TWI393745B - Polyamide resin composition for surface mount type LED reflector - Google Patents

Abstract

Disclosed is a polyamide resin composition used for a reflective plate for a surface mount LED, which contains: a copolymerized polyamide resin (A) that contains 50% by mole or more of a constituent unit obtained from an equimolar salt of terephthalic acid and a diamine having 2-8 carbon atoms and satisfies the conditions (a) and (b) described below; titanium oxide (B); at least one reinforcing material (C) that is selected from the group consisting of fibrous reinforcing materials and needle-like reinforcing materials; and a non-fibrous or non-needle-like filler (D). The polyamide resin composition is characterized by satisfying the condition (c) described below. (a) 7.5 = number of carbon atoms in copolymerized polyamide resin/number of amide bonds in copolymerized polyamide resin = 8.2 (b) 0.27 = number of carbon atoms on aromatic rings in copolymerized polyamide resin/total number of carbon atoms in copolymerized polyamide resin = 0.35 (c) The lowest DSC melting peak temperature assigned to the copolymerized polyamide resin (A) in polyamide resin composition is 300-340°C.

Description

Polyamide resin composition for surface mount type LED reflector

The present invention relates to a polyamide resin suitable for use in a surface-mounted LED reflector which is excellent in moldability, fluidity, dimensional stability, low water absorption, solder heat resistance, surface reflectance and the like. Composition. Further, the present invention relates to a polyamide resin composition which is suitable for use in a surface-mounted LED reflector which is excellent in heat resistance, light resistance, and low water absorbability of gold/tin solder.

In recent years, LEDs (light-emitting diodes) have been used in lighting fixtures, optical components, mobile phones, and backlight modules for liquid crystal displays because of their low power consumption, long life, high brightness, and miniaturization. Car control panels, traffic signs, display panels, etc. In addition, in the use of designing and portability, the surface mounting technology is used to reduce the thickness and thickness.

The surface mount type LED usually includes a light-emitting LED chip, a lead wire, a reflector having a casing, and a sealing resin. In order to bond the entire mounted component to the electronic substrate using non-lead solder, it is necessary to use each component. It is formed by a material resistant to solder reflow at a temperature of 260 ° C. In particular, in addition to such heat resistance, the reflector is required to have surface reflectance, durability against heat and ultraviolet rays in order to efficiently extract light. From this point of view, various heat-resistant plastic materials such as ceramics, semi-aromatic polyamides, liquid crystal polymers, and thermosetting polyfluorenes are reviewed. Among them, semi-aromatic polyamides are used to disperse high-refractive fillers such as titanium oxide. The resin is most widely used because of a good balance between mass productivity, heat resistance, surface reflectance, and the like. Recently, along with the generalization of LEDs, it has been necessary to improve the processability and reliability of the reflector, and semi-aromatic polyamides are also required to use the injection moldability at a low mold temperature and to improve the yield in the solder reflow step. Further, from the viewpoint of improving production efficiency, it is required to increase fluidity in the injection molding system, and it is possible to obtain /1 shots in 256 pieces.

The polyamine resin composition for an LED reflector is proposed, for example, in Patent Documents 1 to 3, and Patent Document 1 proposes a polyamine resin composition which is a copolymerized polyamine containing potassium titanate. Fiber and/or wallastonite, wherein the copolymerized polyamine contains: a dicarboxylic acid unit comprising 100 mol% of a phthalic acid unit; and 50 mol% of each 2-methyl-1,5-pentyl Made of diamine and hexamethylene diamine. Although the resin composition is excellent in whiteness and mechanical properties, since the glass transition temperature is 130 ° C, in order to sufficiently crystallize it, the mold temperature at the time of injection molding is preferably a high temperature of 140 ° C or higher. When the mold temperature is high, the shrinkage of the lead frame and the resin during the cooling process is large, and there are problems such as deformation and peeling easily. For example, even if molding with a low mold temperature can be used, since sufficient crystallization is not completed, deformation and crystal shrinkage occur at the time of heating in the subsequent step, resulting in a problem of peeling from the sealing material and the lead frame and lacking reliability. Further, when the saturated water absorption ratio of the copolymerized polyamine used is about 5%, water absorption is likely to occur, and in the reflow soldering step, expansion or the like occurs on the surface, which is problematic in workability.

Further, Patent Document 2 discloses a polyamide resin composition containing a polyamidamide resin (in the embodiment, only a polyamine 6T66 containing phthalic acid, adipic acid or hexamethylenediamine), and an inorganic substance are contained. a filler and a white pigment, wherein the polyamide resin comprises a dicarboxylic acid unit and 100 mol% of a diamine unit, and the dicarboxylic acid unit comprises: 30 to 100 mol% of a binary derived from tannic acid a carboxylic acid unit, 0 to 70 mol% of an aromatic dicarboxylic acid unit other than citric acid, and/or 0 to 70 mol% of an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms; and the diamine unit is The invention comprises a linear aliphatic diamine unit having 4 to 20 carbon atoms and/or an aliphatic diamine unit having a side chain having 4 to 20 carbon atoms. The polyamine 6T66 resin composition which is carried out in this patent document has a glass transition temperature of about 85 ° C, and the mold temperature at the time of molding can be about 120 ° C. However, the saturated water absorption rate is close to 6%, when water is absorbed. There are problems with dimensional changes and soldering resistance.

Further, Patent Document 3 discloses a polyamine resin composition containing polyamine (hereinafter referred to as polyamine 9T) and titanium oxide, wherein the polyamine contains a dicarboxylic acid unit and a binary An amine unit comprising 60 to 100 mol% of a decanoic acid unit; and the diamine unit contains 60 to 100 mol% of 1,9-nonanediamine units and/or 2-methyl- 1,8-octanediamine unit. This resin composition is excellent in low water absorbability. However, since the glass transition temperature is 125 ° C, there is room for improvement in terms of moldability insofar as the mold temperature at the time of molding is required to reach a high temperature of 140 ° C.

Further, in the resin compositions of Patent Documents 1 and 3, since the glass transition temperature is high, the fluidity in the mold at the time of injection molding is drastically lowered, and it is not suitable for many. On the other hand, in the resin composition of Patent Document 2, since the curing of the resin is too fast, the gate seal is quickly formed at the time of injection molding, and it is not suitable for a plurality of them.

As described above, the aromatic polyamine resin composition proposed in the prior art is used in consideration of moldability, dimensional stability, solder heat resistance, and fluidity.

Moreover, in recent years, the development of lighting applications has also been actively carried out. When considering the development of lighting applications, it is further required to reduce costs and power, improve life, and improve long-term reliability. Therefore, in the bonding between the lead frame and the LED wafer, the prior epoxy resin/silver paste is not used, but gold/tin eutectic soldering with less deterioration and high thermal conductivity is gradually used as a countermeasure for improving reliability. However, since the processing system of the gold/tin eutectic soldering requires a temperature of 280 ° C or more and less than 310 ° C, in order to withstand the step, the resin used is required to have a melting point of 310 ° C or higher. In the processing of gold/tin eutectic soldering, in order to prevent moisture in the resin from causing swelling (foaming) on the surface of the molded article, the resin is also required to have low water absorption.

In the case of the surface-mounted LED reflectors, as reported in Patent Document 3 and Patent Document 4, the use of polyamine 9T (hereinafter referred to as PA9T) containing decane diamine and citric acid has been reviewed and contains ruthenium. A low water-absorbent polyamide such as a diamine and a polydecylamine 10T (hereinafter referred to as PA10T). However, a polyamine which uses a diamine having a carbon number of 9 or more is known to have a melting point of around 300 ° C or less than 300 ° C. Therefore, in the gold/tin eutectic soldering step, the materials are melted without heat resistance and become unusable.

On the other hand, polyamine 6T (hereinafter referred to as PA6T) containing hexamethylenediamine and p-nonanoic acid is a material capable of processing gold/tin eutectic soldering because it has a melting point close to 370 ° C in nature. In actual use, as described in Patent Documents 5 to 7, it is used as a surface mount type by being copolymerized with adipic acid, 2-methyl-pentanediamine or butanediamine to adjust the melting point of easy processing. LED reflector. The polyamine which is obtained by copolymerization using PA6T as a skeleton can be adjusted to have a melting point at 310 ° C or lower, and is a material capable of withstanding the gold/tin eutectic soldering step. However, PA6T, which is a reflector for surface mount type LEDs, has a high water-absorbent concentration in the resin, and has a high water absorption rate in the use environment. Even in the lead-free reflow soldering step, bubbles are generated on the surface of the molded article, which is liable to cause problems. . Moreover, in the case of gold/tin eutectic solder joints which must be at a higher temperature, the foaming becomes remarkable. Further, as in the case of the conventional PA6T, when the amount of the guanamine bond is large, the guanamine bond becomes a starting point at a high temperature, and oxidative degradation causes coloration, and the reliability as a reflector is also greatly lowered.

On the other hand, a method of reducing the amount of amidoxime bond, such as copolymerization with naphthalene dicarboxylic acid or the like, is considered. However, when the concentration of the aromatic ring of the resin skeleton is increased, the conjugated system is formed to easily absorb ultraviolet rays and purple LEDs. The light of the blue LED causes the molecular breakage and coloration of the resin, which is not preferable. Moreover, in order to improve long-term reliability, it is necessary to improve the light resistance at the time of long-term lighting and outside use, and it is preferable to reduce the concentration of the aromatic ring by one of the important factors for reducing the light resistance.

As described above, the polyamide resin composition used for the surface-mounted reflective sheet for LEDs preferably has a melting point of up to 310 ° C or higher, low water absorption, and low aromatic ring concentration. However, the polyamine resin composition which can be used for the surface mount type LED reflector has not been reported so far.

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-194513

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-75994

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2008-274288

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-194513

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2002-294070

[Patent Document 7] Japanese Patent Publication No. 2003-528165

The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a surface which is suitable for use in injection molding, such as formability, fluidity, dimensional stability, low water absorption, solder heat resistance, and surface reflectance. A polyimide resin composition of a reflective plate for mounting LEDs. Further, the object of the present invention is to ensure long-term reliability, to have a high melting point which can be accommodated in the gold/tin eutectic soldering step, to reduce the low water absorption which causes swelling of the molded article in the solder step, and to enhance outdoor use and long-term use. In the case of light resistance, a polyimide resin composition suitable for use in a surface mount LED reflector is provided which has a low aromatic concentration.

[Means for solving the problem]

In order to achieve the above object, the inventors of the present invention have intensively studied to perform the injection molding and reflow soldering steps while satisfying the characteristics as the LED reflecting plate, and the gold/tin eutectic soldering is excellent in heat resistance, low water absorbability, and light resistance. The present invention has been completed as a result of the composition of the polyamine.

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

(1) A polyamide resin composition for use in a surface-mounted reflective sheet for LEDs, comprising a copolymerized polyamine resin (A), titanium oxide (B), and a fiber-reinforced reinforcing material and a needle-like shape. At least one reinforcing material (C) of the group of reinforcing materials, and a non-fibrous or non-acicular filler (D), and containing 0.5 to 100 with respect to 100 parts by mass of the copolymerized polyamide resin (A) Titanium oxide (B) in a ratio by mass, reinforcing material (C) in a ratio of 0 to 100 parts by mass, and polyamine resin in a non-fibrous or non-acicular filler (D) in a ratio of 0 to 50 parts by mass The composition is characterized in that the copolymerized polyamine resin (A) contains 50 mol% or more of a constituent unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and p-citric acid, and satisfies The following (a) and (b), and the polyamide resin composition satisfy the following (c):

(a) 7.5 碳 copolymerized polyamine resin in the number of carbon atoms / copolymerized polyamine resin in the number of guanamine bonds ≦ 8.2;

(b) the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin / the total number of carbon atoms in the copolymerized polyamine resin ≦ 0.35;

(c) The DSC melting peak temperature existing on the lowest temperature side of the copolymerized polyamine resin (A) derived from the polyamide resin composition is from 300 ° C to 340 ° C.

(2) A polyamine resin composition according to (1), wherein the copolymerized polyamine resin (A) is a composition obtained from an equivalent amount of a molar amine having a carbon number of 2 to 8 and a pericic acid The component other than the unit is obtained by copolymerizing one or a plurality of diamines, dicarboxylic acids, amine carboxylic acids or decylamine having 10 to 18 carbon atoms.

(3) The polyamine resin composition according to (1) or (2), wherein the copolymerized polyamine resin (A) is an equivalent molar salt of a diamine having a carbon number of 2 to 8 and a p-citric acid The components other than the obtained constituent unit are obtained by copolymerizing one or a plurality of the amine carboxylic acids having 11 to 18 carbon atoms or the indoleamine.

(4) The polyamide resin composition according to any one of (1) to (3), wherein the copolymerized polyamine resin (A) contains 55 to 75 mol% of hexamethylenediamine and p-citric acid. A constituent unit obtained by measuring a molar salt, and 45 to 25 mol% of a constituent unit obtained from 11-aminoundecanoic acid or undecydecylamine.

(5) The polyamide resin composition of any one of (1) to (4), wherein the copolymerized polyamine resin (A) contains up to 20 mol% of two from the aforementioned carbon number of 2 to 8. a constituent unit obtained by the same amount of a molar salt of a monoamine and a citric acid, or a constituent unit derived from the above-mentioned diamine, dicarboxylic acid, amine carboxylic acid or decylamine having 10 to 18 carbon atoms; Form the unit.

(6) The polyamide resin composition according to any one of (1) to (5), wherein the non-fibrous or non-acicular filler (D) is a talc powder and is copolymerized with respect to 100 parts by mass The guanamine resin (A) contains talc powder in a ratio of 0.1 to 5 parts by mass.

(7) The polyamide resin composition according to any one of (1) to (6) wherein the solder reflow heat resistance temperature is 260 ° C or higher.

(8) The polyamide resin composition according to any one of (1) to (7) wherein the solder reflow heat resistance temperature is 280 ° C or higher.

(9) The polyamide resin composition according to any one of (1) to (8), wherein the polyamine resin composition has a temperature rising crystallization temperature (Tcl) of 90 to 120 °C.

(10) A surface-mounted reflective sheet for LED, which is obtained by molding the polyamidamide resin composition according to any one of (1) to (9).

[Effects of the Invention]

In addition to high heat resistance and low water absorption, the polyamide resin composition of the present invention is industrially advantageous because it is a specific copolymerized polyamide resin which is excellent in workability such as moldability at the time of injection molding and solder heat resistance. A surface-mounted LED reflector for highly satisfying all necessary characteristics is manufactured.

Further, since the polyamine resin composition of the present invention has a high melting point of 300 ° C and excellent heat resistance, the copolymerized polyamine resin of the main component can also be adapted to the gold/tin eutectic soldering step, and Since the number of carbon atoms per guanamine bond in the polyamide resin is in a specific range and the concentration of the aromatic ring is low, the heat resistance, toughness, and light resistance are excellent, and the adhesion to the sealing material can be excellent. Characteristics.

The polyamide resin composition of the present invention is intended to be used for a surface mount LED reflector. The surface mount type LED is a wafer LED type using a printed wiring board, a Gullwing type using a lead frame, a PLCC type, etc., and the polyamide resin composition of the present invention can be produced by injection molding. Wait for all the reflectors.

The polyamidamide resin composition of the present invention contains at least one type of copolymerized polyamine resin (A), titanium oxide (B), and at least one selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material. The material (C), and the non-fibrous or non-acicular filler (D), and the titanium oxide (B) having a ratio of 0.5 to 100 parts by mass, based on 100 parts by mass of the copolymerized polyamide resin (A), A reinforcing material (C) having a ratio of 0 to 100 parts by mass, and a polyamine resin composition of a non-fibrous or non-acicular filler (D) in a ratio of 0 to 50 parts by mass, characterized in that copolymerized polyfluorene The amine resin (A) contains 50 mol% or more of a constituent unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and p-citric acid, and satisfies the following (a) and (b), and The polyamide resin composition satisfies the following (c):

(a) 7.5 碳 copolymerized polyamine resin in the number of carbon atoms / copolymerized polyamine resin in the number of guanamine bonds ≦ 8.2;

(b) the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin / the total number of carbon atoms in the copolymerized polyamine resin ≦ 0.35;

(c) The DSC melting peak temperature existing on the lowest temperature side of the copolymerized polyamine resin (A) derived from the polyamide resin composition is from 300 ° C to 340 ° C.

In order to impart high reliability, in addition to high melting point and low water absorption, it is necessary to formulate a copolymerized polyamine resin (A) in order to achieve excellent UV resistance, which is characterized in that it contains at least 50 mol% or more from a carbon number of 2 A constituent unit derived from a diamine of ~8 and an equivalent molar salt of citric acid.

Examples of the diamine component having 2 to 8 carbon atoms include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 2 -methyl-1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, piperazine , cyclohexanediamine, bisaminomethylcyclohexane, xylene diamine, phenylenediamine, which may be used singly or in plural.

The copolymerized polyamine resin (A) is required to contain at least 50 mol% or more of a constituent unit derived from an equivalent amount of a molar amount of a diamine having 2 to 8 carbon atoms and p-citric acid. When the carbon number of the diamine is 9 or more, the obtained polyamine has a complex melting point, and the DSC melting peak temperature existing on the lowest temperature side is 300 ° C or less, which is not preferable. Further, when the constituent unit obtained from the equivalent amount of the molar amine of 2 to 8 carbon atoms and the equivalent molar salt of citric acid is less than 50 mol%, the crystallinity and mechanical properties are low, which is not preferable.

The copolymerized polyamine resin (A) can be copolymerized with other components in an amount smaller than 50 mol% in the constituent unit. The diamine component which can be copolymerized may, for example, be 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-ten Monoalkyldiamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,16-hexadecyldiamine, 1,18-octadecanediamine, 2,2,4 An aliphatic diamine of -(or 2,4,4)-trimethylhexamethylenediamine; such as bis(3-methyl-4-aminohexyl)methane, bis-(4,4'-aminocyclohexyl An alicyclic diamine of methane, isophorone diamine, an aromatic diamine, and the like.

Examples of the acid component which can be copolymerized include isodecanoic acid, o-nonanoic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 4,4'-diphenyldicarboxylic acid. An aromatic dicarboxylic acid such as 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, sodium 5-sulfonate isophthalic acid or 5-hydroxyisophthalic acid, Fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, sebacic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexane An aliphatic or alicyclic dicarboxylic acid such as a dicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid or a dimer acid. Further, examples thereof include decylamine such as ε-caprolactam, 11-aminoundecanoic acid, undecyl decylamine, 12-aminododecanoic acid, and lauryl decylamine, and the like. The structure in which the ring is opened is also an amine carboxylic acid or the like.

Among them, in terms of the copolymerization component, it is preferred to copolymerize one or more of a diamine having a carbon number of 10 to 18, a dicarboxylic acid, an amine carboxylic acid or an indoleamine. It is more preferable to copolymerize one or more of an amine carboxylic acid or an indoleamine having a carbon number of 11 to 18.

In particular, an amine carboxylic acid or an indoleamine having a carbon number of 11 to 18 has a function of adjusting a melting point and a temperature rising crystallization temperature to improve formability, and a physical property change and a dimensional change upon water absorption by reducing water absorption. The function of improving the problem; and the function of improving the fluidity at the time of melting by introducing a soft skeleton.

The polyamine resin composition (A) of the present invention must satisfy

(a) 7.5 ≦ [Number of carbon atoms in copolymerized polyamine resin / number of guanamine bonds in copolymerized polyamine resin] ≦ 8.2

(The following is the case where [the number of carbon atoms in the copolymerized polyamine resin/the number of guanamine bonds in the copolymerized polyamine resin] is simply referred to as the average number of carbon atoms between the guanamine bonds).

When the number of carbon atoms in the copolymerized polyamine resin/the number of guanamine bonds in the copolymerized polyamine resin is less than 7.5, the water absorbency is too high. On the other hand, when [the number of carbon atoms in the copolymerized polyamine resin/the number of guanamine bonds in the copolymerized polyamine resin] is more than 8.2, in the encapsulation of the LED, the polysiloxane resin and the epoxy resin are used. When sealed in a reflector, the reactivity of the LED package is greatly reduced because the reactivity points with the polyoxyxene resin and the epoxy resin are reduced, and the adhesion is lowered.

Moreover, the polyamine resin composition (A) of the present invention must satisfy

0.27 ≦ [the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin / the total number of carbon atoms in the copolymerized polyamine resin] ≦ 0.35 (the following will be [copolymerized on the aromatic ring in the polyamide resin) The number of carbon atoms / the total number of carbon atoms in the copolymerized polyamine resin], which is simply referred to as the ratio of the number of carbon atoms on the aromatic ring).

LED reflectors for illumination and interior and exterior decoration of automobiles are required to not only receive light emitted from the LED chips continuously, but also receive ultraviolet rays when used outdoors, and the material is required to have high UV resistance. [When the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin/the total number of carbon atoms in the copolymerized polyamine resin] is more than 0.35, the absorption of light particularly in the ultraviolet region becomes large, and the light will be Causes the resin to deteriorate significantly. Further, in the presence of an aromatic ring, a conjugated structure which is an important factor for discoloration due to deterioration of the resin causes significant discoloration. Therefore, the concentration of the aromatic ring in the resin is preferably lower. However, when [the number of carbon atoms in the aromatic ring in the copolymerized polyamine resin/the total number of carbon atoms in the copolymerized polyamine resin] is less than 0.27, it is difficult to obtain a high melting point polyamine.

The copolymerized polyamine resin of the present invention has a constituent unit derived from an equivalent molar salt of a diamine having a carbon number of 2 to 8 and a citric acid, and has a hexamethylenediamine and a citric acid. When the constituent unit obtained by the molar salt is used, in addition to high heat resistance, fluidity, and low water absorbability, in order to achieve excellent formability, 55 to 75 mol% of the constituent unit and 45 to 25 mol% from 11- A copolymerized polyamine resin which is a constituent unit derived from aminoundecanoic acid or undecyl indoleamine is preferred.

Such a copolymerized polyamine resin (A) is not only capable of greatly improving the previous 6T nylon (for example, polyamine 6T6I containing p-citric acid/isodecanoic acid/hexamethylenediamine, including p-citric acid/ Polyamide 6T66 of adipic acid/p-citric acid, polyamine 6T6I66 containing p-citric acid/isodecanoic acid/adipic acid/hexanediamine, containing p-nonanoic acid/hexanediamine/2-methyl-1 , polyamine 6T/M-5T of 5-pentanediamine, polyamine 6T6 containing p-citric acid/hexamethylenediamine/ε-caprolactam, containing p-nonanoic acid/hexamethylenediamine/butanediamine The disadvantage of polyamine 6T/4T) is that it is highly water-absorptive, and it can suppress the oxidative discoloration caused by the guanamine bond, and can also satisfy the heat resistance and surface reflectance which are necessary for the LED reflector. Further, since it has fluidity derived from a soft long-chain fat skeleton derived from the polyamide 11 component, it has a feature of easily securing fluidity.

A component corresponding to polyamine 6T (hereinafter referred to as 6T) obtained by homo-co-condensing polymerization of hexamethylenediamine (6) and p-nonantimonic acid (T), specifically, the following formula (I) ) indicated.

The 6T component is a main component of the copolymerized polyamine resin (A), and has a function of imparting excellent heat resistance, mechanical properties, slidability, and the like to the copolymerized polyamide resin (A). The blending ratio of the 6T component in the copolymerized polyamine resin (A) is preferably 55 to 75 mol%, more preferably 60 to 70 mol%, and most preferably 62 to 68 mol%. When the blending ratio of the 6T component is less than the above lower limit, the crystalline component, that is, the polyamine 6T, is inhibited by the crystallization of the copolymer component, and the moldability and the high-temperature property may be lowered. On the other hand, when the ratio is higher than the upper limit, the melting point may be It becomes too high, and there is a possibility of decomposition during processing, which is not good.

A component corresponding to polyamine 11 (hereinafter referred to as PA11) obtained by polycondensation of 11-aminoundecanoic acid or undecyl indoleamine, specifically represented by the following formula (II) .

The PA11 component is used to improve the disadvantage of the 6T component, that is, water absorption and fluidity, and has a function of adjusting the melting point of the copolymerized polyamide resin (A) and raising the crystallization temperature to improve the formability; The function of improving the problem caused by the change in the physical property and the dimensional change at the time of water absorption, and the function of improving the fluidity at the time of melting by introducing a soft skeleton. The blending ratio of the PA11 component in the copolymerized polyamine resin (A) is preferably 45 to 25 mol%, more preferably 40 to 30 mol%, still more preferably 38 to 32 mol%. When the blending ratio of the PA11 component is less than the above lower limit, the melting point of the copolymerized polyamine resin (A) cannot be sufficiently lowered, and the moldability is insufficient, and the effect of lowering the water absorbability of the obtained resin is insufficient. When water is absorbed, there is a possibility of instability such as a decrease in mechanical properties. When the above upper limit is exceeded, the melting point of the copolymerized polyamine resin (A) is lowered too much, the crystallization rate is slowed, and the formability is rather deteriorated, and the amount of the 6T component is reduced, and mechanical properties and heat resistance are obtained. The possibility of deficiency is not good.

The copolymerized polyamine resin (A) may be a constituent unit obtained from the above-mentioned diamines having a carbon number of 2 to 8 and an equivalent molar salt of citric acid, or a carbon number of 10 to 18 The constituent unit other than the constituent unit obtained by the diamine, the dicarboxylic acid, the amine carboxylic acid or the indoleamine is copolymerized at a maximum of 20 mol%. The (X) component has other properties which cannot be obtained by imparting polyamine amine 6T and polydecylamine 11 to the copolymerized polyamine resin (A), and has been further improved by using polyamine 6T and polyfluorene. The function of the character of the properties obtained by the amine 11. Examples of the preferable (X) component include polyhexamethylene adipamide diamine which imparts high crystallization to the copolymerized polyamine resin (A) to impart lower water absorption. Poly-methylene methyl p-amine, polydodecanamine and the like. The blending ratio of the (X) component in the copolymerized polyamine resin (A) is preferably at most 20 mol%, more preferably from 10 to 20 mol%. When the ratio of the component (X) is less than the above lower limit, the effect of using the component (X) may not be sufficiently exhibited. When the ratio is greater than the upper limit, the amount of the essential component is small, and the original polymerization of the polyamide resin (A) is intended. The effect is not possible, but it is not good.

The catalyst used in the production of the copolymerized polyamine resin (A) may, for example, be phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt thereof, an ammonium salt or an ester. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, rhenium, titanium, ruthenium and the like. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, stearyl ester, decyl ester, stearate, phenyl ester or the like may be added. Further, from the viewpoint of enhancing the stability of the melt retention, it is preferred to add a basic compound such as sodium hydroxide, potassium hydroxide or magnesium hydroxide.

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

The copolymerized polyamine resin (A) is a method of performing polycondensation by adjusting the molar ratio of the amount of the amine group to the molar amount of the carboxyl group, and a method of adding a capping agent, and adjusting the terminal amount of the polyamide And molecular weight. When the molar ratio of the amine group to the carboxyl group is polycondensed at a certain ratio, the molar ratio of the total diamine to the total dicarboxylic acid used is adjusted to diamine/dicarboxylic acid = The range of 1.00/1.05 to 1.10.10.00 is preferred.

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

The acid value and the amine value of the copolymerized polyamine resin (A) are preferably 0 to 200 eq/ton and 0 to 100 eq/ton. When the terminal functional group exceeds 200 eq/ton, gelation and deterioration are promoted not only when the melting point stays, but also causes problems such as coloration and hydrolysis under the use environment. On the other hand, when a reactive compound such as a glass fiber or a maleic acid-modified polyolefin is compounded, the acid value and/or the amine value are 5 to 100 eq/ton in accordance with the reactivity and the reactive group. good.

The copolymerized polyamine resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by co-condensation of a raw material monomer. The order of the co-condensation polymerization reaction is not particularly limited, and all of the raw material monomers may be reacted once, or a part of the raw material monomers may be reacted first, and then the remaining raw material monomers may be reacted. Further, the polymerization method is not particularly limited, and it may be carried out from the raw material addition to the production of the polymer in a continuous step, or after the oligomer is produced at one time, in another step, using an extruder or the like, or by solid phase polymerization. A method of polymerizing an oligomer or the like. By adjusting the addition ratio of the raw material monomers, the ratio of each constituent unit in the synthesized copolymerized polyamine can be controlled. Further, it is also possible to produce a copolymerized polyamine resin by performing a guanamine exchange reaction by melt-kneading two or more kinds of polyamines using an extruder or a polymerization vessel.

In the polyamide resin composition of the present invention, the copolymerized polyamine resin (A) is preferably 25 to 95% by mass, and preferably 40 to 75% by mass. When the ratio of the copolymerized polyamine resin (A) is less than the above lower limit, the mechanical strength is lowered. When the ratio is larger than the above upper limit, the amount of the titanium oxide (B) or the reinforcing material (C) is insufficient, and it is difficult to obtain the desired effect.

The titanium oxide (B) is prepared by increasing the surface reflectance of the reflector, and examples thereof include a rutile type and an anatase type titanium dioxide (TiO) produced by a sulfuric acid method and a chlorination method. ₂ ), titanium oxide (TiO), titanium oxide (Ti ₂ O ₃ ), and the like. It is particularly preferable to use rutile-type titanium oxide (TiO ₂ ). The average particle diameter of the titanium oxide (B) is usually 0.05 to 2.0 μm, preferably in the range of 0.15 to 0.5 μm, and may be used alone or in combination of titanium oxide having different particle diameters. The concentration of the titanium oxide component is 90% or more, preferably 95% or more, and more preferably 97% or more. Further, the titanium oxide (B) can be subjected to surface treatment using a metal oxide such as ceria, alumina, zinc oxide or zirconium oxide, a coupling agent, an organic acid, an organic polyol, or a decane.

The ratio of the titanium oxide (B) is from 0.5 to 100 parts by mass, preferably from 10 to 80 parts by mass, per 100 parts by mass of the copolymerized polyamide resin (A). When the ratio of the titanium oxide (B) is less than the above lower limit, the surface reflectance is low, and when it is larger than the above upper limit, there is a possibility that the moldability is greatly lowered and the moldability is lowered.

The reinforcing material (C) is added to at least one selected from the group consisting of a fibrous reinforcing material and a needle-shaped reinforcing material in order to increase the formability of the polyamide resin composition and the strength of the molded article. Examples of the fibrous reinforcing material include glass fibers, carbon fibers, boron fibers, ceramic fibers, metal fibers, and the like. Examples of the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium carbonate whisker, magnesium sulfate whisker, and wallastonite. As the glass fiber, a short fiber roving or a continuous monofilament fiber having a length of 0.1 mm to 100 mm can be used. As the cross-sectional shape of the glass fiber, a glass fiber of a circular cross section and a non-circular cross section can be used. The diameter of the circular cross section glass fiber is 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. Further, in terms of physical properties and fluidity, a non-circular cross section is preferred. For the non-circular cross-section of the glass fiber, the longitudinal direction of the fiber length is generally elliptical, roughly rectangular, and slightly 茧-shaped, and the degree of flatness is preferably 1.5 to 8. Here, the degree of flatness is assumed to be a rectangle having a minimum area of a cross section perpendicular to the longitudinal direction of the glass fiber, and the length of the rectangle is set to a long diameter, and the length of the short side is set to be a short diameter. The ratio of the diameter to the short diameter. The thickness of the glass fiber is not particularly limited, and the short diameter is 1 to 20 μm and the long diameter is about 2 to 100 μm. Further, the glass fiber can be suitably used in the form of a short fiber roving formed into a fiber bundle and cut into a fiber length of about 1 to 20 mm. Further, in order to increase the surface reflectance of the polyamide resin composition, since the difference in refractive index from the copolymerized polyamide resin is preferably large, it is preferred to use a modified glass composition and a surface treatment to increase the refractive index.

The ratio of the reinforcing material (C) is 0 to 100 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass, per 100 parts by mass of the copolymerized polyamide resin (A). The reinforcing material (C) is not an essential component, but when the ratio is 5 parts by mass or more, the mechanical strength of the molded article is improved, which is preferable. When the ratio of the reinforcing material (C) exceeds the above upper limit, the surface reflectance and the formability tend to be low.

Examples of the non-fibrous or non-acicular filler (D) include reinforcing fillers, conductive fillers, magnetic fillers, flame-retardant fillers, thermally conductive fillers, and fillers for suppressing thermal yellowing, and specific examples thereof may be mentioned. Glass beads, glass shards, glass balloons, cerium oxide, talc, kaolin, mica, alumina, hydrotalcite, montmorillo nite, graphite, carbon nanotubes, fullerene , indium oxide, tin oxide, iron oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, red phosphorus, calcium carbonate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, boric acid Zinc, barium sulfate and non-needle-shaped wallastonite, potassium titanate, aluminum borate, magnesium sulfate, zinc oxide, calcium carbonate, and the like. These fillers may be used alone or in combination of several kinds. Among these, talc is preferred because it lowers Tc1 and improves formability. The amount of the filler to be added may be selected in an optimum amount, and may be added in an amount of up to 50 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A), and from 0.1 to 20 parts by mass from the viewpoint of mechanical strength of the resin composition. Preferably, it is preferably 1 to 10 parts by mass. Further, in order to improve the affinity with the polyamide resin, the fibrous reinforcing material and the filler are preferably used in the case of using an organic treatment and a coupling agent, or a coupling agent in the case of melt compounding, and in the case of a coupling agent, Any one of a decane coupling agent, a titanate coupling agent, and an aluminum coupling agent may be used, and among them, an amino decane coupling agent or an epoxy decane coupling agent is particularly preferred.

The polyamine resin composition of the present invention is capable of using various additives of the polyimide resin composition for a conventional LED reflector. Examples of the additives include stabilizers, impact-improving materials, flame retardants, mold release agents, slidability-improving materials, colorants, fluorescent whitening agents, plasticizers, crystal nucleating agents, and thermoplastics other than polyamides. Resin, etc.

Examples of the stabilizers include organic antioxidants such as hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants, and heat stabilizers, hindered amine-based compounds, diphenylketone-based compounds, and imidazole-based light. Stabilizers and UV absorbers, metal inerting agents, copper compounds, and the like. As the copper compound, cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, copper bromide, copper iodide, copper phosphate, copper pyrophosphate, copper sulfide, copper nitrate, copper acetate can be used. Such as copper salts of organic carboxylic acids and the like. Further, the constituent components other than the copper compound are preferably an alkali metal halide compound, and examples of the halogenated alkali metal compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, and 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 may be added in an amount of up to 5 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A).

The polyimide resin composition of the present invention may be a thermoplastic resin other than polyamine which has a different composition from the copolymerized polyamine resin (A). Examples of the thermoplastic resin other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), fluororesin, aromatic polyamidamine (Aramid) resin, and polycondensation. Ether ether ketone (PEEK), polyether ketone (PEK), polyether quinone imine (PEI), thermoplastic polyimide, polyamidimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE; polyphenylene ether), polyether oxime (PES), polyfluorene (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate , polybutylene naphthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene (PS) ), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS). These thermoplastic resins can also be blended in a molten state by melt kneading. The thermoplastic resin may be dispersed in the polyamide resin composition of the present invention in a fibrous form or in a particulate form. The amount of the thermoplastic resin to be added may be selected in an optimum amount, and may be added in an amount of up to 50 parts by mass based on 100 parts by mass of the copolymerized polyamine resin (A).

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

When a thermoplastic resin other than the copolymerized polyamine resin (A) and an impact-improving material are added to the polyamine resin composition of the present invention, it is preferred to carry out copolymerization of a reactive group reactive with polyamine. The reactive group is a group capable of reacting with a terminal group of a polyamide resin, that is, an amine group, a carboxyl group, and a main chain amide group. Specifically, a carboxyl group, an acid anhydride group, an epoxy group, An oxazolyl group, an amine group, an isocyanate group or the like is the most excellent in acid anhydride group reactivity. In this way, it has also been reported that a thermoplastic resin having a reactive group reactive with a polyamide resin is microdispersed in polyamine and can be greatly improved in impact resistance due to microdispersion and a short distance between particles [S , Wu: Polymer 26, 1855 (1985)].

The flame retardant may be a combination of a halogen-based flame retardant and a flame retardant, and a halogen-based flame retardant is a brominated polystyrene, a brominated polyphenylene ether or a brominated bisphenol type. Epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, all Chlorocyclopentadecane and brominated crosslinked aromatic polymer are preferred. Examples of the flame retardant auxiliary include antimony trioxide, antimony pentoxide, sodium antimonate, zinc stannate, zinc borate, and montmorillonite. A layered bismuth salt such as stone, a fluorine-based polymer, polyfluorene or the like. Among them, from the viewpoint of thermal stability, it is preferred that the halogen-based flame retardant is dibromopolystyrene and the flame retardant auxiliary is a combination of any of antimony trioxide, sodium antimonate, and zinc stannate. . Further, examples of the non-halogen flame retardant include melamine cyanurate, red phosphorus, a metal salt of phosphinic acid, and a nitrogen-containing phosphate-based compound.

In particular, a combination of a metal salt of phosphinic acid and a compound of a nitrogen-containing phosphate system is preferred, and in the case of a nitrogen-containing phosphate compound, it contains melamine or melamine such as melam, melem, and cetylamine. A reaction product of a condensate with polyphosphoric acid or a mixture thereof. In the case of using other flame retardants and flame retardant aids, it is preferable to use a hydrotalcite-based compound and a basic compound as metal mold corrosion when using such a flame retardant. The amount of the flame retardant to be added may be selected in an optimum amount, and may be added up to 50 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A).

The release agent may, for example, be a long-chain fatty acid or an ester thereof and a metal salt, a guanamine-based compound, a polyethylene wax, a polyfluorene oxide or a polyethylene oxide. The long-chain fatty acid is particularly preferably a carbon number of 12 or more, and examples thereof include stearic acid, 12-hydroxystearic acid, carboxylic acid, octadecanoic acid, and the like, and may also be a part or all of a carboxylic acid. It may be esterified with monoglycol and polyglycol or may form a metal salt. Examples of the guanamine-based compound include bis-p-guanamine and methylenebisstearylamine. These release agents can be used singly or as a mixture. The amount of the release agent to be added may be selected in an optimum amount, and up to 5 parts by mass may be added to 100 parts by mass of the copolymerized polyamide resin (A).

The polyamidamide resin composition of the present invention is a DSC melting peak temperature which is present on the lowest temperature side derived from the copolymerized polyamine resin (A) at the time of DSC measurement (the melting peak temperature on the low temperature side at the time of double peak) That is, the low temperature side melting point (Tm) is 300 ° C ~ 340 ° C, preferably 310 ~ 340 ° C. When Tm is larger than the above upper limit, the processing temperature required for injection molding of the polyamide resin composition of the present invention is extremely high, and the polyamide resin composition is decomposed during processing, and the desired physical properties and appearance cannot be obtained. On the other hand, when Tm is less than the above lower limit, the crystallization rate becomes slow, and molding is difficult, and there is a possibility that the solder heat resistance is lowered. When the Tm is 310 to 340 ° C, it is preferable because it can satisfy the reflow soldering heat resistance at 280 ° C and can also be adapted to the gold/tin eutectic soldering step.

Further, in the polyamine resin composition of the present invention, the temperature rise crystallization temperature (Tc1) present at the lowest temperature side is preferably from 90 to 120 ° C in the DSC measurement. The temperature rise crystallization temperature Tc1 is a temperature at which crystallization starts when the temperature is raised from room temperature, and when the ambient temperature of the resin composition at the time of molding is less than Tc1, crystallization is difficult to proceed. On the other hand, when the ambient temperature of the resin composition at the time of molding is larger than Tc1, crystallization proceeds easily, and dimensional stability and physical properties can be sufficiently exhibited. Since the reflector for LED is a fine molded product having a very small thickness, it is considered that the temperature of the resin after injection molding is approximately the same as the temperature of the mold. Therefore, when the Tc1 of the resin composition is high, it is necessary to raise the temperature of the mold in conjunction with it, which causes workability to be lowered. When Tc1 is larger than the above-mentioned upper limit, when the polyamide resin composition of the present invention is injection-molded, the mold temperature required is high, which makes molding difficult, and crystallization is not sufficiently performed in a cycle in which injection molding is short. In the case of the process, the molding is insufficient, or the crystallization is not sufficiently completed, and deformation and crystallization shrinkage occur in the heating of the subsequent step, and the problem of peeling from the sealing material and the lead frame is caused, and the reliability is lacking. . On the contrary, when the Tc1 system is less than the above lower limit, it is necessary to lower the glass transition temperature in terms of the resin composition. Since the Tc1 system is usually at a temperature higher than the glass transition temperature, and the Tc1 is less than 90 ° C, the glass transition temperature is required to be lower, but at this time, the physical properties are greatly lowered and the physical properties after the water absorption cannot be maintained. Waiting for the problem. Since it is necessary to maintain a relatively high glass transition temperature, it is necessary to make Tc1 at least 90 ° C or higher.

The copolymerized polyamine resin (A) of the present invention contains, as a main component, a constituent unit obtained from an equivalent amount of a molar amine having a carbon number of 2 to 8 and an equivalent molar salt of citric acid, and a guanamine bond. Since the concentration and the aromatic ring concentration are set to a specific range, in addition to the high melting point and formability, the balance between low water absorption and fluidity is excellent and the light resistance is excellent. Therefore, the polyamine resin composition of the present invention obtained by such a copolymerized polyamine resin (A) has a high melting point of 300 ° C or higher and low water absorption in addition to the formation of the surface mount type LED reflector. It is also possible to form a thin thickness and a high cycle.

On the other hand, in the case of using polyhexamethylene p-nonylamine (polyamine 9T), although low water absorption, since the glass transition temperature is 125 ° C, inevitably Tc1 is 125 ° C or more, the mold temperature at the time of molding must be Since it is 140 ° C or more, it is difficult to form workability. For example, when molding with a low-temperature mold, there is a problem that the fluidity is insufficient, the subsequent step and the crystallization at the time of use cause secondary shrinkage and deformation, and, in the DSC measurement, since there is a low-temperature side melting point of less than 300 ° C, it is adapted. In the gold/tin eutectic soldering step, the heat resistance is insufficient.

The polyamine resin composition of the present invention can be produced by blending the above constituent components by a conventionally known method. For example, it is possible to add each component during the polycondensation reaction of the copolymerized polyamine resin (A), or to dry-blend the copolymerized polyamine resin (A) with other components, or to use a biaxial screw type. A method of melt-kneading each component by an extruder.

[Examples]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. Further, the measured values described in the examples were measured by the following methods.

(1) Relative viscosity

0.25 g of polyamine resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C using an Oswald viscometer.

(2) Amount of terminal amine group

0.2 g of the polyamidamide resin was dissolved in 20 ml of m-cresol and titrated using a 0.1 mol/l hydrochloric acid ethanol solution. The indicator used was cresol red. It is represented by the equivalent (eq/ton) in the resin 1ton.

(3) Melting point (Tm) of polyamine resin, melting peak temperature of polyamidamide resin composition, and temperature rising crystallization temperature (Tc1)

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 35 ° C, and the UL burning test was performed with a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mmt. The test piece was injection molded to produce a test piece. In order to measure the melting point (Tm) and the temperature rising crystallization temperature (Tc1) of the obtained molded article, one part of the molded article was measured on an aluminum dish and placed in a sealed state using an aluminum cap to prepare a sample for measurement. The measurement was carried out by using a differential scanning calorimeter (SSC/5200 manufactured by SEIKO INSTRUMENTS) and raising the temperature from room temperature to 350 ° C at 20 ° C /min in a nitrogen atmosphere. At this time, the peak top temperature of the lowest peak in the obtained heat generation peak was taken as the temperature rising crystallization temperature (Tc1). Then, the temperature is raised, and the endothermic temperature of the endotherm of the melting is taken as the melting point (Tm). When there is a double peak, the tip of the low temperature side is marked as the low temperature side melting point.

(4) Formability and dimensional stability

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 120 ° C, and a flat plate having a film gate of 100 mm in the longitudinal direction, 100 mm in the lateral direction, and a thickness of 1 mm was used. The mold is machined to perform injection molding. The molding was carried out at an injection speed of 50 mm/sec, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 10 seconds, and the following evaluation was performed in terms of good or poor formability.

○: A molded article can be obtained without problems.

△: The sprue occasionally remains in the mold.

╳: The mold release property is insufficient, and the molded article is stuck to the mold and deformed.

Further, in order to evaluate the dimensional stability of the obtained molded article, the molded article was heated at 180 ° C for 1 hour. The dimension in the direction perpendicular to the flow direction before and after heating was measured, and the dimensional change was determined as follows.

Dimensional change amount (%) = {size before heating (mm) - size after heating (mm)} / size before heating (mm) × 100

The good and bad dimensional stability are evaluated as follows.

○: The dimensional change amount is less than 0.2%

╳: The dimensional change is 0.2% or more

(5) Solder heat resistance

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and the UL burning test was performed with a length of 127 mm, a width of 12.6 mm, and a thickness of 0.8 mmt. The test piece was injection molded to produce a test piece. The test piece was allowed to stand in an environment of 85 ° C and 85% RH (relative humidity) for 72 hours. The test piece was placed in an air reflow oven (AIS-20-82, manufactured by A-TEC), and was heated from room temperature to 150° C. for 60 seconds to perform preliminary heating, and then heated to 190° C. at a temperature increase rate of 0.5° C./min. Preheated. Subsequently, the temperature was raised to a predetermined set temperature at a rate of 10 ° C/min, and cooling was performed after maintaining the predetermined temperature for 10 seconds. The temperature was set to increase from 240 ° C every 5 ° C, and the highest set temperature at which the surface was not expanded and deformed was used as the reflow heat resistance temperature, and was used as an index of solder heat resistance.

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

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

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

(6) Saturated water absorption rate

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a flat plate having a longitudinal direction of 100 mm, a lateral direction of 100 mm, and a thickness of 1 mm was injection molded. Evaluation test piece. The test piece was immersed in hot water at 80 ° C for 50 hours, and the saturated water absorption rate was determined according to the following formula from the weight of saturated water absorption and drying.

Saturated water absorption (%) = {(weight at saturated water absorption - weight at drying) / weight at drying} × 100

(7) Diffusion reflectivity

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a flat plate having a longitudinal direction of 100 mm, a lateral direction of 100 mm, and a thickness of 2 mm was injection molded. Evaluation test piece. Using the test piece, a self-recording spectrophotometer "U3500" manufactured by Hitachi, Ltd. was used to measure the reflectance of a wavelength from 350 nm to 800 nm by integrating an integrating sphere manufactured by the company. The comparison of the reflectances is to obtain a diffuse reflectance at a wavelength of 460 nm. The benchmark is barium sulfate.

(8) Liquidity

Toshiba mechanical injection molding machine IS-100 was used, and the cylinder temperature was set to 330 ° C, the mold temperature was set to 120 ° C, and the injection pressure setting was 40%, the injection speed setting was 40%, and the measurement was 35 mm. In the condition that the injection time was 6 seconds and the cooling time was 10 seconds, the test piece for evaluation was produced by injection molding using a flow length measuring die having a width of 1 mm and a thickness of 0.5 mm. The flow length (mm) of the test piece was measured as the fluidity evaluation.

(9) Polyfluorene adhesion

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a flat plate having a longitudinal direction of 100 mm, a lateral direction of 100 mm, and a thickness of 2 mm was injection molded. Evaluation test piece. On one side of the test piece, a polyxylene sealing material (manufactured by Shin-Etsu Chemical Co., Ltd., ASP-1110, sealing material hardness D60) was applied so as to have a coating thickness of about 100 μm, and preheated at 100 ° C for 1 hour. The sealing material film was formed on one surface of the test piece by a hardening treatment at 150 ° C for 4 hours.

Subsequently, the sealing material film on the test piece was evaluated for adhesion using a checkerboard test based on JIS K5400 (100 mm in a width of 1 mm).

◎: peeling grid is 0

○: The number of stripped grids is 1~10

╳: peeling when forming the lattice before the peeling test

(10) Light resistance

Toshiba mechanical injection molding machine EC-100 was used, and the cylinder temperature was set to the melting point of the resin + 20 ° C, the mold temperature was set to 140 ° C, and a flat plate having a longitudinal direction of 100 mm, a lateral direction of 100 mm, and a thickness of 2 mm was injection molded. Evaluation test piece. The test piece was subjected to UV irradiation at an illuminance of 50 mW/cm ² in an environment of 63° C. and 50% RH using an ultra-promotion weathering tester “EYE SUPER UV TESTER-SUV-F11”. The light reflectance at a wavelength of 460 nm of the test piece was measured after no irradiation and 48 hours after the irradiation, and the evaluation was performed with respect to the retention ratio at the time of non-irradiation.

○: The retention rate is 90% or more

╳: The retention rate is less than 90%.

(11) Average number of carbon atoms between guanamine bonds

H-NMR was measured by dissolving 20 mg of the copolymerized polyamine resin (A) in hexafluoroisopropanol/deuterated chloroform (weight ratio 1/1). The average number of carbon atoms between the theoretical guanamine bonds was calculated from the obtained chemical composition.

(12) Carbon atom ratio on the aromatic ring

H-NMR was measured by dissolving 20 mg of the copolymerized polyamine resin (A) in hexafluoroisopropanol/deuterated chloroform (weight ratio 1/1). The ratio of carbon atoms on the theoretical aromatic ring was calculated from the obtained chemical composition.

<Synthesis Example 1>

In a 50-liter autoclave, 6.96 kg of 1,6-hexanediamine, 9.96 kg of p-citric acid, 8.04 kg of 11-aminoundecanoic acid, 9 g of sodium hypophosphite as a catalyst, and 40 g of acetic acid as a terminal regulator were added. 17.52 kg of ion-exchanged water was pressurized from normal pressure to 0.05 MPa using N ₂ to release the pressure to return to normal pressure. After this operation was performed three times and N ₂ substitution was performed, it was uniformly dissolved at 135 ° C and 0.3 MPa with stirring. Subsequently, the solution was continuously supplied using a liquid feeding pump and heated to 240 ° C using a heating pipe, and heated for 1 hour. Subsequently, the reaction mixture was supplied to a pressurized reaction tank and heated to 290 ° C, and a part of the water was distilled off while maintaining the internal pressure of the tank at 3 MPa to obtain a lower condensate. Subsequently, the lower condensate was directly supplied to a twin-screw extruder (screw diameter: 37 mm, L/D = 60) while maintaining the resin temperature at a melting point of +15 to 20 ° C (synthesis example 1 was 320 ° C). The polycondensation of the polyamide resin (A) was carried out by extracting water from three vent holes while performing polycondensation under melting. The addition ratio of the raw material monomer of the copolymerized polyamine resin (A) of Synthesis Example 1 and its characteristics are shown in Table 1.

<Synthesis Example 2>

The amount of 1,6-hexanediamine was 7.54 kg, the amount of p-citric acid was 10.79 kg, and the amount of 11-aminoundecanoic acid was 7.04 kg, and the resin temperature of the biaxial extruder was 330 °C. The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1 except for the above. The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 2 are shown in Table 1.

<Synthesis Example 3>

The synthesis was carried out in the same manner as in Synthesis Example 1 except that the amount of hexamethylenediamine was 8.12 kg, the amount of citric acid was 11.62 kg, and the amount of 11-aminoundecanoic acid was 6.03 kg. Polyamide resin (A). The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 3 are shown in Table 1.

<Synthesis Example 4>

The amount of 1,6-hexanediamine was 8.12 kg, the amount of citric acid was 9.96 kg, and the amount of 11-aminoundecanoic acid was 6.03 kg, and 1.46 kg of adipic acid was added (other than citric acid). The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1 except for the dicarboxylic acid. The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 4 are shown in Table 1.

<Synthesis Example 5>

The copolymerized polyamine resin (A) was synthesized in the same manner as in Synthesis Example 1, except that 7.04 kg of 11-aminoundecanoic acid was used as 6.41 kg of undecane indoleamine. The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 5 are shown in Table 1.

<Synthesis Example 6>

The synthesis was carried out in the same manner as in Synthesis Example 1 except that the amount of hexamethylenediamine was 8.70 kg, the amount of citric acid was 12.45 kg, and the amount of 11-aminoundecanoic acid was 5.03 kg. Polyamide resin (A). The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 6 are shown in Table 1.

<Synthesis Example 7>

The synthesis was carried out in the same manner as in Synthesis Example 1 except that the amount of 1,6-hexanediamine was 8.12 kg, the amount of citric acid was 11.62 kg, and the amount of 12-aminododecanoic acid was 6.46 kg. Polyamide resin (A). The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 7 are shown in Table 1.

<Synthesis Example 8>

The copolymerization was carried out in the same manner as in Synthesis Example 1 except that the amount of 1,6-hexanediamine was 8.12 kg, the amount of citric acid was 11.62 kg, and the amount of decanolide was 5.92 kg. Indoleamine resin (A). The addition ratio and the characteristics of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 8 are shown in Table 1.

<Comparative Synthesis Example 1: PA6T/66>

In a 50 liter autoclave, 11.6 kg of 1,6-hexanediamine, 10.63 kg of citric acid, 5.26 kg of adipic acid, 9 g of sodium hypophosphite as a catalyst, 40 g of acetic acid as a terminal regulator, and 17.52 kg of ion exchange were added. The water was pressurized from normal pressure to 0.05 MPa using N ₂ to release the pressure to return to normal pressure. After this operation was performed three times and N ₂ substitution was performed, it was uniformly dissolved at 135 ° C and 0.3 MPa with stirring. Subsequently, the solution was continuously supplied using a liquid feeding pump and heated to 240 ° C using a heating pipe, and heated for 1 hour. Subsequently, the reaction mixture was supplied to a pressurized reaction tank and heated to 290 ° C, and a part of the water was distilled off while maintaining the internal pressure of the tank at 3 MPa to obtain a lower condensate. Subsequently, the lower condensate was directly supplied to a twin-screw extruder (screw diameter: 37 mm, L/D = 60) while maintaining the molten resin at a melting point of +15 to 20 (comparative synthesis example 1 was 345 ° C). The polycondensation of the polyamide resin (A) was carried out by extracting water from three vent holes while performing polycondensation under melting. The addition ratio of the raw material monomers of the copolymerized polyamine resin (A) of Synthesis Example 1 and the characteristics thereof are shown in Table 1.

<Comparative Synthesis Example 2~6>

The copolymerized polyamine resin was synthesized by the same method as Comparative Synthesis Example 1 using the dicarboxylic acid component and the diamine component described in Table 1.

Examples 1 to 11 and Comparative Examples 1 to 6

Using Examples 1 to 11 and Comparative Examples 1 to 6 obtained by melt-kneading at a melting point of +15 ° C using a COPERION biaxial extruder STS-35 using the components and weight ratios shown in Table 2 Polyamine resin composition. In Table 2, the materials other than the copolymerized polyamine resin are as follows.

Titanium oxide (B): Tipaque CR-60, rutile TiO ₂ manufactured by Ishihara Sangyo Co., Ltd., average particle size 0.2 μm

Reinforcing material (C): glass fiber (Japan East Textile Co., Ltd., CS-3J-324), needle-shaped apatite (NYCO (share) system, NYGLOS8)

Filler (D): talc powder (MICRON WHITE 5000A made by Lin Huacheng)

Release agent: magnesium stearate

Stabilizer: pentaerythritol-indole [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by CIBA SPECIALTY CHEMICALS, IRGANOX 1010)

The polyamine resin compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 6 were evaluated for various characteristics. The results are shown in Table 3.

From Tables 1 and 3, it was confirmed that the average number of carbon atoms between the guanamine bonds and the carbon atom ratio on the aromatic ring satisfy the specific range of the present invention, and the melting point of the DSC of the polyamide resin composition (the lowest temperature side) When the melting peak temperature is greater than 300 ° C, it can adapt to the reflow soldering step, and when the melting point is greater than 310 ° C, since the reflow heat resistance temperature is 280 ° C or higher, the display can also adapt to the solder heat resistance of the gold/tin eutectic soldering step, The important properties of the LED are excellent in adhesion to the sealing material and surface reflectance, and are excellent in formability, fluidity, dimensional stability, low water absorption, and light resistance. On the other hand, all of the comparative examples cannot satisfy these characteristics. That is, in Comparative Examples 1 to 4, although the melting point of the polyamide resin composition was 300 ° C or more, it was because the water absorption rate was high and the reflow heat resistance temperature was less than 260 ° C, and the solder heat resistance could not be satisfied. In Comparative Examples 5 and 6, the moldability, the dimensional stability, and the adhesion to the sealing material were inferior, and the reflow heat resistance temperature was 260 ° C or more and less than 280 ° C, and the solder heat resistance could not be adapted to the gold/tin eutectic soldering step.

Industrial use possibility

The polyamidamide resin composition of the present invention is excellent in heat resistance, moldability, fluidity, and low water absorbability, and is excellent in adhesion between the LED application and the sealing material, and is also excellent in light resistance. The copolymerized polyamine resin can industrially advantageously produce a surface mount type LED reflector while highly satisfying the necessary characteristics.

Claims (15)

A polyamide resin composition for a surface mount LED reflector comprising a copolymerized polyamide resin (A), titanium oxide (B), and a fiber-reinforced material and a needle-shaped reinforcing material. At least one reinforcing material (C) and a non-fibrous or non-acicular filler (D) of the group, and containing 0.5 to 100 parts by mass based on 100 parts by mass of the copolymerized polyamide resin (A) a ratio of titanium oxide (B), a reinforcing material (C) in a ratio of 0 to 100 parts by mass, and a polyamine resin composition of a non-fibrous or non-acicular filler (D) in a ratio of 0 to 50 parts by mass, It is characterized in that the copolymerized polyamine resin (A) contains 50 mol% or more of a constituent unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and p-citric acid, and satisfies the following ( a) and (b), and the polyamide resin composition satisfies the following (c): (a) 7.5 碳 carbon number in the copolymerized polyamine resin / guanamine bond in the copolymerized polyamine resin ≦8.2; (b) 0.27 ≦ copolymerized polyamine resin in the number of carbon atoms in the aromatic ring / total number of carbon atoms in the copolymerized polyamine resin ≦ 0.35; (c) derived from polyamine Resin group DSC melting peak temperature in the presence of copolymerized polyamide resin composition (A) is the lowest temperature side of 300 ℃ ~ 340 ℃. The polyamine resin composition as claimed in claim 1, wherein the copolymerized polyamine resin (A) is a diamine and a phthalic acid having a carbon number of 2-8. A component other than the constituent unit obtained by the same amount of the molar salt is obtained by copolymerizing one or more of a diamine having a carbon number of 10 to 18, a dicarboxylic acid, an amine carboxylic acid or an indoleamine. The polyamidamide resin composition according to claim 1 or 2, wherein the copolymerized polyamine resin (A) is obtained from an equivalent amount of a molar salt of a diamine having a carbon number of 2 to 8 and a tereic acid. The component other than the constituent unit is obtained by copolymerizing one or a plurality of the amine carboxylic acid or the indoleamine having 11 to 18 carbon atoms. The polyamidamide resin composition according to claim 1 or 2, wherein the copolymerized polyamine resin (A) comprises 55 to 75 mol% of an equivalent molar salt of hexamethylenediamine and p-citric acid. A constituent unit, and 45 to 25 mol% of a constituent unit derived from 11-aminoundecanoic acid or undecydecylamine. The polyamidamide resin composition according to claim 1 or 2, wherein the copolymerized polyamine resin (A) contains up to 20 mol% of a diamine and a para-citric acid having a carbon number of 2 to 8 as described above. A constituent unit derived from an equivalent molar salt or a constituent unit other than the constituent unit obtained from the above-described diamine, dicarboxylic acid, amine carboxylic acid or decylamine having 10 to 18 carbon atoms. The polyamine resin composition according to claim 1 or 2, wherein the non-fibrous or non-acicular filler (D) is a talc powder, and relative to 100 parts by mass of the copolymerized polyamide resin (A), A talc powder having a ratio of 0.1 to 5 parts by mass. The polyamidamide resin composition according to claim 1 or 2, wherein the solder reflow heat resistance temperature is 260 ° C or higher. The polyamidamide resin composition according to claim 1 or 2, wherein the solder reflow heat resistance temperature is 280 ° C or higher. The polyamidamide resin composition according to claim 1 or 2, wherein the polyamine resin composition has a temperature rising crystallization temperature (Tc1) of 90 to 120 °C. A surface-mounted reflector for LEDs, which is obtained by molding a polyimide resin composition as disclosed in claim 1 or 2. The polyamine resin composition according to claim 4, wherein the non-fibrous or non-acicular filler (D) is talc and contains 0.1 with respect to 100 parts by mass of the copolymerized polyamide resin (A). ~5 parts by mass of talc powder. The polyamine resin composition of claim 4, wherein the solder reflow heat resistance temperature is 260 ° C or higher. The polyamine resin composition of claim 4, wherein the solder reflow heat resistance temperature is 280 ° C or higher. The polyamine resin composition of claim 4, wherein the polyamine resin composition has a temperature rising crystallization temperature (Tc1) of 90 to 120 °C. A surface-mounted reflector for LEDs obtained by molding a polyimide resin composition as disclosed in claim 4 of the patent application.