JP2019096845A - Led module, method for manufacturing the same, and liquid crystal polyester resin composition for led module - Google Patents

Abstract

To provide a liquid crystal polyester resin composition for an LED module, which is superior in the formability of a circuit part on a molded product surface and the dimensional stability of the molded product surface after a heat treatment, and which enables the suppression of corrosion of the circuit part owing to a gas generated from a molded product, and an LED module formed from such a liquid crystal polyester resin composition.SOLUTION: An LED module comprises at least one LED package having a light-emitting element and a substrate having the LED package mounted thereon. The LED module has a metal circuit formed on a substrate surface for connecting with the LED package. The substrate includes a liquid crystal polyester resin composition containing a liquid crystal polyester resin and an additive for circuit formation. In the liquid crystal polyester resin, a total amount of a hydroxybenzoic acid-originating structure unit and a terephthalic acid-originating structure unit is 60-77 mol% to 100 mol% of a total amount of structure units of the liquid crystal polyester resin.SELECTED DRAWING: None

Description

  The present invention relates to an LED module and a liquid crystal polyester resin composition for an LED module.

  LEDs (light emitting diodes) have characteristics such as smaller size, longer life, and energy saving than incandescent lamps and fluorescent lamps which are conventional light emitting devices. Therefore, conventional light-emitting devices are being replaced with LED light-emitting devices for lighting applications such as residential lighting, road lighting, and automotive lamps, and for display applications such as indicators and signal lights such as electronic devices and electric bulletin boards . The LED light emitting device comprises an LED package having a structure in which an LED (light emitting diode) element and a bonding wire are sealed with a resin and an electrode portion is drawn out, and the LED package on a substrate having a metal circuit connected to the electrode portion of the LED package. It consists of an LED module which arranges one or more. Here, as a resin material which forms an LED module, application of a liquid crystal polyester resin which is excellent in heat resistance, fluidity, insulation, and water vapor barrier property is proposed (for example, patent documents 1 and 2).

  On the other hand, development of a three-dimensional circuit board forming technology for incorporating an electronic circuit board in a resin component for space saving and weight reduction is required. By forming the electronic circuit pattern three-dimensionally on the surface of the resin molded product, it is possible to liberalize the circuit board design, to miniaturize the module, to reduce the number of parts, and to reduce the number of assembling steps. As a method of forming a circuit on a resin molded product, for example, a combination of a mask forming method of performing masking to portions other than the circuit formation portion by twice molding, a circuit pattern drawing method of laser irradiation and the like and plating Continued to expand. Among them, the laser direct structuring method, which is a method of activating metal additives in a resin composition by laser irradiation to metallize by plating etc. and forming a metal pattern on a portion drawn by laser irradiation, is a pattern Since the drawing and metallization processes are easy, enlargement is continued (for example, Patent Document 3). Application to LED module applications is also being studied, and, for example, application to thermoplastic diode compositions including thermoplastic resin compositions containing additives that define reflectance at a predetermined wavelength (for example, see Patent Documents 4 and 5) ) Has been proposed.

JP 2012-186454 A Japanese Patent Publication No. 2010-528435 Japanese Patent Publication No. 2015-502418 International Publication No. 2013/141157 International Publication No. 2015/033955

  However, in such a prior art, the adhesion between the molded product made of the liquid crystal polyester resin composition and the metal circuit is low, or in the case of an LED module made of a resin composition mainly composed of a polyamide resin etc. The expansion coefficient may be larger than the linear expansion coefficient of the metal circuit. As a result, there has been a problem that the adhesion strength of the metal circuit of the LED module is lowered or the metal circuit is detached or peeled off at the time of the reflow solder processing at the time of manufacture or the heat generation accompanying the LED light emission. In addition, when the temperature around the product increases, corrosion of the metal circuit of the LED module proceeds due to the gas generated from the resin composition, which may cause defects such as disconnection or short circuit of the circuit. Therefore, the conventional LED module and the resin composition for LED modules are not fully satisfied with the said subject, and the further improvement is calculated | required.

  The present invention is excellent in the formability of the circuit portion on the surface of a molded article when circuit formation technology such as laser direct structuring method is applicable, and the adhesion maintenance of the circuit portion when the LED module generates heat. Accordingly, it is possible to provide a liquid crystal polyester resin composition for an LED module, which is excellent in dimensional stability after heat treatment of a molded article, and further suppresses corrosion of a circuit portion due to gas generated from the molded article, and an LED module using the same. As an issue.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors formability of the circuit part of the molded article surface with the liquid crystalline polyester resin composition which contains the additive for circuit formation in liquid crystalline polyester resin which has a specific structural unit. The present invention has been found out that it is possible to obtain an LED module which is excellent in dimensional stability after heat treatment of a molded article and in which corrosion of a circuit portion due to generated gas is suppressed.

That is, the present invention was made in order to solve the above-mentioned subject, and the embodiment of the present invention may include at least one copy of the composition mentioned below.
(1) An LED module comprising: an LED package having a light emitting element; and a substrate on which one or more of the LED packages are mounted, wherein the substrate is a liquid crystal polyester resin composition containing a liquid crystal polyester resin and an additive for circuit formation. The liquid crystal polyester resin is an LED in which the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. module.
(2) The LED module according to (1), wherein the additive for circuit formation is a metal compound consisting of one metal species.
(3) The LED module according to (1) or (2), wherein the compounding amount of the circuit forming additive is 3 to 25 parts by weight with respect to 100 parts by weight of the liquid crystal polyester resin.
(4) The LED module according to any one of (1) to (3), wherein the liquid crystal polyester resin composition contains an inorganic filler.
(5) A liquid crystal polyester resin composition containing a liquid crystal polyester resin and an additive for forming a circuit, wherein the liquid crystal polyester resin has a total of a structural unit derived from hydroxybenzoic acid and a structural unit derived from terephthalic acid, The manufacturing method of the LED module including the process of forming a metal part in the surface of the molded article which consists of a liquid crystal polyester resin composition which is 60-77 mol% with respect to 100 mol% of total structural units of liquid crystal polyester resin.
(6) A liquid crystal polyester resin composition containing a liquid crystal polyester resin and an additive for forming a circuit, wherein the liquid crystal polyester resin has a total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid, The liquid-crystal polyester resin composition for LED modules which is 60-77 mol% with respect to 100 mol% of total structural units of liquid-crystal polyester resin.

  The LED module composed of the liquid crystal polyester resin composition for an LED module of the present invention is excellent in the formation of the circuit portion on the surface of the molded article, the dimensional stability after heat treatment of the molded article, and the circuit by the gas generated from the molded article. Corrosion of parts is suppressed. Therefore, the LED module of the present invention is excellent in adhesion of the metal circuit portion even at the time of heat treatment in the manufacturing process or at the time of heat generation due to light emission, and defects due to corrosion of the circuit portion are suppressed.

  Hereinafter, the present invention will be described in detail.

<Liquid crystal polyester resin composition for LED module>
The liquid crystal polyester resin composition for an LED module of the present invention comprises a liquid crystal polyester resin and an additive for circuit formation, and the liquid crystal polyester resin is a total of a structural unit derived from hydroxybenzoic acid and a structural unit derived from terephthalic acid. The liquid crystal polyester resin composition is 60 to 77 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin.

  The components contained in the liquid crystal polyester resin composition for an LED module will be described.

[Liquid crystal polyester resin]
The liquid crystalline polyester resin used in the present invention is a polyester forming an anisotropic melt phase. Examples of the liquid crystalline polyester resin include polyesters composed of structural units selected to form an anisotropic melt phase from oxycarbonyl units, dioxy units, dicarbonyl units, etc. described later.

  Next, structural units constituting the liquid crystal polyester resin will be described.

  As an oxycarbonyl unit, a structural unit derived from hydroxybenzoic acid can be used in combination with a structural unit derived from an aromatic hydroxycarboxylic acid such as 6-hydroxy-2-naphthoic acid. The structural unit derived from hydroxybenzoic acid is a structural unit derived from p-hydroxybenzoic acid from the viewpoint of excellent dimensional stability after heat treatment of the molded article, and from the viewpoint of suppression of corrosion of the circuit part by the gas generated from the molded article. Is particularly preferred.

  Specific examples of the dioxy unit include 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, t-butylhydroquinone, phenylhydroquinone, chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'- Dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone and the like Structural units derived from aromatic diols of the above, structures derived from aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like Position, 1,4-cyclohexanediol, and structural unit derived from alicyclic diol such as 1,4-cyclohexanedimethanol. From the viewpoint of suppressing the corrosion of the circuit part by the gas generated from the molded article, structural units derived from aromatic diols are preferable, and structural units derived from 4,4'-dihydroxybiphenyl and hydroquinone are particularly preferable.

  Examples of the dicarbonyl unit include structural units derived from terephthalic acid, and further include, for example, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 2'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4 ' Structural units derived from aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, structural units derived from aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexahydroterephthalic acid, 1,4-cyclohexane Structures derived from alicyclic dicarboxylic acids such as dicarboxylic acids and 1,3-cyclohexanedicarboxylic acid It can be used in combination, such as a unit. It is preferable to use a structural unit derived from terephthalic acid and isophthalic acid in combination from the viewpoint of excellent dimensional stability after heat treatment of the molded article.

  Further, in addition to the above structural units, structural units produced from p-aminobenzoic acid, p-aminophenol and the like can be further provided within a range that does not impair liquid crystallinity and properties.

  Specific examples of the liquid crystalline polyester resin include a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, a structural unit derived from hydroquinone, a structural unit derived from terephthalic acid, isophthalic acid Liquid crystalline polyester resin comprising a structural unit derived from a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from ethylene glycol, a structural unit derived from 4,4'-dihydroxybiphenyl, an aromatic dicarbon containing terephthalic acid Liquid crystalline polyester resin comprising structural units derived from acid, structural unit derived from p-hydroxybenzoic acid, structural unit derived from hydroquinone, structural unit derived from 4,4′-dihydroxybiphenyl, 2,6-naphthalene dicarboxylic acid , Aromatic dicarboxylic acid containing terephthalic acid Liquid crystalline polyester resin comprising structural units derived from acid, structural unit derived from p-hydroxybenzoic acid, structural unit derived from 2,6-dihydroxynaphthalene, structural unit derived from 4,4'-dihydroxybiphenyl, terephthalic acid Liquid crystalline polyester resin comprising a structural unit derived from an aromatic dicarboxylic acid containing a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl The liquid crystal polyester resin etc. which consist of a structural unit derived from, and a structural unit derived from the aromatic dicarboxylic acid containing a terephthalic acid are mentioned.

  Particularly preferred is a structural unit derived from p-hydroxybenzoic acid, 4,4 ′ from the viewpoint of excellent dimensional stability after heat treatment of the molded article, and from the viewpoint of suppression of corrosion of the circuit portion due to gas generated from the molded article. -A liquid crystal polyester resin comprising a structural unit derived from dihydroxybiphenyl, a structural unit derived from hydroquinone, a structural unit derived from terephthalic acid, and a structural unit derived from isophthalic acid.

  The raw material monomer constituting each structural unit described above is a structure capable of forming each structural unit, for example, an acylated compound of a hydroxyl group of each structural unit, an esterified product of a carboxyl group of each structural unit, an acid halide, an acid anhydride Or the like may be used.

  The total of dioxy units constituting the liquid crystalline polyester resin and the total of dicarbonyl units are substantially equimolar. "Substantially equimolar" as used herein indicates that the structural units constituting the polymer main chain excluding the terminal are equimolar. For this reason, an aspect which is not necessarily equimolar when including the structural units constituting the end can also satisfy the “substantially equimolar” requirement.

  In the liquid crystal polyester resin used in the present invention, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. . By setting the content ratio of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid to the total structural units of the liquid crystal polyester resin in the above range, the liquid crystal polyester is excellent in heat resistance. The adhesion of the circuit portion on the surface of the molded article of the LED module using the resin composition is excellent, and the dimensional stability of the molded article after heat treatment is excellent. Furthermore, the corrosion of the circuit portion due to the gas generated from the molded article is suppressed. In addition, since the liquid crystal polyester resin is constituted by the structural unit in the above range, the melting point of the liquid crystal polyester resin is controlled, and it becomes possible to mold the LED module without excessively raising the temperature at the molding process. Deterioration of the liquid crystal polyester resin composition at the time is suppressed. As a result, the moldability of the LED module is excellent.

  On the other hand, when the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is less than 60 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin, the heat resistance of the liquid crystal polyester resin is Since it falls, the adhesiveness of the circuit part of the molded article surface of the LED module using the liquid-crystal polyester resin composition falls. In addition, the dimensional stability of the molded product after heat treatment is poor, the circuit portion of the molded product may be peeled off, the gas generated from the molded product may be increased, and the circuit portion may be corroded and broken. Further, if it exceeds 77 mol%, the crystallinity and melting point of the liquid crystalline polyester resin become excessively high, so that the deterioration of the liquid crystalline polyester resin composition at the time of molding progresses and the circuit portion is corroded by the gas generated from the molded article. Will increase.

  The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is preferably 65 mol% or more, more preferably 69 mol% or more, relative to 100 mol% of the total structural units of the liquid crystal polyester resin. On the other hand, 76 mol% or less is preferable.

  The structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid may have any one structural unit, and the other structural unit may be 0 mol%, but each is 0 mol% It is preferable to exceed.

  The liquid crystal polyester resin of the present invention preferably has 2 mol% or more of a structural unit derived from hydroquinone with respect to 100 mol% of the total amount of structural units of the liquid crystal polyester resin. With the above structure, the crystallinity of the liquid crystal polyester resin can be appropriately controlled, the formability of the circuit portion on the surface of the molded article is excellent, and the corrosion of the circuit portion by the gas generated from the molded article is suppressed. can get. More preferably, it is 4 mol% or more, more preferably 7.5 mol% or more. On the other hand, it is preferable to have 20 mol% or less of the structural unit derived from hydroquinone. By setting it as said structure, crystallinity of a liquid-crystal polyester resin does not become low too much, and it is excellent in the dimensional stability after heat processing of a molded article. More preferably, it is 15 mol% or less, still more preferably 12 mol% or less.

The calculation method of content of each structural unit is shown below about the liquid-crystal polyester resin of this invention. First, it was weighed liquid crystal polyester resin NMR (nuclear magnetic resonance) tube, liquid crystal polyester resin is dissolved in soluble solvents (e.g., pentafluorophenol / heavy tetrachloroethane -d ₂ solvent mixture). Next, ¹ H-NMR spectrum measurement is performed on the obtained solution, and it can be calculated from the peak area ratio derived from each structural unit.

  The melting point (Tm) of the liquid crystal polyester resin of the present invention is preferably 220 ° C. or more, more preferably 270 ° C. or more, and still more preferably 300 ° C. or more from the viewpoint of heat resistance. On the other hand, from the viewpoint of processability, the melting point (Tm) of the liquid crystal polyester resin is preferably 360 ° C. or less, more preferably 355 ° C. or less, and still more preferably 350 ° C. or less.

The measurement of the melting point (Tm) is performed by differential scanning calorimetry. Specifically, first, the endothermic peak temperature (Tm ₁ ) is observed by heating the polymer after completion of the polymerization from room temperature to 20 ° C./min. After observation of an endothermic peak temperature (Tm _1), holding the polymer for 5 minutes at a temperature of the endothermic peak temperature _(Tm 1) + 20 ℃. Thereafter, the polymer is cooled to room temperature under a temperature decrease condition of 20 ° C./min. Then, the endothermic peak temperature (Tm ₂ ) is observed by heating the polymer under a temperature rising condition of 20 ° C./min. The melting point (Tm) refers to the endothermic peak temperature (Tm ₂ ).

  The melt viscosity of the liquid crystalline polyester resin of the present invention is preferably 1 Pa · s or more, more preferably 5 Pa · s or more, and still more preferably 15 Pa · s or more from the viewpoint of mechanical strength. On the other hand, from the viewpoint of fluidity, the melt viscosity of the liquid crystalline polyester resin is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, and still more preferably 50 Pa · s or less.

  In addition, this melt viscosity is a value measured with a temperature-increase type flow tester under the conditions of a melting point (Tm) + 20 ° C of a liquid crystal polyester resin and a shear rate of 1000 / sec.

  The method for producing the liquid crystalline polyester resin of the present invention is not particularly limited, and can be produced according to a known polyester polycondensation method. Examples of known polycondensation methods for polyesters include structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, structural units derived from terephthalic acid, and Taking the liquid crystalline polyester resin comprising a structural unit derived from isophthalic acid as an example, the following may be mentioned.

  (1) A process for producing a liquid crystalline polyester resin from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene and terephthalic acid and isophthalic acid by a deacetic acid polycondensation reaction.

  (2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acetylate a phenolic hydroxyl group, and then deacetylated and polymerized to obtain a liquid crystal polyester How to make a resin.

  (3) A method for producing a liquid crystalline polyester resin by dephenolization polycondensation reaction from phenyl p-hydroxybenzoate and 4,4'-dihydroxybiphenyl, hydroquinone and diphenyl terephthalate and diphenyl isophthalate.

  (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to make each into a phenyl ester, and then an aroma such as 4,4'-dihydroxybiphenyl and hydroquinone Group dihydroxy compound is added and the liquid crystal polyester resin is manufactured by dephenolation polycondensation reaction.

  Among them, (2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acetylate the phenolic hydroxyl group, and then deacetylated polycondensation reaction is performed. The method for producing a liquid crystalline polyester resin is preferably used from the viewpoint of industrially excellent control of the terminal structure of the liquid crystalline polyester resin and control of the degree of polymerization.

  As a method for producing the liquid crystalline polyester resin used in the present invention, it is also possible to complete the polycondensation reaction by solid phase polymerization. Examples of the treatment by solid phase polymerization include the following methods. First, the polymer or oligomer of the liquid crystal polyester resin is ground by a grinder. The pulverized polymer or oligomer is heated under nitrogen flow or under reduced pressure to polycondensation to a desired degree of polymerization to complete the reaction. The heating can be performed in the range of melting point −50 ° C. to melting point −5 ° C. (for example, 200 to 300 ° C.) of the liquid crystal polyester resin for 1 to 50 hours.

  The polycondensation reaction of the liquid crystalline polyester resin proceeds without a catalyst, but stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metallic magnesium and the like can also be used as a catalyst.

[Additive for circuit formation]
The liquid crystal polyester resin composition for an LED module of the present invention contains a circuit forming additive. In addition, the additive for circuit formation points out the additive which can form a metal part in the molded article surface which consists of a resin composition containing the said additive for circuit formation. The circuit forming additive is preferably a laser direct structuring additive. Here, the additive for direct laser structuring is added to the liquid crystal polyester resin composition for an LED module of the present invention, so that the additive for direct laser structuring at the time of laser irradiation to a molded article comprising the composition is It refers to an additive that is exposed to the surface of a molded article and denatured, and from that point, gives an ability to form a metal part in a laser-irradiated part by a method such as electroless plating.

  It is preferable that the additive for circuit formation of this invention consists of 1 type of metal seed | species. Examples of metal species constituting the circuit-forming additive include copper, tin, cobalt, nickel or silver. As a metal species, copper and tin are preferable, and copper is particularly preferable. The additive for circuit formation may be used as a metal alone or as a compound containing a metal. As the compound containing a metal, oxides, sulfides, sulfates, nitrides, nitrates, carbonates, phosphates, halides, hydroxides, organometallic compounds, complexes, and the like can be used. Among them, oxides and phosphates are preferred. The circuit-forming additive is particularly preferably copper phosphate. The circuit-forming additive is suitably dispersed in the liquid-crystalline polyester resin composition by being composed of one metal species, in particular, a single metal compound comprising the above metal species, and a metal compound, to form a circuit portion on the surface of a molded article It is preferable because it has excellent properties and dimensional stability during heat treatment of a molded article. Moreover, since reaction and decomposition of the additive for circuit formation at the time of shaping | molding processing of a liquid-crystal polyester resin composition are suppressed, and it is excellent in the formation property of the circuit part of LED module components, it is preferable. Furthermore, it is preferable because the corrosion of the circuit portion due to the gas generated from the molded product is suppressed.

  It is preferable that the liquid crystal polyester resin composition for LED modules of this invention contains 3-25 weight part with respect to 100 weight part of liquid crystal polyester resin of the additive for circuit formation. By making the compounding quantity of the additive for circuit formation into 3 weight part or more, since formation of the circuit part of the LED module component which consists of a liquid-crystal polyester resin composition advances easily, it is preferable. The compounding amount of the circuit-forming additive is preferably 3.5 parts by weight or more, and more preferably 5 parts by weight or more. On the other hand, by making the compounding quantity of the additive for circuit formation into 25 weight part or less, since it is excellent in the mechanical strength of the LED module component which consists of a liquid-crystal polyester resin composition, it is preferable. Moreover, since corrosion of the circuit part by the gas generated from a molded article is suppressed, it is preferable. 21 weight part or less is preferable, and, as for the compounding quantity of the additive for circuit formation, 19 weight part or less is more preferable.

  The additive for circuit formation of the present invention preferably has an average particle diameter of more than 1 μm. The average particle size referred to herein is a volume average particle size and can be determined by the following method. The resin component is removed by heating 50 g of the liquid crystal polyester resin composition at 550 ° C. for 3 hours, and when a circuit forming additive or an inorganic filler is blended, the mixture of the circuit forming additive and the inorganic filler is taken out. . The inorganic fillers in the mixture can be separated by specific gravity differences. For example, a mixture of a circuit forming additive and an inorganic filler from which a resin component has been removed is taken out, and this is methylene iodide (specific gravity 3.33) or 1,1,2,2-tetrabromoethane (specific gravity 2.970) And ethanol (specific gravity 0.789) or the like to be dispersed in a mixed solution appropriately mixed so as to have a specific gravity between the additive for circuit formation and the inorganic filler, and centrifuged at a rotational speed of 10000 rpm for 5 minutes, The suspended inorganic filler is removed by decantation, and the precipitated circuit forming additive is removed by filtration. 100 mg of the obtained additive for circuit formation is weighed, dispersed in water, and measured using a laser diffraction / scattering particle size distribution measuring apparatus ("LA-300" manufactured by HORIBA).

  When the average particle diameter of the additive for circuit formation is larger than 1 μm, when the inorganic filler is compounded, kneading of the additive for circuit formation and the inorganic filler occurs at the time of production or molding processing of the liquid crystal polyester resin composition. Since it accelerates | stimulates, each aggregation is suppressed and the additive for circuit formation and the inorganic filler are excellent in the dispersibility respectively in the obtained LED module. Thereby, it is preferable because the formability of the circuit part of the LED module is excellent and the dimensional stability at the time of heat treatment of the molded article is excellent. 1.5 micrometers or more are preferable and 2.0 micrometers or more are more preferable. On the other hand, from the viewpoint of improving the dispersibility of the additive for circuit formation in the liquid crystal polyester resin composition, the upper limit of the average particle diameter of the additive for circuit formation is preferably 350 μm or less, more preferably 100 μm or less, and 50 μm or less More preferable.

[Filling material]
The liquid crystal polyester resin composition of the present invention may contain a filler to impart mechanical strength and other characteristics of the liquid crystal polyester resin. The filler is a filler which does not impart the property of forming a metal part on the surface of a molded product even when it is mixed with a liquid crystal polyester, and is different from the above-described additive for circuit formation. As a filler, the filler of various shapes, such as fibrous form, whisker shape, plate shape, powder form, a granular form, etc. can be mentioned, for example. Specifically, examples of fibrous and whisker-like fillers include glass fibers, carbon fibers of polyacrylonitrile (PAN) type and pitch type, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, and aromatic polyamide fibers. Organic fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers , Warasteite, and acicular titanium oxide. Plate-like fillers include mica, talc, kaolin, glass flakes, clay, graphite, and molybdenum disulfide. As powdery and granular fillers, silica, calcium carbonate, glass beads, glass microballoons, titanium oxide, zinc oxide, calcium polyphosphate and the like can be mentioned. Two or more of these may be contained.

  Among the above-mentioned fillers, the kind of glass fiber is not particularly limited as long as it is generally used for reinforcement of resin, and examples thereof include chopped strands of long fiber type and short fiber type, and milled fibers.

  The surface of the filler may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent. The glass fiber may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin.

  Among the above-mentioned fillers, the reinforcing effect is excellent, and the dispersibility at the time of kneading with the additive for circuit formation is excellent, so that the dimensional stability after heat treatment of a molded article made of the obtained liquid crystal polyester resin composition is excellent. And plate-like fillers are preferred. Examples of the plate-like filler include mica and glass flakes, and among them, the reinforcing effect is high, and the formability of the circuit part on the surface of the molded article made of the liquid crystalline polyester resin composition obtained is excellent, and the dimensions of the molded article after heat treatment Mica is preferable because it is excellent in stability and further suppresses the corrosion of the circuit portion due to the gas generated from the molded product.

  The Mohs hardness of the filler is preferably in the range of 2.0 to 7.0. The Mohs hardness can be determined by the presence or absence of a scratch caused by rubbing with a Mohs hardness of 1 to 10 standard substances. When the filler has a Mohs hardness within the above range, the dispersibility of each of the resin composition can be improved by kneading with the circuit-forming additive at the time of production and molding of the liquid crystal polyester resin composition, and the obtained resin composition The formability of the circuit portion on the surface of a molded article made of a material is improved, and the dimensional stability of the molded article after heat treatment is excellent, which is preferable. The Mohs hardness of the filler is preferably 2.5 or more from the viewpoint of dimensional stability after heat treatment of the molded article. On the other hand, it is preferably 6.5 or less, more preferably 4.0 or less, from the viewpoint of suppressing abrasion of the cylinder and screw of the injection molding machine at the time of molding and processing.

  In the liquid crystal polyester resin composition of the present invention, the content of the filler is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the liquid crystal polyester resin. If the filler content is 10 parts by weight or more, the mechanical strength of the molded article can be improved, which is preferable. 15 parts by weight or more is more preferable, and 20 parts by weight or more is more preferable. On the other hand, a filler content of 200 parts by weight or less is preferable because a liquid crystal polyester resin composition excellent in moldability and flowability can be obtained. 150 parts by weight or less is more preferable, and 100 parts by weight or less is more preferable.

  The filler preferably has an average particle size of 10 to 1000 μm. The average particle size as referred to herein is a volume average particle size, and can be determined by the method described above. When the average particle diameter of the filler is 10 μm or more, the reinforcing effect is excellent, and thus the dimensional stability of the molded article made of the liquid crystalline polyester resin composition obtained is excellent, which is preferable. 15 micrometers or more are more preferable, and 20 micrometers or more are further more preferable. On the other hand, since the dispersibility in a liquid-crystal polyester resin composition improves that the average particle diameter of a filler is 1000 micrometers or less, since it is excellent in the formation of the circuit part surface of the molded article of the liquid-crystal polyester resin composition obtained, it is preferable. . 900 micrometers or less are more preferable, and 700 micrometers or less are further more preferable.

  In the liquid crystal polyester resin composition of the present invention, the average particle diameter of the filler is preferably 0.1 to 20 times the average particle diameter of the circuit-forming additive. When the relationship of the average particle diameter of the additive for circuit formation and the filler is in the above-mentioned range, the additive for circuit formation and the filler are kneaded at the time of manufacturing processing of the liquid crystal polyester resin composition. Cohesion is suppressed, and in the resulting molded article, the additive for circuit formation and the filler are each excellent in dispersibility, which is preferable. From the viewpoint of improving the dispersibility of the circuit-forming additive and the filler, the average particle diameter of the filler is preferably 0.5 or more times the average particle diameter of the circuit-forming additive. On the other hand, from the viewpoint of improving the reinforcing effect of the filler, 15 times or less is preferable, and 10 times or less is more preferable.

  The liquid crystal polyester resin composition of the present invention further contains an antioxidant, a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and their substituted compounds, etc.), as long as the effects of the present invention are not impaired. Agents (eg, resorcinol, salicylate), phosphites, coloring inhibitors such as hypophosphites, lubricants and mold release agents (long chain fatty acids such as montanic acid, esters thereof, half esters thereof, silicones, higher alcohols , Higher fatty acid amides, and polyethylene wax, etc., colorants including dyes or pigments, carbon black as conductive agent or colorant, crystal nucleating agent, plasticizer, flame retardant (brominated flame retardant, phosphorus based flame retardant, red phosphorus) , Silicone-based flame retardants, etc., flame retardant aids, and antistatic agents. That. Alternatively, a polymer other than the liquid crystal polyester resin can be blended to further impart predetermined properties. When mix | blending polymers other than liquid crystalline polyester resin, it is preferable that the ratio of liquid crystalline polyester resin is most large among the resin seed | species in liquid crystalline polyester resin composition.

  Examples of the method for incorporating the circuit-forming additive, filler, and other additives into the liquid-crystalline polyester resin composition of the present invention include, for example, the liquid-crystalline polyester resin, circuit-forming additive, filler, and the like. Dry blending method of blending solid additives and the like, solution blending method of blending liquid crystalline polyester resin, additive for circuit formation, and other liquid additive and the like to filler, additive for circuit formation, filling A material and other additives may be added at the time of polymerization of the liquid crystal polyester resin, and a method of melt-kneading the liquid crystal polyester resin with an additive for circuit formation, a filler and other additives may be used. Among them, a method of melt-kneading is preferable. A well-known method can be used for melt-kneading. For example, using a Banbury mixer, a rubber roll, a kneader, a single screw or twin screw extruder, etc., it can be melt-kneaded at the melting point + 50 ° C. or less of the liquid crystal polyester resin to make a liquid crystal polyester resin composition. Among them, a twin-screw extruder is preferred.

  In the twin-screw extruder, in order to improve the dispersibility of the liquid crystal polyester resin, the additive for circuit formation, and the filler, it is preferable to provide one or more kneading parts, and to provide two or more kneading parts. More preferable. For example, when the filler is added from the side feeder, the installation location of the kneading section is filled with the liquid crystal polyester resin and one or more places on the upstream side of the filler side feeder in order to promote plasticization of the liquid crystal polyester resin. In order to improve the dispersibility with the material, it is preferable to install a total of two or more locations at one or more locations downstream of the side feeder.

  Moreover, in order to remove the water | moisture content in a twin-screw extruder, and the decomposition product which arose during kneading | mixing, it is preferable to provide the vent part, and it is more preferable to provide two or more places. For example, when the filler is added from the side feeder, the installation location of the vent portion is one or more upstream of the side feeder to which the filler is charged in order to remove the attached moisture of the liquid crystal polyester resin, at the time of melt kneading. In order to remove the decomposition gas and the brought-in air at the time of supply of the filler, it is preferable to install two or more places in total at one place or more downstream of the side feeder. The vent portion may be under normal pressure or under reduced pressure. Moreover, it is preferable that the largest shear stress at the time of melt-kneading shall be 5000-20000 Pa. Preferably, it is 7500 to 18000 Pa, more preferably, 8000 to 16000 Pa. Maximum shear stress is the enhanced flow tester CFT-500D (orifice 0.5φ × at the maximum shear rate during kneading calculated from the resin temperature in the extruder, extruder cylinder diameter, screw rotation speed, and clearance of the kneading section) It can measure using 10 mm) (made by Shimadzu Corp.). By making the maximum shear stress at the time of melt-kneading into the above-mentioned range, deterioration of the resin composition is suppressed while improving the dispersibility of the additive for circuit formation and the filler. Therefore, it is preferable because the formability of the circuit portion on the surface of the resulting molded article and the dimensional stability after heat treatment of the molded article are excellent, and the corrosion of the circuit portion due to the gas generated from the molded article is suppressed.

  1) liquid crystal polyester resin, additive for circuit formation, filler, and other additives are charged at once from a backfill feeder and kneaded (collective kneading method), 2) liquid crystalline polyester resin, circuit Method of adding forming additives and other additives from a backfill feeder and kneading, then adding fillers and other additives from a side feeder and kneading (side feed method), 3) liquid crystalline polyester resin and A method (master pellet method) in which a master pellet containing a high concentration of circuit-forming additives and other additives is prepared, and then the master pellet is kneaded with a liquid crystal polyester resin and a filler so as to reach a specified concentration. It does not matter which method is used.

  The liquid crystal polyester resin composition of the present invention has excellent surface appearance (color tone) and machine by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning and the like. Into heat-resistant and flame-retardant molded articles. The molded articles referred to here include injection molded articles, extruded articles, press molded articles, sheets, pipes, unstretched films, uniaxially stretched films, various films such as biaxially stretched films, unstretched yarns, super-stretched yarns, etc. Various fibers can be mentioned. In particular, injection molding is preferable from the viewpoint of processability.

[LED module]
The liquid crystal polyester resin composition for LED modules of this invention can be used as a raw material for shape | molding the board | substrate which is the components which comprise an LED module. Hereinafter, the LED module in which the liquid crystal polyester resin composition for LED modules of this invention is used is demonstrated.

  The LED module formed by molding the liquid crystal polyester resin composition for an LED module of the present invention comprises an LED (light emitting diode) element, an LED package having a structure in which a bonding wire is sealed with a resin and an electrode portion is drawn. And a substrate having a metal circuit connected to the electrode portion.

  The LED package may be bullet-shaped or surface-mounted, with surface-mounted being suitable for lighting applications being preferred. One or more LED packages may be disposed on the LED module substrate.

  The substrate is a molded article molded using the liquid crystal polyester resin composition for an LED module of the present invention. Therefore, the adhesion of the circuit portion is excellent even at the time of reflow soldering processing at the time of manufacture of the LED module or at the time of heat generation due to LED light emission, and detachment and peeling of the metal circuit are suppressed. Further, even when the temperature around the product increases, the gas generated from the resin composition is reduced, and the corrosion of the metal circuit of the LED module is suppressed. The shape of the substrate may be planar or three-dimensional. The substrate has a metal circuit connected to the LED package on the surface, and the metal circuit may be a three-dimensional circuit.

  The LED module incorporates an LED controller and can be connected directly to a commercial power supply, as well as an "instrument-integrated LED module" integrated with lighting equipment and an LED controller, and lighting “Integrated with LED with integrated controller” that is a part of the device, “Integrated with LED with module” designed to be incorporated into lighting equipment, enclosed devices, etc., with integrated LED controller Designed with built-in control unit built-in type LED module designed to be incorporated into cage light fixtures, enclosed devices, etc., designed to be used in the same way as the light fixtures, equipped with the protection devices necessary for safety Has been designed to be installed separately from lighting equipment, closed-type devices, etc. It may be any form of control device built-in stand-alone LED module ".

  The LED module substrate described above has a metal circuit portion on the surface, but the method for forming the metal circuit portion on the surface is not particularly limited, and methods using various plating processes including application of a catalyst to a molded product, 2 Examples of such methods include a mask forming method in which masking is performed to portions other than the circuit forming portion by single molding, modification of the surface of a molded article by laser irradiation, a method by partial removal, and a combination thereof. In particular, a method of selectively forming a metal circuit portion at a laser irradiation portion including a pattern drawing step by laser irradiation to a molded product and a metallizing step by plating, represented by a laser direct structuring method etc., is one time It is preferable because it has advantages such as the ability to make molded articles by molding, easy pitch narrowing of circuits, no need to change molds when changing circuit patterns, and only changing the laser irradiation pattern.

There is no particular limitation on the laser to be irradiated to the metal circuit portion forming part, and YVO ₄ laser, CO ₂ laser, Ar laser, excimer laser and the like can be mentioned. In particular, an Nd: YAG laser, a YVO ₄ laser, or a FAYb laser operating at a fundamental wavelength of 1064 nm or a second high wavelength of 532 nm is preferable because of excellent formation of the metal circuit portion. The oscillation method of the laser beam may be continuous oscillation laser or pulse laser. The laser irradiated to the metal circuit portion forming portion is preferably a pulse laser which irradiates strong laser output for a short time from the viewpoint of suppressing thermal deterioration of the surface of the molded product and embedding of the additive for circuit formation by the molten resin.

  Gold, silver, copper, platinum, zinc, tin, nickel, cadmium, chromium and alloys containing them may be mentioned as metal species of the circuit part formed by the above method, and gold, copper and nickel are particularly metal circuits. It is preferable from the point of the formation property of a part, and adhesiveness. In addition, from the viewpoint of improving the stability of the metal circuit portion and conductivity, a metal layer made of a different kind of metal may be formed on the metal circuit portion of the molded product by a method such as plating.

  The LED module substrate formed with the metal circuit obtained by the above-mentioned method is space-saving as compared with a circuit member formed of a circuit forming a circuit according to the prior art and a molded product holding the same. It is useful because it can be simplified and it is easy to form a three-dimensional substrate having a three-dimensional circuit.

  Hereinafter, the present invention will be described in more detail by way of examples, but the gist of the present invention is not limited to the following examples.

  The liquid crystal polyester resin used for each Example and a comparative example is shown next.

  The compositional analysis and the characteristic evaluation of the liquid crystalline polyester resin were performed by the following method.

(1) Composition analysis of the liquid crystal polyester resin composition analysis LCP ^was carried out by 1 H- nuclear magnetic resonance spectrum ⁽¹ H-NMR) measurement. 50 mg of liquid crystalline polyester resin is weighed into an NMR sample tube, and dissolved in 800 μL of a solvent (pentafluorophenol / 1,1,2,2-tetrachloroethane-d ₂ = 65/35 (weight ratio) mixed solvent) to obtain UNITY INOVA 500 ¹ H-NMR measurement is performed at an observation frequency of 500 MHz and a temperature of 80 ° C. using a scanning NMR apparatus (manufactured by Varian), and the composition is determined from the peak area ratio derived from each structural unit observed around 7 to 9.5 ppm analyzed.

(2) Melting point (Tm) measurement of liquid crystalline polyester resin An endothermic peak observed when the liquid crystalline polyester resin is measured at a temperature rise of 20 ° C./min from room temperature by a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) After the temperature (Tm ₁ ) was observed, the temperature was kept at Tm ₁ + 20 ° C. for 5 minutes, and then it was temporarily cooled to room temperature under a temperature drop of 20 ° C./min, and measured again under a temperature rise condition of 20 ° C./min The observed endothermic peak temperature (Tm ₂ ) was taken as the melting point (Tm). In the following production examples, the melting point is described as Tm.

(3) Melt Viscosity Measurement of Liquid Crystalline Polyester Resin Using a heightening type flow tester CFT-500D (orifice 0.5φ × 10 mm) (manufactured by Shimadzu Corporation), a heightening type flow tester set to the melting point + 20 ° C. of the liquid crystal polyester resin After loading the liquid crystal polyester resin for melting the liquid crystal polyester resin in a furnace, the melt viscosity was measured at a shear rate of 1000 / sec after holding for 5 minutes.

Production Example 1 Liquid Crystalline Polyester Resin (A-1)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4'-dihydroxybiphenyl, 99 parts by weight of hydroquinone, 284 parts by weight of terephthalic acid, 90 parts by weight of isophthalic acid And 1252 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C while stirring under nitrogen gas atmosphere, then jacket temperature is changed from 145 ° C to 350 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-1) was obtained.

  Compositional analysis of the liquid crystal polyester resin (A-1) revealed that the proportion of structural units derived from p-hydroxybenzoic acid is 60.0 mol%, and the proportion of structural units derived from 4,4'-dihydroxybiphenyl is 12 .0 mol%, the proportion of structural units derived from hydroquinone is 8.0 mol%, the proportion of structural units derived from terephthalic acid is 15.2 mol%, the proportion of structural units derived from isophthalic acid is 4.8 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 75.2 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 330 degreeC and melt viscosity was 28 Pa.s.

Production Example 2 Liquid Crystalline Polyester Resin (A-2)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 870 parts by weight of p-hydroxybenzoic acid, 302 parts by weight of 4,4'-dihydroxybiphenyl, 119 parts by weight of hydroquinone, 247 parts by weight of terephthalic acid, 202 parts by weight of isophthalic acid And 1302 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C with stirring under a nitrogen gas atmosphere, then the jacket temperature is changed from 145 ° C to 330 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 330 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was further continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-2) was obtained.

  Compositional analysis of the liquid crystal polyester resin (A-2) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 53.8 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 13 .8 mol%, the proportion of structural units derived from hydroquinone is 9.2 mol%, the proportion of structural units derived from terephthalic acid is 12.7 mol%, and the proportion of structural units derived from isophthalic acid is 10.4 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 66.5 mol% relative to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 310 degreeC and melt viscosity was 30 Pa.s.

Production Example 3 Liquid Crystalline Polyester Resin (A-3)
1057 parts by weight of p-hydroxybenzoic acid, 151 parts by weight of 4,4'-dihydroxybiphenyl, 59 parts by weight of hydroquinone, 202 parts by weight of terephthalic acid, 22 parts by weight of isophthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillation tube And 1152 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C with stirring under a nitrogen gas atmosphere, then the jacket temperature is changed from 145 ° C to 365 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 365 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-3) was obtained.

  Compositional analysis of this liquid crystal polyester resin (A-3) revealed that 73.9 mol% of the structural unit derived from p-hydroxybenzoic acid and 7 ratio of the structural unit derived from 4,4'-dihydroxybiphenyl were obtained. .8 mol%, the proportion of structural units derived from hydroquinone is 5.2 mol%, the proportion of structural units derived from terephthalic acid is 11.7 mol%, and the proportion of structural units derived from isophthalic acid is 1.3 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 85.7 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 351 degreeC and melt viscosity was 31 Pa.s.

Production Example 4 Liquid Crystalline Polyester Resin (A-4)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl / g 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total of phenolic hydroxyl groups) are charged, reacted at 145 ° C. for 1 hour while stirring under a nitrogen gas atmosphere, and then 4 from 145 ° C. to 320 ° C. The temperature was raised over time. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-4) was obtained.

  Compositional analysis of this liquid crystal polyester resin (A-4) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 66.7 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 6 .3 mol%, the proportion of ethylenedioxy units derived from polyethylene terephthalate was 10.4 mol%, and the proportion of structural units derived from terephthalic acid was 16.7 mol%. The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 83.3 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 313 degreeC and melt viscosity was 13 Pa.s.

  The nylon resin used for the comparative example is shown below.

Production Example 5 Nylon Resin (A-5)
1000 parts by weight (6.84 moles) of adipic acid is charged into a 5 L reaction vessel equipped with a stirring blade, a dropping device, and a distillation tube, and heated at 170 ° C. for 1 hour while stirring under a nitrogen gas atmosphere. The temperature was raised to ° C., and 930 parts by weight (6.83 mol) of metaxylenediamine was added dropwise over 2.5 hours. Thereafter, the temperature was raised, and at 250 ° C., the inside of the can was depressurized and held at 260 ° C. for 20 minutes. Thereafter, the polymer was discharged in a gut form from the polymerizer and pelletized to obtain PAMXD6 (A-5) having a melting point of 238 ° C.

The additive for circuit formation used in each Example and the comparative example is shown next.
(B-1): Copper (II) phosphate (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter 3 μm)
(B-2): Copper pyrophosphate (II) (manufactured by Kanto Kagaku, average particle size 1 μm)
(B-3): Copper oxide (II) (manufactured by Wako Pure Chemical Industries, Ltd., average particle diameter 3 μm)
(B-4): tin oxide (II) (Wako Pure Chemical Industries, average particle diameter 3 μm)
(B-5): Copper-chromium oxide Black 3702 (manufactured by Asahi Kasei Kogyo Co., Ltd., average particle size 0.8 μm)

The filler used in each example and comparative example is shown below.
(C-1): mica AB-25S (Yamaguchi Mica, average particle diameter 24 μm, Mohs hardness 2.8)
(C-2): Glass milled fiber EPDE-40M-10A (manufactured by Nippon Electric Glass, average fiber length 40 μm, average fiber diameter 9 μm, Mohs hardness 5.5)

Examples 1 to 9 and Comparative Examples 1 to 5
In a Toshiba machine TEM35B type twin screw extruder equipped with a side feeder, 100 parts by weight of the liquid crystal polyester resin (A-1) to (A-4) and nylon resin (A-5) obtained in each production example The additives for circuit formation (B-1) to (B-5) are introduced from the backfill feeder in the compounding amounts shown in Table 1, and the compounding amounts shown in Table 1 with respect to 100 parts by weight of the liquid crystal polyester resin Fillers (C-1) to (C-2) are charged from the side feeder, and the cylinder temperature is adjusted to the melting point + 10 ° C. of liquid crystal polyester resins (A-1) to (A-4) and nylon resin (A-5). The pellet was set and melt-kneaded into pellets. The pellets of the obtained liquid crystal polyester resin composition are dried at 150 ° C. for 3 hours using hot air drying, and the pellets of the obtained nylon resin composition are vacuum dried at 80 ° C. for 24 hours using a vacuum dryer. The following (4) to (8) were evaluated. The results are shown in Table 1.

(4) Measurement of average particle diameter of additive for circuit formation and filler: 50 g of the pellet of the resin composition obtained by each example and comparative example is heated at 550 ° C. for 3 hours to remove the resin component, and the resin composition The mixture of the circuit forming additive and the filler in the product was taken out. The obtained mixture is dispersed in methylene iodide (specific gravity 3.33) and centrifuged at a rotational speed of 10000 rpm for 5 minutes, the suspended filler is removed by decantation, and the precipitated additive for circuit formation is filtered Taken out. 100 mg of the obtained additive for circuit formation and filler were weighed, dispersed in water, and measured using a laser diffraction / scattering particle size distribution measuring apparatus ("LA-300" manufactured by HORIBA), and volume average particle size The diameter was calculated.

(5) Formability of Circuit Portion The resin composition obtained by each Example and Comparative Example is applied to FANUC α30C injection molding machine (manufactured by FANUC, screw diameter 28 mm), and the cylinder temperature is the melting point of the liquid crystal polyester resin and nylon resin. A square molded article 70 mm × 70 mm × 1 mm thick was molded at + 20 ° C., a mold temperature of 90 ° C. for liquid crystal polyester resin, and 80 ° C. for nylon resin. Laser irradiation was performed on the surface of the obtained molded article using a LP-V10U FAYb laser apparatus manufactured by Panasonic under the conditions of wavelength 1064 nm, frequency 50 Hz, laser output 5.0 W, and scanning speed 3000 mm / s. The molded product is subjected to a 6 μm thick electroless copper plating treatment, and then cooled to −40 ° C. in 5 minutes from room temperature and held for 30 minutes with a thermal shock device (TSA-70L manufactured by ESPEC), then 5 minutes The temperature was raised to 150 ° C., and the cold heat treatment was performed under the test condition repeated ten times with 30 minutes of holding as one cycle. Using a commercially available NT cutter (blade with a width of 9 mm and a 35 ° inclination), the cold heat-treated molded product is cut with a depth reaching the resin molded product so that 100 squares of 1 mm intervals can be made. The Apply a tape (adhesive strength 3.4-3.9 N / cm, Nichiban Sellotape (registered trademark), width 18 mm) to the grid sufficiently and hold the tape at both ends and peel it off instantaneously in the vertical direction, plating The number of squares remaining without peeling of the surface was measured. Moreover, what did not form plating in the molded article surface was made into "x". The formability of the circuit portion of the molded product is considered to be excellent as the number of squares (number of remaining plating treated surfaces) remaining without peeling of the plating treated surface increases.

(6) Evaluation of dimensional stability The resin composition obtained by each example and comparative example is supplied to FANUC α30C injection molding machine (manufactured by FANUC, screw diameter 28 mm), and the cylinder temperature is the melting point of liquid crystal polyester resin and nylon resin. A rod shape molded of 150 mm long × 12.7 mm wide × 0.5 mm thick, side gate 0.5 mm × 0.5 mm, with a mold temperature of 90 ° C. for liquid crystalline polyester resin and 80 ° C. for nylon resin . The obtained rod-like molded product is heated to 200 ° C. at 1.6 ° C./sec with a reflow simulator core 9030 c (manufactured by Coors Co., Ltd.) and preheated for 2 minutes, and reflowed at a maximum surface temperature of 260 ° C. for 30 seconds The substrate was cooled to room temperature, reflowed, and the amount of warpage after the reflow was evaluated. The length before and after the reflow process is measured using a universal projector (V-16A (made by Nikon)) for the 10 mm length of the central part of the rod-like molded product, and the elongation percentage of the length before and after heat treatment is the dimensional change Asked as. The smaller the change in length (rate of dimensional change) before and after heat treatment, the better the dimensional stability of the molded article after heat treatment.

(7) Low-Gas Evaluation Using the thermogravimetric analyzer TGA-7 (manufactured by Perkin Elmer), the resin compositions obtained by the respective Examples and Comparative Examples were subjected to a liquid crystal polyester resin and a melting point of nylon resin for 30 minutes at + 10 ° C. The reduction rate of the weight at the time of holding was measured, and it was set as the amount of generated gas. The smaller the amount of generated gas, the better the corrosion of the circuit due to the gas generated from the molded product is suppressed.

(8) Reliability of LED Module The resin composition obtained in each Example and Comparative Example is applied to FANUC α30C injection molding machine (FANUC product, screw diameter 28 mm), and the cylinder temperature is the melting point of liquid crystal polyester resin and nylon resin. A square molded product having a thickness of 70 mm × 70 mm × 7.8 mm was molded at + 20 ° C., a mold temperature of 90 ° C. for liquid crystal polyester resin, and 80 ° C. for nylon resin. On the surface of the molded product obtained, using LP-V10U FAYb laser made by Panasonic, wiring pattern with 0.2 mm width and 1 mm interval under the condition of wavelength 1064 nm, frequency 50 Hz, laser output 5.0 W, scanning speed 3000 mm / s Laser irradiation was performed. The molded product was subjected to electroless copper plating of 6 μm thickness. The surface mount type LED package was mounted by the reflow soldering process of the conditions described in the evaluation (6) so as to connect with the wiring pattern, to obtain an LED module. Then, it is cooled to -40 ° C in 5 minutes from room temperature and held for 30 minutes with a thermal shock device (TSA-70L manufactured by ESPEC), then heated up to 150 ° C in 5 minutes and held for 30 minutes as one cycle 10 times Cold heat treatment of the LED module was performed under repeated test conditions. The continuity of the wiring of the LED module after processing was evaluated by a tester. Those with continuity after cold heat treatment are "○", those with LED package and wiring peeled off etc. by cold heat treatment so that they are broken or shorted by "×", and those with no wiring pattern formed by plating- ". It is considered that the more conductive the better the reliability of the LED module.

  From the results of Table 1, the liquid crystal polyester resin composition for an LED module according to the embodiment of the present invention is excellent in the formation of the circuit portion on the surface of the molded article, the dimensional stability after heat treatment of the surface of the molded article, and further from the molded article It can be seen that the amount of generated gas is small. Therefore, even when the product peripheral temperature increases during manufacture or use, the adhesion of the metal circuit portion is excellent, the occurrence of corrosion of the metal circuit portion can be suppressed, and the LED module substrate having the metal circuit on the surface is obtained. It is suitable for the use of

The liquid crystal polyester resin composition for an LED module of the present invention is excellent in the formability of the circuit portion on the surface of the molded article, the dimensional stability after heat treatment of the surface of the molded article, and further suppresses the corrosion of the circuit portion by the gas generated from the molded article. Therefore, it is useful for use in an LED module substrate having a metal circuit on the surface.

Claims (6)

It is an LED module provided with the LED package provided with a light emitting element, and the board | substrate which mounted one or more of the said LED package, Comprising: The said LED module forms the metal circuit connected with a LED package in the substrate surface, The substrate is made of a liquid crystal polyester resin composition containing a liquid crystal polyester resin and an additive for forming a circuit, and in the liquid crystal polyester resin, the total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid is liquid crystal The LED module which is 60-77 mol% with respect to 100 mol% of all the structural units of polyester resin. The LED module according to claim 1, wherein the circuit forming additive is a metal compound consisting of one metal species. The LED module according to claim 1, wherein a compounding amount of the circuit-forming additive is 3 to 25 parts by weight with respect to 100 parts by weight of the liquid crystal polyester resin. The LED module according to any one of claims 1 to 3, wherein the liquid crystal polyester resin composition contains an inorganic filler. A liquid crystal polyester resin composition comprising a liquid crystal polyester resin and an additive for forming a circuit, wherein the liquid crystal polyester resin is a liquid crystal polyester resin in which a total of a structural unit derived from hydroxybenzoic acid and a structural unit derived from terephthalic acid The manufacturing method of the LED module including the process of forming a metal part in the surface of the molded article which consists of a liquid crystalline polyester resin composition which is 60-77 mol% with respect to 100 mol% of all the structural units. A liquid crystal polyester resin composition comprising a liquid crystal polyester resin and an additive for forming a circuit, wherein the liquid crystal polyester resin is a liquid crystal polyester resin in which a total of a structural unit derived from hydroxybenzoic acid and a structural unit derived from terephthalic acid The liquid crystal polyester resin composition for LED modules which is 60-77 mol% with respect to 100 mol% of all the structural units of this.