JP7290084B2 - Thermoplastic polyester resin composition, molded article and method for producing molded article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic polyester resin composition and molded articles using the same.

Thermoplastic polyester resins are excellent in mechanical properties, heat resistance, and moldability. Therefore, it is used in a wide range of fields such as electric/electronic parts and automobile parts that require these properties. By the way, in electrical and electronic component applications, as products become lighter and thinner, electrical and electronic components are becoming smaller and thinner. ing. By forming a three-dimensional electronic circuit pattern on the surface of a resin molded product, it becomes possible to liberalize circuit board design, reduce module size, reduce the number of parts, and reduce assembly man-hours. Methods for forming circuits on resin molded products include, for example, a mask forming method in which areas other than the circuit formation area are masked by two-step molding, and a combination of a circuit pattern drawing method using laser irradiation and a metallization technique such as plating. and continues to expand. Among them, the laser direct structuring method, which is a method of forming a metal pattern in the part drawn by laser irradiation by activating the metal additive in the resin composition by laser irradiation and metallizing by plating etc. It continues to expand due to the ease of drawing and metallization processes. In the laser direct structuring method, additives are included in order to obtain desired properties, for example, a polyamide resin composition that contains a composite oxide containing copper, chromium, and manganese and has excellent mechanical strength (for example, Patent Document 1 Reference), a polyamide resin composition that contains titanium oxide and has excellent plating properties (see, for example, Patent Document 2), and a polycarbonate resin composition that contains titanium oxide and has excellent plating properties (see, for example, Patent Documents 3 and 4). It is

JP 2014-58604 A WO2014/042071 WO2014/163242 JP 2013-544296 A

However, in the resin composition described in Patent Document 1, the additive has a high laser absorbency, an exothermic reaction occurs during laser irradiation, and the adhesiveness between the molded product surface and the metal conductive portion is reduced, and the resin portion is damaged. There is a problem that detachment or peeling occurs due to carbonization or the like. In addition, the resin compositions described in Patent Documents 2 to 4 are still insufficient in the formation of the metal conduction part, and when the metal part is formed at a narrow interval on the surface of the molded product, the formation of the metal conduction part is poor. , problems such as short-circuiting of adjacent metal parts occur. Therefore, the resin composition corresponding to the conventional technique for forming a three-dimensional circuit board is not sufficiently satisfactory for the above problems, and further improvement is required.

Therefore, the present invention solves the above-mentioned problems and provides a thermoplastic polyester resin composition which is excellent in adhesion between a resin molded article and a metal conductive part, and which is excellent in fine circuit formability on the surface of the molded article, and molding using the same. The challenge is to provide products.

The inventors of the present invention conducted intensive studies to solve the above problems, and found that a thermoplastic polyester was added with at least one additive selected from circuit-forming additives, titanium oxynitride, and composite oxides containing titanium, calcium and manganese. The thermoplastic polyester resin composition containing the The inventors have found that a suitable molded article, particularly a molded article having a metal portion on the surface thereof, can be obtained, and arrived at the present invention.

That is, the present invention has been made to solve the above-described problems, and embodiments of the present invention can include at least part of the configurations listed below.
(1) 100 parts by weight of thermoplastic polyester (A), 5 to 25 parts by weight of circuit-forming additive (B), titanium oxynitride (C1) and composite oxide containing titanium, calcium and manganese (C2 ) containing 0.1 to 20 parts by weight of at least one additive (C) selected from ), a thermoplastic polyester resin composition.
(2) The thermoplastic polyester resin composition according to (1), wherein the thermoplastic polyester is a liquid crystalline polyester.
(3) The thermoplastic polyester resin composition according to (2), further comprising 5 to 150 parts by weight of filler (D).
(4) The liquid crystalline polyester is characterized in that the sum of aromatic oxycarbonyl units and terephthalic acid units is 60 to 77 mol% with respect to 100 mol% of all structural units of the liquid crystalline polyester. Or the thermoplastic polyester resin composition according to (3).
(5) A molded article made of the thermoplastic polyester resin composition according to any one of (1) to (4).
(6) The molded article according to (5), which has a metal portion on its surface.
(7) A method for producing a molded product having a metal portion on its surface, comprising a pattern drawing step by laser irradiation of the molded product according to (5) and a metallization step on the laser irradiated portion by plating.
(8) The molded article according to (5) or (6), which is any one of a sensor, an LED lamp substrate, a camera module, an antenna, and a wearable terminal member.

By using the thermoplastic polyester resin composition of the present invention, it is possible to obtain a molded article having excellent adhesiveness between the resin molded article and the metal conductive portion, and further excellent fine circuit formability on the surface of the molded article. These molded articles are particularly suitable for use in electrical and electronic parts having metal parts on their surfaces.

The present invention will be described in detail below.

[Thermoplastic polyester]
The thermoplastic polyester (A) used in the present invention includes (a) dicarbonyl units (or ester-forming derivatives thereof) and dioxy units (or ester-forming derivatives thereof), (b) oxycarbonyl units (or esters thereof) formable derivative), (c) a polymer or copolymer obtained by a condensation reaction having at least one type selected from lactone units as a main structural unit, or a mixture thereof.

Specific examples of oxycarbonyl units in each structural unit constituting the thermoplastic polyester (A) used in the present invention include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, glycol Structural units derived from hydroxycarboxylic acids such as acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, and the like, and p-hydroxybenzoic acid is preferred.

Specific examples of dioxy units include 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, t-butylhydroquinone, 3,3′,5,5′-tetramethyl-4,4′-dihydroxybiphenyl, phenylhydroquinone, chloro hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl ether, 4,4'- Structural units generated from aromatic diols such as dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol , Structural units generated from aliphatic diols such as neopentyl glycol; Structural units generated from alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; 4,4'- Dihydroxybiphenyl and hydroquinone are preferred.

Specific examples of dicarbonyl units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, Aromas such as 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid Structural units generated from group dicarboxylic acids; Structural units generated from aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexahydroterephthalic acid; 1,4-cyclohexanedicarboxylic acid, 1,3- Structural units generated from alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid are included, and terephthalic acid and isophthalic acid are preferred.

Specific examples of lactone units include caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, and the like.

Specific examples of the thermoplastic polyester (A) used in the present invention include structural units derived from p-hydroxybenzoic acid, structural units derived from 6-hydroxy-2-naphthoic acid, and structures derived from aromatic dihydroxy compounds. Polyester consisting of units and structural units derived from aromatic dicarboxylic acids, structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid Polyester consisting of structural units derived from, structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, dicarboxylic acids such as terephthalic acid and isophthalic acid Polyester consisting of structural units derived from, structural units derived from p-hydroxybenzoic acid, structural units derived from aromatic dihydroxy compounds, derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, 2,6-naphthalene Examples include polyesters composed of structural units derived from dicarboxylic acid, and structural units derived from ethylene glycol and terephthalic acid.

Raw material monomers constituting each structural unit described above are not particularly limited as long as they have a structure capable of forming each structural unit. , carboxylic acid derivatives such as acid anhydrides, and the like may also be used.

The thermoplastic polyester (A) used in the present invention is composed of the structural units described above, so that the obtained thermoplastic polyester resin composition has excellent heat resistance. Therefore, a molded article using the thermoplastic polyester resin composition has excellent adhesion between the resin molded article and the metal conductive portion, and further has excellent fine circuit formability on the surface of the molded article.

Liquid crystalline polyester is particularly preferred from the viewpoint of improving the heat resistance of the thermoplastic polyester (A) used in the present invention and improving the adhesion between the resin molded product and the metal conductive portion. Liquid crystalline polyester is a polyester called thermotropic liquid crystal polymer that exhibits optical anisotropy when melted. It is a liquid crystalline polyester that forms a liquid crystalline melt phase. Examples of liquid crystalline polyesters include structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. It is a liquid crystalline polyester consisting of a structural unit that

The total amount of dioxy units constituting the liquid crystalline polyester and the total amount of dicarbonyl units are substantially equimolar. The term "substantially equimolar" as used herein means that the structural units constituting the polymer main chain excluding the terminals are equimolar. For this reason, an aspect in which equimolarity is not necessarily obtained when structural units constituting terminals are included can also satisfy the requirement of "substantially equimolar".

In the liquid crystalline polyester used in the present invention, the total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid is preferably 60 to 77 mol% with respect to 100 mol% of all structural units of the liquid crystalline polyester. .

If the total amount of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid is less than 60 mol% with respect to 100 mol% of the total structural units of the polyester, the heat resistance of the liquid crystalline polyester is lowered. The adhesiveness between the resin molding using the liquid crystal polyester resin composition and the metal conduction part is lowered, and furthermore, it becomes difficult to form a fine circuit on the surface of the molding. On the other hand, when the sum of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid exceeds 77 mol% with respect to 100 mol% of all structural units of the liquid crystalline polyester, the crystallinity of the liquid crystalline polyester increases. In addition, the adhesion between the resin molded product and the metal conductive portion is lowered, and furthermore, it becomes difficult to form a fine circuit on the surface of the molded product.

From the viewpoint of improving the adhesion between the resin molded product and the metal conductive part, the total of the structural units derived from hydroxybenzoic acid and the structural units derived from terephthalic acid with respect to 100 mol% of the total structural units of the liquid crystal polyester is 65 mol. % or more is more preferable, and 69 mol % or more is even more preferable. On the other hand, 76 mol % or less is preferable. Further, the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid may have either one of the structural units, and the other structural unit may be 0 mol%, but each is 0 mol. % is preferred.

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 within the above range, the crystallinity of the liquid crystal polyester is controlled, and the resin molded product and the metal conductive portion It is preferable because it is excellent in adhesion with. Further, when the liquid crystalline polyester is composed of structural units within the above range, the melting point of the liquid crystalline polyester can be controlled, and as a result, a molded article having excellent heat resistance and moldability can be obtained, which is preferable. In addition, it is possible to mold a molded product without excessively high temperature during molding, and as a result of suppressing deterioration of the liquid crystal polyester resin composition during molding, it is possible to obtain a molded product with excellent mechanical strength. It is preferable because it can be done.

The method for calculating the content of each structural unit in the thermoplastic polyester (A) of the present invention is shown below. First, the thermoplastic polyester (A) is weighed into an NMR (nuclear magnetic resonance) test tube and dissolved in a polyester-soluble solvent (for example, pentafluorophenol/heavy tetrachloroethane- _d2 mixed solvent). Next, the resulting solution is subjected to ¹ H-NMR spectrum measurement, and calculation can be made from the peak area ratio derived from each structural unit.

From the viewpoint of heat resistance, the melting point (Tm) of the thermoplastic polyester (A) of the present invention is preferably 220°C or higher, more preferably 270°C or higher, and even more preferably 300°C or higher. On the other hand, from the viewpoint of workability, the melting point (Tm) of the thermoplastic polyester is preferably 350°C or lower, more preferably 345°C or lower, and even more preferably 340°C or lower.

Melting points (Tm) are measured by differential scanning calorimetry. Specifically, first, the endothermic peak temperature (Tm ₁ ) is observed by heating the polymer that has completed polymerization from room temperature at a temperature rising condition of 20° C./min. After observing the endothermic peak temperature (Tm ₁ ), the polymer is held at a temperature of endothermic peak temperature (Tm ₁ )+20° C. for 5 minutes. After that, the polymer is cooled to room temperature under the temperature decreasing condition of 20°C/min. Then, the endothermic peak temperature (Tm ₂ ) is observed by heating the polymer at a temperature rising condition of 20° C./min. Melting point (Tm) refers to the endothermic peak temperature (Tm ₂ ).

The method for producing the thermoplastic polyester (A) used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. As known polycondensation methods for thermoplastic polyesters, thermoplastic polyesters are converted to structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, and terephthalic acid. Examples of polyesters composed of structural units derived from isophthalic acid and structural units derived from isophthalic acid include the following.
(1) A method of producing polyester from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid and isophthalic acid by deacetic acid condensation polymerization reaction.
(2) Polyester is produced by reacting p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and hydroquinone with terephthalic acid and isophthalic acid with acetic anhydride to acetylate the phenolic hydroxyl groups, followed by deacetic acid polymerization. how to.
(3) A method of producing a polyester from phenyl p-hydroxybenzoate and 4,4'-dihydroxybiphenyl, hydroquinone, diphenyl terephthalate and diphenyl isophthalate by dephenol polycondensation reaction.
(4) Aromatic dicarboxylic acids such as p-hydroxybenzoic acid, terephthalic acid, and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to obtain phenyl esters, respectively, followed by aromatic dicarboxylic acids such as 4,4'-dihydroxybiphenyl and hydroquinone. A method for producing polyester by adding a group dihydroxy compound and performing a dephenol 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 groups, followed by a deacetic acid polycondensation reaction to produce a polyester. is preferably used because it is industrially excellent in controlling the terminal structure of the polyester and controlling the degree of polymerization.

As a method for producing the thermoplastic polyester (A) used in the present invention, it is also possible to complete the polycondensation reaction by a solid phase polymerization method. Examples of the treatment by solid phase polymerization include the following methods. First, a polymer or oligomer of thermoplastic polyester (A) is pulverized with a pulverizer. The pulverized polymer or oligomer is heated under a stream of nitrogen or under reduced pressure to polycondense to the desired degree of polymerization to complete the reaction. The heating can be carried out for 1 to 50 hours at a melting point of -50°C to -5°C (for example, 200 to 300°C) of the polyester.

The polycondensation reaction of the thermoplastic polyester (A) proceeds without a catalyst, but stannous acetate, tetrabutyl titanate, potassium acetate, sodium acetate, antimony trioxide, metallic magnesium, etc. can also be used as catalysts.

[Additive for circuit formation]
The thermoplastic polyester resin composition of the present invention is characterized by containing a circuit-forming additive (B). The circuit-forming additive (B) used in the present invention is incorporated into the thermoplastic polyester resin composition of the present invention so that the molded article made of the thermoplastic polyester resin composition is irradiated with a laser. (B) is exposed on the surface of the molded article, degraded, and is used as a starting point by a method such as electroless plating to impart a property that a metal portion can be formed in the laser-irradiated portion.

Examples of metal species constituting the circuit-forming additive (B) used in the present invention include copper, tin, cobalt, nickel, antimony, neodymium, molybdenum, bismuth, and silver. Note that composite oxides containing titanium, calcium and manganese as metal species are not included. The circuit-forming additive (B) may be used as a single metal or as a compound containing a metal. As compounds containing metals, oxides, sulfides, sulfates, nitrides, nitrates, carbonates, phosphates, pyrophosphates, halides, hydroxides, organometallic compounds, complexes, and the like can be used. . The oxide may also have a spinel structure consisting of at least two different cations. Furthermore, it may be an oxide doped with antimony. Among them, oxides, phosphates, and pyrophosphates, which suppress the reaction and decomposition of the circuit-forming additive during the molding process of the thermoplastic polyester resin composition and are excellent in the fine circuit formability on the surface of the molded product. , hydroxides are preferred. In addition, since the circuit-forming additive (B) is composed of any one of the above metals, it is dispersed appropriately in the thermoplastic polyester resin composition, and the circuit-forming property on the surface of the molded article is excellent. Therefore, it is preferable. Among them, tin oxide, copper oxide, copper phosphate, and copper pyrophosphate are preferred, and copper phosphate and copper pyrophosphate are particularly preferred. By using the above particularly preferable compound as the circuit-forming additive (B), heat deterioration during processing of the thermoplastic polyester resin composition containing these additives is prevented due to the excellent thermal stability of the circuit-forming additive. Suppressed. Therefore, it is preferable because the adhesion between the resin molded product and the metal conductive portion is excellent.

The thermoplastic polyester resin composition of the present invention is characterized by containing 3 to 25 parts by weight of the circuit-forming additive (B) with respect to 100 parts by weight of the thermoplastic polyester (A). If the circuit-forming additive is added in an amount of less than 3 parts by weight or if the circuit-forming additive is not added, the metal part of the molded article is not formed, or the amount of formation is insufficient and the metal part cannot obtain conductivity. The circuit formability of the surface of the molded product is also lowered. From the viewpoint of circuit-forming properties on the surface of the molded product, the amount of the circuit-forming additive is preferably 3.5 parts by weight or more, more preferably 5 parts by weight or more. On the other hand, if the amount of the circuit-forming additive exceeds 25 parts by weight, the mechanical strength of the molded article made of the thermoplastic polyester resin composition is lowered, and the adhesion between the resin molded article and the metal conductive portion is lowered. In addition, during extrusion production of the thermoplastic polyester resin composition, it has adverse effects such as strand breakage. From the viewpoint of maintaining the adhesion between the resin molded product and the metal conductive portion, the amount of the circuit-forming additive compounded is preferably 21 parts by weight or less, more preferably 19 parts by weight or less.

The circuit-forming additive (B) used in the present invention preferably has an average particle size of more than 1 μm. The average particle size here is the volume average particle size, and can be obtained by the following method. The resin component is removed by heating 50 g of the thermoplastic polyester resin composition at 550° C. for 3 hours, and the circuit-forming additive (B) is taken out. For example, when a filler is added in addition to the circuit-forming additive (B), it can be separated by the difference in specific gravity. For example, a mixture of a circuit-forming additive and a filler from which the resin component has been removed is taken out, and this is treated with methylene iodide (specific gravity 3.33), 1,1,2,2-tetrabromoethane (specific gravity 2.970), Ethanol (specific gravity 0.789) or the like was used to disperse in a mixed solution that was appropriately mixed so as to have a specific gravity between the circuit-forming additive and the filler, centrifuged at 10000 rpm for 5 minutes, and then floated. The filler is removed by decantation and the settling circuit-forming additive is removed by filtration. 100 mg of the resulting circuit-forming additive is weighed, dispersed in water, and measured using a laser diffraction/scattering particle size distribution analyzer ("LA-300" manufactured by HORIBA).

When the average particle size of the circuit-forming additive (B) is larger than 1 μm, the circuit-forming additive (B) and titanium oxynitride (C1) described below are used during the production and molding of the thermoplastic polyester resin composition. And at least one additive (C) selected from composite oxides (C2) containing titanium, calcium and manganese and kneading with the filler (D) is promoted, so that aggregation of each is suppressed and obtained In the molded article, at least one additive (C) selected from a circuit-forming additive (B), titanium oxynitride (C1), and a composite oxide (C2) containing titanium, calcium and manganese, and a filler ( D) is excellent in dispersibility. This is preferable because it improves the laser circuit formability of the molded product. 1.5 μm or more is preferable, and 2.0 μm or more is more preferable. On the other hand, from the viewpoint of suppressing uneven distribution of the circuit-forming additive (B) in the thermoplastic polyester resin composition, the upper limit of the average particle size of the circuit-forming additive (B) is preferably 350 μm or less, and 100 μm or less. is more preferable, and 50 μm or less is even more preferable.

[At least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese]
The thermoplastic polyester resin composition of the present invention is characterized by containing at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese. . By using these additives (C), during laser irradiation, the exothermic reaction caused by the laser causes a decrease in adhesion to the metal conduction part on the surface of the molded product, carbonization of the resin part, etc., resulting in detachment or peeling. can prevent In addition, if the metal parts are formed on the surface of the molded product at narrow intervals, problems such as short-circuiting of adjacent metal parts occur due to poor plating of the metal parts. Therefore, by using at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, the thermoplastic polyester resin composition of the present invention can When irradiated with a laser, it is possible to obtain a molded article having improved adhesion between the resin molded article and the metal conduction part and excellent fine circuit formability on the surface of the molded article. Titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese do not show characteristics as circuit-forming additives (B) by themselves.

Titanium oxynitride (C1) is a composite of titanium oxide and titanium nitride. The proportion of titanium oxide and titanium nitride may be arbitrary as long as it does not impair the effects of the present invention. The composite oxide (C2) containing titanium, calcium and manganese may contain other components as long as they do not impair the effects of the present invention.

As at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, only one type may be used, or two or more types may be used in combination. However, it is preferable to use a composite oxide (C2) containing titanium, calcium and manganese from the viewpoint of improving the adhesion between the resin molded product and the metal conductive portion.

The amount of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese is, relative to 100 parts by weight of the thermoplastic polyester (A), It is characterized by being 0.1 to 20 parts by weight. When the blending amount of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese is less than 0.1 part by weight, the laser is irradiated. However, depending on the laser intensity, the laser cannot be absorbed, and the metal part of the molded product is not formed, or the amount of formation is insufficient and the metal part cannot obtain conductivity, and the circuit formability of the surface of the molded product is also poor. descend. In addition, if the metal parts are formed on the surface of the molded product at narrow intervals, problems such as short-circuiting of adjacent metal parts occur due to poor plating of the metal parts. From the viewpoint of circuit formation, the amount of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese is 0.5 parts by weight or more. is more preferred, and 1 part by weight or more is even more preferred. Further, when the blending amount of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese exceeds 20 parts by weight, the thermoplastic polyester resin composition The mechanical strength of the molded article made of the material is lowered, and the adhesion between the resin molded article and the metal conduction part is lowered. Blending of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, from the viewpoint of improving the adhesion between the resin molded article and the metal conductive part. The amount is more preferably 15 parts by weight or less, more preferably 10 parts by weight or less.

At least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese used in the present invention has an average particle size of 0.01 to 10 μm. is preferred. The average particle size here is the volume average particle size, and can be obtained by the method described above.

When the average particle size of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese is 0.01 μm or more, the thermoplastic polyester resin composition At least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, and a circuit-forming additive (B) during manufacturing and molding of an object Since kneading with the filler (D) described below is promoted, the aggregation of each is suppressed, and the titanium oxynitride (C1) and the composite oxide containing titanium, calcium and manganese ( At least one additive (C) selected from C2), the circuit-forming additive (B), and the filler (D) have excellent dispersibility. This is preferable because the formation of fine circuits on the surface of the molded article is improved. 0.05 μm or more is preferable. On the other hand, from the viewpoint of suppressing uneven distribution of at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese in the thermoplastic polyester resin composition. , titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese. The upper limit of the average particle size of at least one additive (C) is preferably 5 μm or less, more preferably 3 μm or less preferable.

[Filling material]
The thermoplastic polyester resin composition of the present invention may further contain a filler (D). The filler that can be used in the present invention is at least one additive selected from circuit-forming additives (B), titanium oxynitride (C1), and composite oxides (C2) containing titanium, calcium and manganese. Other than (C), it is not particularly limited, but examples thereof include fibrous, whisker-like, and non-fibrous (for example, plate-like, powdery, granular, amorphous) fillers. Specifically, fibrous and whisker-like fillers include glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, and organic fibers such as aromatic polyamide fibers and polyester fibers. Fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, Examples include wollastonite and acicular titanium oxide. Platey fillers include mica, glass flakes, talc, kaolin, clay, graphite, and molybdenum disulfide. Powdery and granular fillers include silica, glass beads, titanium oxide, zinc oxide, and calcium polyphosphate.

The above fillers that can be used in the present invention may have their surfaces treated with known coupling agents (e.g., silane-based coupling agents, titanate-based coupling agents, etc.) or other surface treatment agents. good.

The content of the filler (D) is preferably 5 to 150 parts by weight per 100 parts by weight of the thermoplastic polyester (A). From the viewpoint of improving adhesion, the amount of the filler compounded is more preferably 15 parts by weight or more, and even more preferably 20 parts by weight or more. From the viewpoint of fine circuit formability, the amount of the filler compounded is more preferably 150 parts by weight or less, and even more preferably 100 parts by weight or less.

The filler (D) used in the present invention preferably has an average particle size of 10 to 1000 μm. The average particle size here is the volume average particle size, and can be obtained by the method described above. When the average particle size of the filler (D) is 10 μm or more, the reinforcing effect is excellent, and the circuit-forming additive (B), the titanium oxynitride (C1) and the composite oxide containing titanium, calcium and manganese (C2) Since kneading with at least one additive (C) selected from At least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese has excellent dispersibility. This is preferable because it improves the formation of fine circuits in the molded article.

The filler (D) used in the present invention is more preferably non-fibrous, and particularly preferably mica, glass flakes, or talc because of their excellent adhesion between the resin molded product and the metal conductive portion.

The thermoplastic polyester resin composition of the present invention further contains antioxidants, heat stabilizers (for example, hindered phenols, hydroquinones, phosphites and substituted products thereof), ultraviolet Absorbents (e.g., resorcinol, salicylates), anti-coloring agents such as phosphites and hypophosphites, lubricants and release agents (long-chain fatty acids such as montanic acid and their metal salts, their esters, their half esters , silicones, higher alcohols, higher fatty acid amides, polyethylene wax, etc.), coloring agents containing dyes or pigments, conductive agents, crystal nucleating agents, plasticizers, flame retardants (brominated flame retardants, phosphorus flame retardants, red phosphorus , silicone flame retardants, etc.), flame retardant aids, and antistatic agents. Alternatively, a polymer other than the thermoplastic polyester (A) can be blended to impart further desired properties. When blending a polymer other than the thermoplastic polyester (A), it is preferable that the proportion of the thermoplastic polyester (A) is the highest among the resin types.

The method for compounding the polyester composition of the present invention is not particularly limited. For example, thermoplastic polyester (A), circuit-forming additive (B), titanium oxynitride (C1), and at least one additive (C) selected from composite oxides (C2) containing titanium, calcium and manganese , a dry blending method of blending a filler (D) and other solid additives, etc., a thermoplastic polyester (A), a circuit forming additive (B), titanium oxynitride (C1) and titanium, calcium and At least one additive (C) selected from manganese-containing composite oxides (C2), a solution blending method in which other liquid additives are blended with the filler (D), and an additive for circuit formation (B), at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, a filler (D) and other additives in a thermoplastic Select from a method of adding during polymerization of polyester (A), thermoplastic polyester (A) and circuit-forming additive (B), titanium oxynitride (C1) and composite oxide containing titanium, calcium and manganese (C2) A method of melt-kneading at least one additive (C), a filler (D) and other additives contained in the mixture can be used, and a method of melt-kneading is preferable. A known method can be used for the melt-kneading. For example, a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like can be used to melt-knead the mixture at the melting point of the polyester plus 50° C. or less to form a thermoplastic polyester resin composition. Among them, a twin-screw extruder is preferred.

For the twin screw extruder, at least one selected from thermoplastic polyester (A) and circuit forming additive (B), titanium oxynitride (C1) and composite oxide (C2) containing titanium, calcium and manganese In order to improve the dispersibility of the additive (C) and the filler (D), it is preferable to provide one or more kneading portions, more preferably two or more. For example, when the filler is added from the side feeder, the kneading part is installed at one or more points upstream of the side feeder of the filler in order to promote the plasticization of the polyester. In order to improve the efficiency, it is preferable to install at least one place downstream of the side feeder, that is, at least two places in total.

Also, in order to remove moisture in the twin-screw extruder and decomposition products generated during kneading, it is preferable to provide vents, more preferably two or more vents. For example, when the filler is added from the side feeder, the vent part is installed at one or more points upstream of the side feeder that feeds the filler in order to remove the moisture attached to the polyester. In order to remove air brought in during the supply of components and fillers, it is preferable to install a total of two or more locations, one or more locations downstream of the side feeder. The vent section may be under normal pressure or under reduced pressure.

As a kneading method, 1) at least one selected from thermoplastic polyester (A), circuit-forming additive (B), titanium oxynitride (C1) and composite oxide (C2) containing titanium, calcium and manganese A method in which the additive (C), the filler (D), and other additives are added at once from a main feeder and kneaded (batch kneading method), 2) thermoplastic polyester (A), circuit-forming additive ( B), at least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese, and other additives were charged from a main feeder and kneaded. After that, a method of adding filler (D) and other additives from a side feeder and kneading (side feed method), 3) thermoplastic polyester (A) and circuit forming additive (B), titanium oxynitride (C1 ) and at least one additive (C) selected from composite oxides (C2) containing titanium, calcium and manganese, and other additives at a high concentration. Any method such as a method of kneading master pellets with the thermoplastic polyester (A) and filler (D) (master pellet method) may be used.

The thermoplastic polyester resin composition of the present invention can be obtained by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc., to obtain excellent surface appearance (color tone) and It can be processed into moldings with mechanical properties, heat resistance, and flame resistance. The molded products here include injection molded products, extrusion molded products, press molded products, sheets, pipes, various films such as unstretched films, uniaxially stretched films, biaxially stretched films, unstretched yarns, super stretched yarns, etc. Examples include various fibers. Injection molding is particularly preferred from the viewpoint of workability.

Molded articles made of the thermoplastic polyester resin composition thus obtained include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, relay bases, spools for relays, switches, Coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, board-to-board joints, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings , semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, thermal protectors, antennas, wearable terminal parts, computer-related parts; VTR parts, TV parts , irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, sound equipment parts such as audio equipment, laser discs (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, washing jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, motor parts , machine parts such as writers and typewriters, camera module parts such as lens holders, bases, barrels, covers, sensor covers, actuators, microscopes, binoculars, cameras, watches, medical equipment, etc. Representative optical equipment, precision machinery related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, various valves such as exhaust gas valves, fuel related / exhaust system / intake system various pipes, air intake nozzle snorkel, intake Manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat for air conditioner Bases, air conditioner motor insulators, automotive motor insulators for power windows, etc., heating hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, dust tributors, starter switches, starter relays , wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, fuel-related solenoid valve coils, fuse connectors, handles, horn terminals, electrical component insulation plates, step motor rotors, lamp bezels, lamp sockets, lamp reflectors, lamps It can be used for automobiles and vehicle-related parts such as housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and sensors.

Among the various uses described above, the molded product of the present invention is excellent in adhesion of the metal part on the surface of the molded product during cold heat treatment, excellent shape retention of the molded product during heat treatment, and excellent slidability of the molded product. Taking advantage of this, it is useful for small electric and electronic parts having a metal part on the surface of the molded product, such as sensors, LED lamp substrates, camera modules, antennas, and wearable terminal members.

The molded article of the present invention preferably has a metal portion on its surface. The method of forming a metal portion on the surface is not particularly limited, and includes various plating methods including applying a catalyst to a molded product, a mask forming method in which areas other than circuit formation areas are masked by two-step molding, and a molded product by laser irradiation. Methods by surface modification, partial removal, and combinations thereof. In particular, the method of forming a selective metal part on the laser irradiation part, which includes a pattern drawing process by laser irradiation to the molded product and a metallization process by plating, represented by the laser direct structuring method, is a one-time molding. It is preferable because it has advantages such as the ability to produce a molded product with , the ease of narrowing the pitch of the circuit, and the need to change the laser irradiation pattern without changing the mold when changing the circuit pattern.

There are no particular restrictions on the laser that is irradiated onto the metal part formation location, and YVO ₄ laser, CO ₂ laser, Ar laser, excimer laser, and the like can be mentioned. In particular, an Nd;YAG laser, a _YVO4 laser, and a FAYb laser, which operate at a fundamental wavelength of 1064 nm or a second high wavelength of 532 nm, are preferable because they are excellent in formability of metal parts. Further, the oscillation method of the laser beam may be a continuous wave laser or a pulse laser. A pulsed laser that irradiates a strong laser output for a short period of time is preferable as the laser to irradiate the metal part forming part, from the viewpoint of suppressing thermal deterioration of the surface of the molded article and burying of the circuit forming additive in the molten resin.

The metal species of the metal portion formed by the above method include gold, silver, copper, platinum, zinc, tin, nickel, cadmium, chromium, and alloys containing them. It is preferable from the viewpoint of adhesion after forming the metal conductive portion. In addition, from the viewpoint of improving the stability and conductivity of the metal portion, a metal layer made of a different kind of metal may be formed on the metal portion of the molded article by a technique such as plating.

The molded article having a metal part on the surface obtained by the above method is space-saving and simplifies the manufacturing process compared to conventional circuit members consisting of a substrate forming a circuit and a molded article holding it. can be achieved, it is useful for use as a small electric/electronic component.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the gist of the present invention is not limited only to the following examples.

The thermoplastic polyester (A) used in each example and comparative example is shown below.

Compositional analysis and property evaluation of the polyester were carried out by the following methods.

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

(2) Melting point (Tm) measurement of thermoplastic polyester An endothermic peak observed when measuring a thermoplastic polyester at a temperature rising condition of 20 ° C./min from room temperature with a differential scanning calorimeter DSC-7 (manufactured by PerkinElmer) After the temperature (Tm ₁ ) was observed, the temperature was kept at Tm ₁ +20°C for 5 minutes, then cooled to room temperature at a temperature decrease of 20°C/min, and measured again at a temperature increase of 20°C/min. The observed endothermic peak temperature (Tm ₂ ) was defined as the melting point (Tm). In the production examples below, the melting point is referred to as Tm.

Production Example 1 Thermoplastic polyester resin (A-1)
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, and 90 parts by weight of isophthalic acid were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. and 1252 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) were charged, and the mixture was reacted at 145°C for 1 hour while stirring in a nitrogen gas atmosphere. The temperature was raised. Thereafter, the polymerization temperature was maintained at 350° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, and the reaction was continued until the torque required for stirring reached 20 kg·cm, and polymerization was completed. 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 through a mouthpiece having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A thermoplastic polyester (A-1) was obtained.

A composition analysis of this thermoplastic polyester (A-1) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 60.0 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 12. 0 mol %, the proportion of structural units derived from hydroquinone was 8.0 mol %, the proportion of structural units derived from terephthalic acid was 15.2 mol %, and the proportion of structural units derived from isophthalic acid was 4.8 mol %. rice field. The sum total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid was 75.2 mol % with respect to 100 mol % of all structural units of the polyester. Moreover, Tm was 330 degreeC.

Production Example 2 Thermoplastic polyester (A-2)
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, and 202 parts by weight of isophthalic acid were placed in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. and 1302 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) were added, and the mixture was reacted at 145°C for 1 hour while stirring in a nitrogen gas atmosphere, and then the jacket temperature was increased from 145°C to 330°C in 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) over 1.0 hour, the reaction was continued, and 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 through a mouthpiece having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A thermoplastic polyester (A-2) was obtained.

A composition analysis of this thermoplastic polyester (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 was 9.2 mol%, the proportion of structural units derived from terephthalic acid was 12.7 mol%, and the proportion of structural units derived from isophthalic acid was 10.4 mol%. rice field. The sum total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid was 66.5 mol% with respect to 100 mol% of all structural units of the polyester. Moreover, Tm was 310 degreeC.

Production Example 3 Thermoplastic polyester (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 and 22 parts by weight of isophthalic acid were placed in a 5 L reactor equipped with a stirring blade and a distillation tube. and 1152 parts by weight of acetic anhydride (1.09 equivalents of the total phenolic hydroxyl groups) were added, and the mixture was reacted at 145°C for 1 hour while stirring in a nitrogen gas atmosphere, and then the jacket temperature was increased from 145°C to 365°C in 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) over 1.0 hour, and the reaction was continued until the torque required for stirring reached 20 kg·cm, and polymerization was completed. 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 through a mouthpiece having a circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A thermoplastic polyester (A-3) was obtained.

A composition analysis of this thermoplastic polyester (A-3) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 73.9 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 7. 8 mol%, the proportion of structural units derived from hydroquinone was 5.2 mol%, the proportion of structural units derived from terephthalic acid was 11.7 mol%, and the proportion of structural units derived from isophthalic acid was 1.3 mol%. rice field. The total amount of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid was 85.7 mol% with respect to 100 mol% of all structural units of the thermoplastic polyester. Moreover, Tm was 351 degreeC.

(A-4): Thermoplastic polyester: A polyethylene terephthalate resin having a carboxyl group amount of 40 eq/t manufactured by Toray Industries, Inc. was used. Moreover, Tm was 250 degreeC.

The circuit-forming additive (B) used in each example and comparative example is shown below.
(B-1): Copper (II) phosphate (manufactured by Wako Pure Chemical Industries, average particle size 3 μm)
(B-2): Copper (II) pyrophosphate (manufactured by Kanto Chemical, average particle size 1 μm)
(B-3): Tin oxide (manufactured by Wako Pure Chemical Industries, average particle size 3 μm)
(B-4): Copper chromium oxide Black 3702 (manufactured by Asahi Chemical Industry Co., Ltd., average particle size 0.8 μm).

At least one additive (C) selected from titanium oxynitride (C1) and composite oxides (C2) containing titanium, calcium and manganese used in Examples and Comparative Examples, and other additives (c) The following are shown.
(C-1): SG-101 (manufactured by Ishihara Sangyo, composite oxide of calcium, titanium and manganese (C2), particle size 0.95 μm)
(C-2): SG-103 (manufactured by Ishihara Sangyo, a mixture of a composite oxide (C2) of calcium, titanium and manganese and aluminum oxide, particle size 1.2 μm)
(C-3): Titanium Black 13M (manufactured by Mitsubishi Materials, titanium oxynitride (C1), average particle size 0.075 μm)
(c-4): 42-303B (manufactured by Tokan Material Technology, a complex oxide of copper, chromium and manganese, average particle size 0.6 μm).
(c-5): CR-63 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, average particle size 0.21 μm)
(c-6): #45 (manufactured by Mitsubishi Chemical, carbon black, average particle size 24 nm).

The filler (D) used in each example is shown below.
(D-1): Mica AB-41 (manufactured by Yamaguchi Mica, average particle size 47 μm, Mohs hardness 2.8)
(D-2): Glass fiber T-747H (manufactured by Nippon Electric Glass, chopped strand)
(D-3): Glass milled fiber EPDE-40M-10A (manufactured by Nippon Electric Glass, average fiber length 40 μm, average fiber diameter 9 μm, Mohs hardness 6.5).

Examples 1-18, Comparative Examples 1-7
Using a Toshiba Machine TEM35B twin-screw extruder equipped with a side feeder, 100 parts by weight of the thermoplastic polyesters (A-1) to (A-4) obtained in each production example are blended in the amounts shown in Table 1. , At least one additive selected from circuit-forming additives (B-1) to (B-4) and titanium oxynitride and composite oxides containing titanium, calcium and manganese (C-1) to (C- 3) and other additives (c-4) to (c-6) are charged from the main feeder, fillers (D-1) to (D-3) are charged from the side feeder, and the cylinder temperature is heated. The melting point of the plastic polyester (A) was set to +10° C., and melt-kneaded to obtain pellets. After drying the obtained pellets of the thermoplastic polyester resin composition at 150° C. for 3 hours with a hot air dryer, the following evaluations (3) to (5) were performed. Results are shown in Table 1.

(3) Evaluation of Formability of Metal Continuity Portion The thermoplastic polyester resin compositions obtained in each example and comparative example were subjected to a Fanuc α30C injection molding machine (manufactured by Fanuc, screw diameter 28 mm), and the cylinder temperature was adjusted to that of the thermoplastic polyester. +20°C of the melting point and the mold temperature of 90°C, a square shaped article of 70 mm x 70 mm x 1 mm thickness was molded. Using a Panasonic LP-V10U YAG laser device on the surface of the resulting molded product, the wavelength is 1064 nm, the frequency is 50 Hz, and the laser output is 1.2, 2.4, 3.6, 4.8, 6.0, 7.2 W, the scanning speed was changed to 1000, 2000, 3000, 4000, 5000, and 6000 mm/s, and laser irradiation was performed on a range of 5 mm×5 mm. The molded product is subjected to electroless copper plating treatment, and among 36 locations with different laser irradiation conditions, the greater the number of copper plating formed (the number of metal conductive portions formed), the better the formation of metal conductive portions on the molded product. and evaluated. Here, for the molded article in which the copper plating was not completely formed on the surface of the molded article, the formability of the metal conductive portion was given as "x".

(4) Evaluation of the adhesion between the surface of the molded product and the metal conduction part. -70 L), the temperature was lowered from room temperature to -40 ° C. in 5 minutes, held for 30 minutes, and then heated to 150 ° C. in 5 minutes and held for 30 minutes. . After the treatment, a tape (Nichiban Cellotape (registered trademark) with an adhesive strength of 3.4 to 3.9 N/cm, width 18 mm) is sufficiently adhered to each metal conductive part formation location, and the tape is held at both ends and momentarily held in the vertical direction. Of the 180 locations (36 locations/sheet×5 sheets) under different laser irradiation conditions, the number of locations where metal conductive portions were formed without being peeled off was measured. Here, the part where the metal conduction part was not partially formed on the surface of the molded product was not counted as the part where the metal conduction part formation part remained without peeling off. The greater the number of metal conduction portion formation locations that remained without peeling (the number of remaining metal conduction portions), the more excellent the adhesion to the metal conduction portion on the surface of the molded product was evaluated. In (3), the adhesiveness was given as "-" for molded products in which no metal conductive parts were formed on the surface of the molded product.

(5) Evaluation of fine circuit formability The resin compositions obtained in each example and comparative example were subjected to a Fanuc α30C injection molding machine (manufactured by Fanuc, screw diameter 28 mm), and the cylinder temperature was set to the melting point of the thermoplastic polyester resin +20. °C and a mold temperature of 90°C, a square shaped article of 70 mm x 70 mm x 1 mm thick was molded. On the surface of the resulting molded product, using a Panasonic LP-V10U FAYb laser device, under the conditions of a wavelength of 1064 nm, a frequency of 50 Hz, a laser output of 5.0 W, and a scanning speed of 3000 mm / s, a width of 0.2 mm and an interval of 0.1 mm A wiring pattern was irradiated with a laser. The molded article was subjected to electroless copper plating treatment of 6 μm thickness. After that, the conduction of the molded product wiring was evaluated with a tester. "○" indicates continuity, "X" indicates disconnection or short circuit, and "-" indicates that no wiring pattern is formed by plating. It was judged that the more conductive the surface of the molded product, the better the fine circuit property.

From the results of Table 1, the thermoplastic polyester resin composition of the embodiment of the present invention has excellent adhesion between the resin molded product and the metal conductive part after circuit pattern formation by laser irradiation, and furthermore, the fine circuit on the surface of the molded product It can be seen that the formability is excellent. Therefore, it can be said that it is particularly suitable for use in electrical and electronic parts having a metal part on the surface.

The thermoplastic polyester resin composition of the present invention is excellent in adhesion between the resin molded article and the metal conductive part after the circuit pattern is formed by laser irradiation, and is excellent in fine circuit formability on the surface of the molded article.・Useful for electronic parts.

Claims (8)

Based on 100 parts by weight of the thermoplastic polyester (A), 5 to 25 parts by weight of the circuit-forming additive (B) is selected from titanium oxynitride (C1) and composite oxides containing titanium, calcium and manganese (C2). A thermoplastic polyester resin composition containing 0.1 to 20 parts by weight of at least one additive (C). 2. The resin composition according to claim 1, wherein said thermoplastic polyester is a liquid crystalline polyester. The thermoplastic polyester resin composition according to claim 2, further comprising 5 to 150 parts by weight of a filler (D). Claim 2 or Claim 2, wherein the total amount of the aromatic oxycarbonyl units and the terephthalic acid units in the liquid crystalline polyester is 60 to 77 mol% with respect to 100 mol% of all structural units of the liquid crystalline polyester. 3. The thermoplastic polyester resin composition according to 3. A molded article made of the thermoplastic polyester resin composition according to any one of claims 1 to 4. 6. The molded article according to claim 5, which has a metal portion on its surface. 6. A method for producing a molded product having a metal part on its surface, comprising a pattern drawing step by irradiating the molded product according to claim 5 with a laser, and a metallization step of the laser-irradiated part by plating. 7. The molded article according to claim 5 or 6, which is any one of a sensor, an LED lamp substrate, a camera module, an antenna, and a wearable terminal member.