), the initial peelability was evaluated and for 3 hours in a 170 ° C constant temperature oven. It can be seen that there is an aqueous ink permeation phenomenon in the peelability evaluation after standing. When the amorphous polyamide resin was used alone (Comparative Example 2), the initial peelability evaluation result was excellent, but it was found that the aqueous ink permeation phenomenon occurred in the peelability evaluation after being left for 3 hours in a constant temperature oven at 170 ° C. have.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications are considered to be included within the scope of the present invention.

Claims (14)

(A) 10 to 70% by weight of the crystalline polyamide resin;
(B) 10 to 70% by weight of an amorphous polyamide resin having a glass transition temperature of 110 to 200 ° C;
(C) 10 to 60% by weight of the inorganic filler,
(D) 10 to 50% by weight of a white pigment; And
0.05 to 2 parts by weight of (E) light stabilizer, based on 100 parts by weight of the total amount of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D);
Polyamide resin composition comprising a.
According to claim 1, (F) inorganic fine particles from 0.05 to 100 parts by weight of the total content of the crystalline polyamide resin (A), amorphous polyamide resin (B), inorganic filler (C) and white pigment (D) Polyamide resin composition, characterized in that it further comprises 3 parts by weight.
The polyamide resin composition according to claim 1, wherein the crystalline polyamide resin (A) has a melting point of 260 to 350 ° C, a crystallization temperature of 260 to 320 ° C, and a glass transition temperature of less than 100 ° C.
The method of claim 1, wherein the crystalline polyamide resin (A) consists of a unit derived from (a-1) dicarboxylic acid and a unit derived from (a-2) diamine; 30-100 mol% of the unit (a-1) derived from the said dicarboxylic acid derived from terephthalic acid, 0-70 mol% of the unit derived from aromatic dicarboxylic acid other than terephthalic acid, and 4-4 carbon atoms 0 to 70 mol% of units derived from 20 aliphatic aliphatic dicarboxylic acids or 0 to 70 mole% of units derived from aromatic dicarboxylic acids other than terephthalic acid and the above-mentioned aliphatic dicarboxylic acids having 4 to 20 carbon atoms. 70 mole%; The polyamide resin composition, wherein the unit (a-2) derived from the diamine is a unit derived from a linear or branched aliphatic diamine having 4 to 20 carbon atoms.
The polyamide resin composition according to claim 1, wherein a glass transition temperature of the amorphous polyamide resin (B) is 120 to 160 ° C.
2. The polyamide of claim 1, wherein the amorphous polyamide resin (B) is a polyamide prepared from terephthalic acid, 2,2,4-trimethyl hexamethylene diamine and 2,4,4-trimethyl hexamethylene diamine; Polyamides prepared from isophthalic acid and 1,6-hexamethylene diamine; Polyamides prepared from terephthalic acid, isophthalic acid and 1,6-hexamethylenediamine; Copolyamides prepared from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam; Polyamides prepared from 1,12-dodecanoic acid and 4,4'-diaminodicyclohexylmethane; Polyamide resin composition, characterized in that it is selected from the group consisting of copolyamides prepared from terephthalic acid, isophthalic acid, 3,3-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam and mixtures thereof .
The polyamide resin composition according to claim 1, wherein the inorganic filler (C) comprises glass fibers having an average length of 0.1 to 20 mm and an aspect ratio of 10 to 2,000.
The polyamide resin composition according to claim 1, wherein the white pigment (D) is selected from the group consisting of titanium oxide, zinc sulfide, lead white, zinc sulfate, alumina oxide and mixtures thereof.
The polyamide resin composition according to claim 1, wherein the light stabilizer (E) is a hindered amine compound.
The method of claim 2, wherein the inorganic fine particles (F) are calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, barium sulfate, zinc emulsion, alkaline carbonate, mica titanium, antimony oxide, magnesium oxide, calcium phosphate, silica, alumina, Polyamide resin composition, characterized in that it is selected from the group consisting of mica, talc, kaolin and mixtures thereof.
The method of claim 1, further comprising an additive selected from the group consisting of antioxidants, heat stabilizers, flame retardants, fluorescent brighteners, plasticizers, thickeners, antistatic agents, mold release agents, pigments, nucleating agents and mixtures thereof. Amide resin composition.
A molded article prepared from the polyamide resin composition according to any one of claims 1 to 11.
The molded article according to claim 12, wherein the reflectance of the light having a wavelength of 440 nm is 80 to 90%, measured after irradiating an LED light source having a wavelength of 460 nm for 200 hours.
The molded article according to claim 12, wherein the yellowness is 1 to 5, measured after irradiating an LED light source having a wavelength of 460 nm for 200 hours.